MICROPOROUS MATERIALS

ELSEVIER Microporous Materials 4 ( 1995) 239-242

Short communication

Role of homogeneous nucleation in the formation of primary zeolite particles

J. Bronid, B. Subotid *
Ruder Bogkovik Institute, Bijeni6ka 54, P.O. Box 1016, 41001 Zagreb, Croatia

Received 4 July 1994; accepted 4 November 1994

Abstract
Different mechanisms of nucleation in the liquid phase, such as homogeneous, heterogeneous, secondary and autocatalytic nucleation, were assumed in the literature as the dominant processes of the formation of primary zeolite particles. Since just homogeneous nucleation was very frequently pointed out as possible process of the formation of primary zeolite particles, the possibility of the occurrence of homogeneous nucleation during zeolite crystallization from aluminosilicate gels was analyzed in accordance with the classical theory of homogeneous nucleation. Analysis of three different crystallizing systems show that the rate of homogeneous nucleation is extremely low under the given synthesis conditions, so the other nucleation processes must be considered relevant for the formation of primary zeolite particles.
Keywords: Zeolites; Homogeneous nucleation; Heterogeneous nucleation; Rate of nucleation; Crystallization

1. Introduction
Various nucleation mechanisms have been proposed for the formation of zeolite particles, and the controversy over the mechanism of zeolite nucleation is persisting. Today's prevalent opinion is that the formation of primary zeolite particles can occur by homogeneous [1-4], heterogeneous [5,6] and secondary [1,7,8] nucleation in the liquid phase supersaturated with soluble silicate, aluminate and aluminosilicate species, or by heterogeneous nucleation at the liquid-solid interface of the gel [9]. Crystallization of various types of zeolites from clear solutions [2,10-12] has undoubtedly demonstrated that nucleation may * Corresponding author 0927-6513/95/$9.50 1995 ElsevierScienceB.V. All rights reserved SSDI 0927-6513(94)00087-5

occur in the liquid phase, in the absence o f a solid precursor (gel). Homogeneous nucleation [1-4,13] was frequently assumed as a possible process for the formation of primary zeolite particles in the liquid phase. Thus, the objective of this work is to elucidate the real role of homogeneous nucleation in the formation of primary particles of zeolites during their hydrothermal synthesis. For this reason we analyzed the possibility of the occurrence of homogeneous nucleation during three different zeolite syntheses.

2. Theory of homogeneous nucleation

According to the classical theory of homogeneous nucleation [14 16], it can occur only in a

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solution supersaturated to a sufficient extent. In a system with constant overall energy there are local fluctuations around the mean value, and in some regions the energy level is high enough for nucleation to occur as a result of collision between molecules or ions [17]. The aggregate of molecules will grow only if it exceeds a critical size which depends on supersaturation (critical size of nuclei decreases with increasing supersaturation) [ 14-17]. So, in low and moderately supersaturated homogeneous solutions crystals cannot be formed spontaneously (without the presence of seed crystals and/or active centers on impurity particles), because only a very little proportion of embryos can attain the critical size, i.e., the size at which the growth rate is higher than the dissolution rate [18]. According to the classical nucleation theory, the rate of nucleation, J = dN/dz, is usually written as [15]:

than 0.1 mol dm -3, can be calculated as [19], a = -18.3 log C* +34.5 mJ m -2 (4)

3. Analysis of the kinetics of homogeneous nucleation

Using Eqs. 1-4, the kinetics of homogeneous nucleation of zeolite A [5,13] and zeolite Y [20] were analyzed as follows.

3.1. Example 1: crystallization of zeolite A [13]

Zeolite A was crystallized at 100C with an "excess" of aluminate in the liquid phase (Si/A1 = 0.117, see Run No. 5 in Table 1 of Ref. [13]). Hence, the solubility, C*, of zeolite A under the synthesis conditions was equivalent to the concentration of silicon in the liquid phase after the gel had been transformed completely into zeolite A (C* = 7.5.10- 3 mol d m - 3, see Fig. 2 of Ref. [ 13 ]). Using Eq. 4 the zeolite A-liquid phase interfacial tension, calculated for the given synthesis conditions is a=73.4 mJ m -2. The concentration, C, of silicon dissolved in the liquid phase was constant during the synthesis and was 2.08 times higher than the solubility concentration (see Fig. 2 and Table 1 of Ref. [ 13]). At the end of the crystallization process the concentration of silicon in the liquid phase sharply decreased to the equilibrium concentration C*. Hence, the supersaturation during the synthesis was S ~<2.08. For an assumed cubic shape of nuclei of zeolite A, the geometrical shape factor /3=32 (according to Table 1.1. of Ref. [15]), the formula weight M=182.5 g (the formula weight was calculated on the basis of the formula Na(A102) (SIO2)'2.25 H20), p =2 g cm -3 and the molecular volume, v, of zeolite A is 7.58-10 -23 cm 3. Now, using Eq. 1 and the numerical values of/3, a, v and S calculated as explained above as well as k = 1.38"10 -~6 erg/deg and T = 373 K (temperature of crystallization) it is easy to calculate that J ~<10-4oo nuclei/(cm 3 s). This means that the first nucleus of zeolite A in 1 dm 3 of the system would be formed after approximately 10395 years! If the molecular volume, v, of zeolite A was calculated not on the basis of the simplified for-

J= A exp[-~a3vZ/(kT)3(ln S) z]

(1)

where A is the pre-exponential factor which is a function of molecular diameter and diffusion rate of molecules or ions in the solution, fl is the geometrical shape factor of critical nuclei, a is the solid-liquid interfacial tension, v is the molecular volume of the solid phase, k is the Boltzman constant, T is the absolute temperature and S= C/C*, C being the actual concentration of molecules or ions in the liquid phase and C* the concentration of molecules or ions which corresponds to the solubility of the solid phase at given conditions. Using a rough estimate of the preexponential factor, A~103cm -3 s -1 [15], the logarithm of the nucleation rate can be expressed as [15]: log J = 30 - fla3v2/(kT In 10)3(log S) z (2)

The numerical values of/3 for the nuclei of different geometrical shapes are listed in Table 1.1 of Ref. [15]. The molar volume of the solid phase, v, can be calculated as [15]:

v = M/( 2pA ,)

(3)

where M and p are, respectively, formula weight and the density of the solid phase, and A, is Avogadro's number. The solid-liquid interfacial tension, a, of the compounds with solubility lower

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mula (M= 182.5 g), but on the basis of the formula of one unit cell of zeolite A (M=2190.96 g), then v = 9.1.10- 22 c m 3 and, consequently, J <~10 - 1oooo nuclei/(cm3 s).

4. Discussion and conclusion

3.2. Example 2: crystallization of zeolite A [5]

Zeolite A was crystallized at 80C at an "excess" of aluminate in the liquid phase (Si/AI=0.509). From the equilibrium concentration, C*, of silicon in the liquid phase (C* =0.0299 mol dm -3) it was calculated by Eq. 4 that a = 6 2 . 4 m J m -2 for the given synthesis conditions. The concentration, C, of silicon dissolved in the liquid phase was constant during the synthesis and was 1.7 times higher than the solubility concentration C*. At the end of the crystallization process the concentration of silicon in the liquid phase sharply decreased to the equilibrium concentration C*. Hence, the supersaturation, S, during the synthesis was 4 1.7. Under the given synthesis conditions (T=353 K, C ~<0.0509 tool dm- 3, C* = 0.0299 tool din- 3), the numerical values o f / / a n d v were identical as in Example 1, and hence, J~< 10 -540 nuclei/(cm -3 s). This means that the first nucleus of zeolite A in 1 dm 3 of the system would be formed after approximately 10~3 years!

3.3. Example 3: crystallization of zeolite Y [20]

Zeolite Y was crystallized in "excess" of silicate in the liquid phase (Si/AI--48, see Table 1 in Ref. [20]). From the equilibrium concentration, C*, of aluminium in the liquid phase (C* =0.027 mol dm -3) it was calculated by Eq. 4 that a = 63 mJ m-2 for the given synthesis conditions. For C~<0.054mol dm -3 (see Table 1 in Ref. [20]), S~<1.95, T = 3 7 3 K , fl=32 and v= 1.22.10 -22 cm 3, it was calculated that J~<10 -97 nuclei/(cm3 s). This means that the first nucleus of zeolite Y in 1 dm 3 of the system would be formed after 10960 years! If molecular volume, v, of zeolite Y was calculated not on the basis of the simplified formula (M=312.8 g), but on the basis of the formula of one unit cell of zeolite Y (M=17518 g), then v=7.27.10 -21cm 3 and, consequently, J ~<10- lo oooooo nuclei/(cm3 s).

The above analyses show that the homogeneous nucleation is extremely slow under the g~ven synthesis conditions; the time needed for the appearance of the first nucleus in 1 dm 3 of the system is much longer than the age of universe. This was expected because the supersaturation, S, typical for most zeolite synthesis (S~ 2-4) [5,6,13,20-23], is considerably lower than the critical Supersaturation, S*, needed for homogeneous nucleation of most inorganic compounds [14]. Analysis of the condensation degree of silicate anions in the liquid phase during the crystallization of zeolite A showed that the liquid phase contained only monomers at all stages of the crystallization process [22,23]. Hence, it is reasonable to calculate the supersaturation, S, by the simple enpression: S = C/C* (C is the concentration of silicon in the liquid phase during the crystallization and C* is the concentration of silicon in the liquid phase at the end of the crystallization process) in the cases of crystallization of zeolite A (examples 1 and 2). On the other hand, silicates and aluminosilicates are present in the liquid phase in different monomeric and polymeric entities during the crystallization of zeolite Y [20]. Although the nature of the species in solution mostly remained unchanged, the distribution of the silicate and aluminosilicate species slightly changed during the crystallization. However, the change in distribution can be neglected (increase in concentration of Qo species for ca. 5%, decrease in concentration of QI(0AI) and Q/(2AI) species for ca. 5%; see Fig. 10 of Ref. [20]) during the relevant time of crystallization (10 h, i.e. after the amorphous gel has been transformed completely into zeolite Y ) and, hence, the supersaturation can be calculated in ~he simple way explained earlier in the case of the crystallization of zeolite Y as well. The duration of crystallization in the above examples is within a range of a few hours and, consequently, it is evident that homogeneous nucleation can be neglected as a process of the formation of primary zeolite particles of, at least, low-silica zeolites. Earlier studies of cryslal-~crystal transformations, i.e. transformation of zeolite A into hydroxysodalite [24], showed that primary

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[5] J. Broni6, B. Suboti6 and I. Emit, Stud. Surf Sci. Catal., 37 (1988) 107. 16] B. Suboti6 and J. Broni6, in R. yon Ballmoos, J.B. Higgins and M.J.M. Treacy (Eds.), Proceedings of the 9th International Zeolite Conference, Montreal, 1992, Butterworth Heinemann, Boston, 1993, p. 321. [7] J. Warzywoda, R.D. Eldman and R,W. Thompson, Zeolites, 11 (1991) 318, [8] E.A. Tsokanis and R.W. Thompson, Zeolites, 12 (1992) 369. [9] J.C. Jansen, Stud. Surf Sei. Catal., 58 (1991) 77. [10] E. Narita, K. Sato, N. Yatabe and T. Okabe, Ind. Eng. Chem. Prod. Res. Dev., 24 (1985) 507. [11] S. Ueda and M. Koizumi, Am. Miner., 64 (1979) 172. [12] S. Gouthier, L. Gora, I. Guray and R.W. Thompson, Zeolites, 13 (1993) 414. [13] J. Ciric, Colloidlnterface Sci., 28 (1968) 315. [14] A.G. Walton, in A.C. Zenlemoyer (Ed.), Nucleation, Marcel Dekker, New York, 1969, p. 225. [15] A.E. Nielsen, Kinetics of Precipitation, Pergamon Press, Oxford, 1964. [16] A.G. Walton, The Formation and Properties of Precipitates, Interscience Publishers, New York, London, Sydney, 1967. [17] R. Boistelle, Estudos Geol., 38 (1982) 135. [18] A.E. Nielsen and J. Christoffersen, in G.H. Nancollas (Ed.), Biological Mineralization and Demineralization, Springer-Verlag, Berlin, Heidelberg, New York, 1982, p. 37. [19] O. S6hnel, J. Cryst. Growth, 63 (1983) 174. [20] N. Dewaele, P. Bodart, Z. Gabelica and J.B. Nagy, Acta Chim. Hung., 119 (1985) 233. [21] E.F. Freund, J. Cryst. Growth, 34 (1976) 11. [22] W. Wicker and B. Fahlke, Stud. Surf Sci. Catal., 24 (1985) 161. [23] B. Fahlke, D. Miiller and W. Wicker, Anorg. Allg. Chem., 562 (1988) 191. [24] E. Gruji6., B. Suboti6 and L.A. Despotovi6, Stud. Surf Sci. Catal., 49A (1989) 261. [25] S.P. Zhdanov, Adv. Chem. Ser., 101 (1971) 20. [26] B. Suboti6 and A. Graovac, Stud. Surf Sci. Catal., 24 (1985) 199. [27] W. Meise and F.E. Scwochow, Adv. Chem. Ser., 121 (1973) 169. [28] A. Katovi6, B. Suboti6, I. Emit, L.A. Despotovi6 and M. (~uri6, Am. Chem. Soc. Symp. Set., 398 (1989) 124. [29] H. Lechert, in P.A. Jacobs (Ed.), Structure and Reactivity of Modified Zeolites, Elsevier, Amsterdam, 1984, p. 107. [30] S.P. Zhdanov and N.N. Samulevitch, in L.V.C. Rees (Ed.), Proceedings of the 5th International Zeolite Conference, Naples, 1980, Heyden, London, Philadelphia, Rheine, 1980, p. 75.

particles of hydroxysodalite were formed by rapid heterogeneous nucleation caused by the presence of impurity particles in the liquid phase of the system. The supersaturation of the liquid phase with reactive silicate, aluminate and/or aluminosilicate species is similar in both crystal-crystal and gel-crystal (crystallization of zeolites from gels) transformations. So, it is realistic to expect that heterogeneous nucleation is also relevant for the crystallization of zeolites from gels. However, some effects observed during the crystallization of zeolites from gels, as for instance the increasing rate of nuclei formation (autocatalytic nucleation) [2,5,25,26], the large portion of fine particles in the crystalline end-product [5,27], the influence of gel ageing on the crystallization process [5,20,28-30], the bimodal particle size distribution in the crystalline end-product [5,10,25,27], etc., cannot be readily explained by the heterogeneous nucleation alone. Hence, it can be concluded that only a part of primary particles of zeolite is formed by heterogeneous nucleation and that the rest is formed by other nucleation processes during zeolite crystallization from gels, as discussed elsewhere [5,9,25,28,30].

Acknowledgement The authors thank the Ministry of Science and Technology of the Republic Croatia for financial support.

References
[1] L.M. Truskinovkiy and E.E. Senderov, Geokhimiya, 3 (1983) 450. [2] R.W. Thompson and A. Dyer, Zeolites, 5 (1985) 302. [3] C.L. Huang, W.C. Yu and T.Y. Lee, Chem. Eng. Sci., 41 (1986) 625. [4] J.D. Cook and R.W. Thompson, Zeolites, 8 (1988) 322.