ELSEVIER

Quantitative relations of the batch composition and the Si/AI ratio in the product of zeolites
H. Lechert, P. Staelin, and C. Kuntz

Institute of Physical Chemistq,

An analysis phase from of the correlation which they were

University of Hamburg,

Hamburg,

Germany
of the solution

of the Si/AI ratio of faujasites with the composition crystallized gives with good accuracy an equation

(Si/AI) prOdUCt= 1 + b . (ISiO~l/IOH-I),o,,~i,, where b is a constant that can be taken from the experiments. be observed. The batch composition can be described formally by NaAIO, With some : n (Na,H, simplifying _ ,SiO,) : p H,O. it can be concluded that For a series of faujasites

(Al 1 b = 2 can

(A21

assumptions

(Si/AI) ,,roduct = (b + n-d . Mb + n . n-t)

(A31

where n is the SVAI ratio and m the excess alkalinity (NaOH - NaAIO,)/SiO, of the batch. From a comparison with a large number of experimental data it can be seen that Equation (A3) describes the SVAI ratios for an extended range of batch compositions and different zeolites with good accuracy, allowing a reliable prediction of the composition of the final product from the parameters of the batch composition. Deviations observed for low SVAI ratios can be corrected by an additional empirical term 0.3/n - 0.3. The validity of the equation and its limits are tested also for data from the literature, including unusual batch compositions.
Keywords: Zeolite; crystallization; Si/Al-ratio

INTRODUCTION
Zeolites are produced in large amounts for various fields of industrial application. Large quantities of Y zeolites are used in cracking and hydrocracking catalysts; A and X zeolites are used as ion exchangers in laundry detergents and for sorption and separation processes. Others, such as ZSM-5, are applied in more special catalytic processes where an improved selectivity is demanded. The current knowledge and a large amount of data about the crystallization of zeolites have been summarized in the books of Barrer and Breck2 and more recently in various articles in a series of books by Occelli and Robson, Szostak, and Van Bekkum et al. Further reviews can be obtained from the roceedL ings of the International Zeolite Conferences.

Address reprint requests to Prof. ical Chemistry; University of D-20146 Hamburg, Germany. Received 29 May 1995; accepted

Lechert at the Institute Hamburg, Bundestrasse 27 July 1995

of Phys45,

For application in industrial processes generalb highly reproducible materials with respect to the composition and other parameters such as particle size are wanted. Therefore, a thorough understanding of the mechanisms of the crystallization is interesting not onh for a deeper insight into the principles of zeolite crystallization but also for industrial application. In reality, crystallization is done mostly according to carefully tested recipies that are more or less well dcscribed in the open and the patent literature and which are often a matter of extensive additional experimentation in the course of the final establishment of thl: applied process. Generally, zeolites crystallize in the presence of a gel phase that is dissolved during crystallization, supporting the growing crystal with the matt.rial necessary for growth. The gel and the solution phases are often regarded to be in some kind of dlanamic equilibrium at least during the growth process It is now generally accepted that crystallization proceeds via the solution phase and not by a direct tranr formation of the gel.

Zeolites 16:149-156,
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1996 Science Inc. 1996 of the Americas,

New

York,

NY 10010

SSDI

0144-2449/96/$15.00 0144-2449(95)00096-O

Si/AI

ratio of different

zeolites:

H. Lechert

et al. 2.5 mol of Al(OH), and 5 mol of NaOH. For the experiments of ser-ies 4 and 5 the aluminate was made of commercial AlCl, (Merck) and NaOH. An equivalent amount of AlCl, was used, and the NaOH concentration was adjusted. The silica source was commercial water glass (density 1.37) with 273.5 g (4.6 mol) of SiO, and 83.0 g (1.3 mol) in a 1,000-g solution. To obtain comparable conditions, in the crystallizing batches the composition was chosen so that the total concentration of the solid remained constant at 50 g of (AlO,Generally, NaAlO, + n. SiO,)/l,OOO g of H,O. by (1)

In earlier investigations we have studied extensively the kinetics of growth and the composition of Y zeolites in their dependence on batch composition.12-5 For studies of zeolite crystallization, faujasites are very convenient. The faujasite structure is cubic, and only one constant of linear growth has to be taken into account for the kinetic studies. Faujasite crystallizes mostly in octahedra and has a comparatively low tendency for twinning and intergrowth. In the range of Si/Al ratios of about 1.1 to about 3.4, which can be obtained by direct synthesis, a wide range of rate constants of linear growth can be observed. This means that general information about the mechanisms of zeolite crystallization can be obtained, especially regarding the dependence of rate contents on composition. As has been discussed in detail in several papers 12-14,18-21 nucleation of faujasite does not occur below an alkali concentration of about 2 mol of NaOH/ liter. Batches of this alkali concentration give a composition of the crystallizing faujasites of only about 1.41.5. For application in catalysts, higher Si/Al ratios are needed. It is well known that for the higher Si/Al ratios the alkali concentration must be lowered to a level where only nucleation of P zeolite takes place. For lower alkalinities, Y zeolite can be crystallized only if nuclei are added or otherwise created in the batch. This offers the chance to study the processes of growth and nucleation separately with great accuracy. Nucleation must be achieved by X seeds or by appropriate nucleation gels&*l that were first described by McDaniel and co-workers.22,2s Later discussions of these gels can be found by Kasahara et a1.24 The procedure of creating faujasite nuclei in the batch has been analyzed by Ginter et a1.25 using n.m.r. methods. Many have been published about the composition of the silicate solutions and the ossible building units of the zeolites grown from it.* B Investigators have subsequently tried to conceptualize the structure of the crystallizing zeolite and the silicate species found in the solution phase. Until now, only qualitative relations among the batch composition, the solution phase, the composition of the final product, and the rate of crystallization could be obtained. The aim of this study was to attempt to find some quantitative relations among the parameters characterizing the batch composition and the solution phase and the Si/Al ratio of the final product. The obtained relation will also be checked for zeolites other than faujasite. Finally, it should be mentioned that Y zeolites are still used in much larger quantities than any other zeolite in the cracking processes so that an improvement of faujasite synthesis is still interesting from a commercial point of view.

the compositions : IZ (Na,H,-,SiO,)

can be described : p H,O.

(2)

On the whole, five series of experiments were carried out, varying n and m in the reaction gels. In series 1, crystallization of X-type zeolites was performed without seeds or nucleation gel (see also Ref. 16). In series 2, crystallization of Y-type zeolites was done with the addition of seeds (see also Refs. 13 and 14). In series 3-5, crystallization of Y-type zeolites was done with the addition of nucleation gel. The compositions of the gels were similar to those of the gels in Refs. 12 and 13. For the preparation of the batches for crystallization the solutions were mixed at room temperature in 100or 300-ml polyethylene bottles under stirring, where the silicate was added to the aluminate and NaOH solution. The stirring was continued for about 2 h for homogenization. For the experiments of series 3-5 the homogenization was done by shaking the reaction mixtures. In preliminary experiments it was shown that this kind of homogenization did not cause formation of any P nuclei. Before heating to 88C seeds were added to the gels of series 2. Into the gels of series 3-5 1 ml of nucleation gel/loo-ml reaction gel was added. The homogenization was then continued for another 30 min. The batches were left in the bottles for crystallization. The batches of series 1 were heated to 88C immediately after homogenization. The NaOH content of these batches was above 2 mol/liter. The seeds were prepared from batches with the composition NaAlO, : n (Na,H,-,SiO,) : p H,O chosen in the ranges which is characteristic zeolites. Preferably n = for the

where the parameters where 2-5, m = 1.4-4.4, p = 180-450, the crystallization of X-type composition NaAlO, : 2 (Na,SiO,)

: 200 H,O

EXPERIMENTAL
The batches for the faujasite syntheses were generally prepared by mixing two solutions, one containing the alumina and the other the silica source. As alumina source Na-aluminate was used which was prepared from aluminum hydroxide (Merck, Al (OH) s) dissolved in an NaOH solution prepared from NaOH beads (Merck, analysis grade). One thousand g of solution contained

was used for the preparation of the nuclei. The reaction mixture was stirred for at least 8 h at ambient temperature before heating to 88C for crystallization. This ensures a rather homogeneous nucleation. After about 5 h of crystallization, nuclei with an average radius of 1.8 pm with a rather narrow particle size distribution were obtained (see also Ref. 17). The nucleation gel had the composition NaAlO, : 7.5 (Na,H,SiO,) by dissolving : 153 H,O. 21.8 g of NaAlO, (Merck,

It was prepared

150

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pure) in 375.2 g of water. A second solution was prepared from 420 g of waterglass (density 1.37, Merck), 3.8 g of silicic acid (Fallungskieselsiure, Merck), and 115.6 g of NaOH in 100 g of water. Both solutions were mixed under cooling and stirred for 1 h. A clear liquid formed which was aged at room temperature for at least 2 days before use. Gels prepared in this way are active for several weeks. For crystallization, about 1 ml of nucleation gel for 100 ml of synthesis gel was added. In the experiments of series 3-5 1 ml of this gel was added to 100 ml of the reaction mixture after homogenization of the mixture. The homogenization was then carried on 0.5 h. When the crystallization was finished the samples were filtered, washed to near neutrality, dried, and equilibrated over saturated NaCl solution. For analysis of the solution phase after the gel formation, both were separated by centrifugation. To obtain the SiO, content a defined part was dried, weighed, fumed with hydrofluoric acid, and weighed again. There was always only a little Al,O, remaining, indicating that only very little aluminate goes into the solution phase. In the later experiments the silicate and the aluminate were determined directly by ICP-AES analysis. The aluminum could not be detected by titration with EDTA. The OH concentration in the liquid phases was obtained by direct pH measurement and also by titration with hydrochloric acid. Calculation of the alkali concentration will be discussed later. For kinetic studies, the bottles were taken from the oven, shaken, and 2 ml of the crystallizing mixture was removed by a pipette. The bottle was then put back into the oven. The synthesis of mordenite and L followed procedures described in Ref. 51. The synthesis of zeolite W is described in Ref. 52. The Dhase comDosition and the crystallinity of all sample; were che:ked by X-ray diffraction. The composition of the samples was analyzed by X-ray fluorescence spectroscopy _ , and by EDfi analysis.

often mentioned in the literature and have been studied extensively. In Ref. 53 it is shown that the aluminate content in the solution increases strongly for %/Al ratio below 1.0, which are usually not applied in zeolite crystallization. In several papers it has been shown that the gel contains an amount of sodium corresponding to the aluminum content.33-g From the formula the OH concentration in the solution is given by IOH-I = n. m . 55/p. (3)

This OH content has been checked by pH measurements and by titration with HCl. This gives the sum of the excess NaOH and also the silicate present as Na[Si(OH),O-] or as Na,[Si(OH),022-]. The values of the titration and the SiO, content are slightly higher than those obtained from Equation (3) from the parameters of the batch composition. This may be due to a partial hydrolyzation of the aluminate in the gel during the period of homogenization, which is not taken into account in Equation (3). The silicate in the solution is dependent on the Si/Al ratio IZ of the batch and the Si/Al ratio of the gel phase. The mechanisms leading to formation of a well aged gel may not be much different from those leading to zeolite formation. Therefore should be @i/W prod = W/W gel (4)

From Refs. 33-39 and 53 and also from studies done in our laboratory it can be seen that this is only a rough approximation which will nevertheless prove to be highly useful in the following. From Equation (4) it follows that ISiO,l,,, or ISiO,l,,, = [ (Si/Al),,,,, [n- (Si/Al) - (Si/Al) prudl* 55.5/p prodl. x23/p. = = [(Si/Al),,,,, - (Si/Al),,,] . 55.5/p (5)

(6)

For the system NaAlO, : n (Na,H,_,SiO,) : 1, H,O.

RESULTS

AND

DISCUSSION the

Derivation of a general relation between Si/Al ratio of zeolite products and the parameters of batch composition

As a basis for the derivation of a general relation between the Si/Al ratio of the product and the parameters of the solution phase and the batch, data from our earlier experiments were used.*- The relative concentrations of the different components of the batch can be described formally by NaAlO, : n (Na,H,-,SiO,) : p H,O.

The total alkali concentration is finally given by the excess alkalinity m, the Si/Al ratio n, and the water content p, which are adjusted in the batch. The low Al concentrations in the solution show that after mixing the silicate and the aluminate components almost all of the aluminate vanishes in the gel. Similar results are

in which zeolite A, faujasite, NaPl, sodalite, mordenite, and analcime are crystallizing, a great deal of data has been gathered in Refs. 12-15 connecting the Si/Al ratio in the final product with the Si/Al ratio and the excess alkalinity in the batch. The studies have been extended with ions other than Na in the batch, leading to a series of other zeolites52 similar studies have been reported by Zhdanov.j4 In Ref. 15 the attempt has been made to obtain a common function for the composition of zeolites by the development of a general model of the crystallization process. It is well known that the Si/Al ratio of the final products in all zeolites increases with decreasing excess alkalinity m. Plotting the (Si/Al),,,, of various zeolites against m for a larger number of batches, a correlation of the form (Si/Al),,,,, = 1 + d/ m (7)

may be suspected, where the constant d can be obtained by a fit to the experimental values. Similar re-

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H. Lechert

et al.

suits have been obtained by Zhdanovs4 for an extended number of zeolite types. The general experience, expressed with some approximation by Equation (7)) indicates that for the establishment of the %/Al ratio of the zeolites a pHdependent equilibrium should be involved in the crystallization process. In our papers,16 the assumption of such an equilibrium at the surface of the growing zeolite =Si-OH + OHu =Si-O+ H,O (8)

W/W,,,d
or CWAl),,,d From Figure

o(b+n.m)=n.m+b.n

= (b+ 1 follows

m) . n/(b+

n. m).

(13)

b= 1.92 = 2 which gives; as an approximate pendence on the n and m,

WAl) prod

(14) of the (Si/Al),,,, de(15)

=(2+m).n/(2+n.m).

was discussed in detail. Assuming further that the minate from the solution is added preferably to charged silicate groups =Si-Oat the surface, for steady state of the incorporation of both silicate aluminate species, the Si/Al ratio of the product @i/N prod = 1 + u/lOH-I

aluthe the and

(9)

can be obtained, where IOHis the hydroxyl concentration in the solution phase. Inspection of the data of our earlier papers shows that the Si/Al ratio of the batch has a distinct influence on the Si/Al ratio at least for the low silica X zeolites. This dependence is obviously not described by the reported model leading to Equation (9). Plotting the Si/Al ratios of the products versus the relation at the right side of the Equations (7) and (9) it can be seen that the correlation is rather poor. A much better correlation can be obtained taking = @VAUprod 1 + b . ISiO,I,,,/IOH-I

(10)

instead of Equation (9). Generally, the ratio ISiO,l/ IOH-I determines the distribution of different silicate species in the solution phase.265 In Figure 1 the data from Refs. 12-16 are related by Equation (10). Using Equation (10) and the estimations of ISiO,l,,, and IOH- from Equations (3) and (6), one obtains WAl)
Pi/W

prod = 1 + b. [nprod . n. m= n. m+

(Si/Al),,,,,]/n. b. [n-

m (Si/Al),,,,l

(11)

(12)

y=a+bx a = 0.89 b = 1.92 carr.caeff. = 0.993

The importance of Equation (13) and the approximation of Equation (15) is that the Si/Al ratio of the product can be calculated directly from parameters n and m of the batch composition, without referring to the data in the solution phase. These relations can be tested easily by experiment. The parameters in the solution phase are difficult or at least unconvenient to control in routine work. Equation (13) contains, besides n and m, only the parameter b, which has been fitted from Figure 1 to the concentrations of SiO, and OH- in the solution phase. Parameter b is important for crystallization but has no simple meaning. A parameter in the solution which is proportional to the ratio ISiO,I/IOH-I is the concentration of the undissociated silicic acid Si(OH),. The possibility of such an interpretation demands further investigation and careful analysis of the data of the silicate species in the solution. Further, it may be expected that b is dependent on temperature and possibly on the presence of templates or complexing agents. In Figure 2 the results of crystallization experiments with nucleation gels (series 3-5) are compared with the data from our earlier papersi2-15 (series 1 and 2). It can be seen that the observed Si/Al ratios can be predicted well from Equation (15) within the limits of experimental error. Looking at the data from the earlier experiments (series 1 and 2) in which care had been taken for exactly uniform conditions of gel aging and crystallization, it can be seen that for low Si/Al ratios the deviations are comparatively larger than for the samples with the higher Si/Al ratios. For a further analysis, the region in question is plotted separately in Figure 3, where samples with different Si/Al ratios n of the batch are characterized by different symbols. There is a systematic variation of the Si/Al ratio in the batches. Empirically, all data can be fitted by a function
(si/AI) prod

=(2+m).n/(2+n.m)+0.3/n-0.3

(16)
which is demonstrated in Figures 4 and 5 for the region of series 1 and the extended region of series 2. Figure Gshows a comparison of the data obtained with faujasite with some data for mordenite and zeolites L and W. Additionally, in this figure some data obtained by Zhdanov are included in which chabazite and erionite were obtained besides Y. Equation (15) describes also the data in the extended range of Si/Al ratios with satisfying accuracy. The points for mordenite increase more steeply, which can be explained by a slightly larger value of 6.

0,o

0,3

0,5 SiOZ/NaOH

0,8 in solution

14

1.3

Figure 1 ISiO,I/IOH-1

Dependence of the Si/AI in the solution phase.

ratio

of faujasites

on the ratio

152

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.9/A/
4

ratio

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H. Lecher?

et al.

!
e a .r i s CJJ

( .. *
. . l . . l

Si/Al in batch
I + l

series I series 2

+ . . 0 .

1.4,1.5 2.0 3.0 4.0 5.0

.t
. . . 3-T---I

series 3 series 4
series5

--.---&L8.
:.JF*
1

1 ;p**

i--

. 7
3 + n*m) 4

1,. 2 (2 + m)*n/(2

1.o

I,1 12 12+ m)*W +

1,3 n*m) +0.3/n

1,4 - 0.3

13

Figure 2 Dependence of the Si/AI ratio of faujasites from different series of experiments on (2 + m) . n/(2 + n. m) according to Equation (15). For details see text.

Figure 4 Dependence of the SVAI ratio of faujasites on the corrected function (2 + m) . n/(2 + n . m) + 0.3/n - 0.3 according to Equation (16) in the range of low Si/AI ratios. The Si/AI ratios n in the batch are demonstrated by different symbols.

Comparison with some data from the literature Studies of the compositions of the zeolites from completely inorganic batches have been reported in earlier literature. Extensive studies in the system NaAlO, : n (Na,H,-,SiO,) : p H,O.

have been reported by Zhdanov.53 In this paper a thorough review of the early literature can be found. Besides the batch composition in the paper of Zhdanov the composition of the gel directly after the mixing, a detailed composition of the liquid phase, and the composition of the final products of the crystallization are given. The Si/Al ratios n and the excess alkalinities m in batches of the described composition are varied within large regions. The Si/Al ratio varied from 0.33 to 25. Excess alkalinity m varied from 25 to 0.7. Values of n below 1.0 and values of m above 5.0 are normally not used for the crystallization of zeolites. As mentioned,

some of these data are included in Figure 6. Excess alkalinity m for chabazite and erionite of these samples consists of NaOH and KOH, as is usual for the synthesis of these zeolite types. In Figure 7 the data obtained applying Equation (15) are compared with data obtained from Equation (10) using the results of the analysis of the gel and liquid phases of the batch. To calculate the OH- concentration the concentration of [AI(OH in the solution is subtracted from the values obtained according to Equation (3). This correction is important only for the region with n < 1.0. Outside this region the aluminate concentrations in the liquid phase are negligible. These data are demonstrated by the triangles in Figure 7. Finally, the Si/Al ratio of the final product has been estimated from the values obtained from the data about the gel composition using Equation (11) with (Si/Al) .-, instead of (Si/Al) rrod. The results are demonstrated % y the asterisks in Figure 7. It can be seen that the results are consistent with Equation (10) as well as with Equation

Si/AI in botch 1.4, 2.0 3.0 4.0 5.0 1.5

+
.

series 1,2 series 3

l,ol..f....~....l....i
l,o 1,l

12

,,,.
1,3 + n-m) 1,4 1,5

61
1 2 (2 + m)*n/(2 3 + nm) + 0.3/n _ 0.3 4

(2 + m)*n/(2

Figure 3 Dependence of the Si/AI ferent series of experiments on (2 + to Equation (15) in the range of low n in the batch are demonstrated by

ratio of faujasites from difm) n/(2 + n ml according Si/AI ratios. The Si/AI ratios different symbols.

Figure 5 Dependence of the Si/AI ratio of faujasites on the corrected function (2 + m) .n/(2 + n. m) + 0.3/n - 0.3 according to Equation (16) for different series of experiments.

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152,

%A/ a-

ratio

of different

zeolites: l
-.-.

H. Lechert

et al.

i.
7 --T-..-j--

t 62 . e Q 5 1. ---.~~~~--..--.. .F , . 2 . m 3:
p

. -7--A * I -----I--;
---(

+ A

faujasite mordenite zeolite L,W

.
q

ZDHANOV[53]

8 ,,,,
1 2 3

---7--.-.--. . ..I....
5 6 Si/AI colculated

I ,..,!,...
7 8

From an unseeded gel aged for 5 weeks and heated for 30 h, NaP with Si/Al = 2.87 is obtained, determined by MAS n.m.r. ICP-AES gives for the same sample Si/Al = 3.11. After 8 h of heating seeding and no aging yield NaYwith Si/Al = 2.55. Aging for 1 day and heating for 6 h produce NaY Si/Al = 2.56 with ICP-AES. The values with the other methods are slightly lower. From two of the reported experiments amorphous products with higher Si/Al ratios were obtained. It should be mentioned that the batches have a comparatively low water content. Similar experiments are reported in the paper of Kasahara et al. 24 These authors analyzed the Toyo Soda Process. They used a seed gel with the composition NaAlO, : 5 (Na,,,,H,,,,SiO,) : 92 HZ0

Figure 6 Dependence of the (2 + m) . n/(2 + n. m) according

Si/AI ratio of different to Equation (15).

zeolites

on

(15) within the range of experimental error. In the following some results from papers using unusual batch compositions will be used to test our results. In the paper of Ginter et al. a batch of a nucleation gel of the composition NaAlO, : 5 (Na,,94H2.06Si04) : 90 H,O

yielding, after 6 h, a crystalline product with Si/Al = 1.3; after 24 h, a product with Si/Al = 1.15. Sometimes an amorphous product with Si/Al = 1.6 is obtained. Equation (15) gives Si/Al = 1.49; after correction with Equation (16) Si/Al = 1.25 is found. After mixing with the nucleation gel the reaction mixture had a composition NaAlO, : 5 (Na,.4H,,6Si04) : 92 H,O.

was analyzed. A solid phase, precipitated after I day of aging, was analyzed by MAS n.m.r., FT i.r., and ICP-AES, giving Si/Al ratios of 1.96, 2.0, and 2.06, respectively. One day of aging and 1 day of heating gave a product with Si/Al = 1.95. With Equation (15) a value of 1.69 can be obtained, Equation (16) gives Si/Al = 1.45. This is because the Si/Al ratios of the amorphous gels and products of the early stages of crystallization are usually slightly higher if an excess of silicate is in the batch. From these gels, synthesis gels have been prepared by neutralizing a part of the Na,O by H&SO,. Further the results of the crystallization for a batch composition NaAlO, : 5 (Na,,,,Hs,,,SiO,) : 90 H,O

The crystalline product is reported to have Si/Al = 2.75. Equation (15) gives Si/Al = 3.0; Equation (16) Si/Al = 2.76. Generally, it can be concluded from these data that Equation (15) is less exact, if the water content of the batches is low. This effect will be studied in a separate paper. In a paper of Senderov and Khitarov5 the geologic formation of natrolite and analcime has been simulated from formally neutral batches of the composition NaAlO, : 2.3 SiO,.

are reportedZ5 for different conditions of aging and seeded and unseeded batches. Equation (15) gives a value of Si/Al = 2.86; from Equation (16)) Si/Al = 2.62.

+(2 + im)*n/(Z n*m)

From Eq. (15) can be concluded that in this case both the batch composition and the composition of the product should be equal. In the experiments for the lowest temperature of 423 K in accordance with this argument an Si/Al ratio of 2.35 was found. For temperatures up to 623 K the Si/Al ratio in the product decreases to 1.85, indicating that in a refined theory the temperature dependence of b in Equation (13) must be taken into account. Finally, a paper of Collela et al. should be mentioned in which several rare zeolites are crystallized from batches of the composition 1.40 L&O : 2.11 M,O : f&O, : 2 SiO, : 130 H,O. with = 1.76) = 1.6). the

A *

1 + Z*(SiO2/(NoOH-Al( 1 + 2*] n

)j

(Si/AI$,, ]/ (n*m)

If M is Rb or Cs, cancrinite compositions Li 5,05Rb1.24[A14,5Si07,6204)

can be obtained 4.63 H,O 5.70 H,O (Si/Al (Si/Al

Li 2.88Cs,,,, [Alu4,7:iSi0,.(i204)
1 2 S/AI calculated 3 4

Figure 7 Si/Al ratio for the samples, lated to Equations (15) and (IO) using the composition of the solution phase.

described different

in Ref. 53, information

reon

From Equation (15) Si/Al = 1 .O follows, which is obviously different from the observed values. Again, the water content of the batches is rather low. The value obtained from Equation (16) would be below 1.0. A more systematic review of the importance of Equation

154

Zeolites

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.%/A/

ratio

of different

zeolites:

H. Lecher?

et a/.

(15) for data from arate paper.

the literature

will

be given

in a sep-

ACKNOWLEDGEMENT
This work was supported schungsgemeinschaft. by the Deutsche For-

Some remarks

on limitations

of the theory REFERENCES

Barrer, R.M. Hydrothermal Chemistry ofZeo/ites, Academic Press, London, 1981 Breck, D.W. Zeolite Molecular Sieves, Wiley, New York, 1974 Occelli, M.L. and Robson, H.E. (Eds.) Zeolite Synthesis, ACS Symp. Ser. 398, Am. Chem. Sot. Washington, DC, 1989 Occelli, M.L. and Robson, H.E. (Eds.) Molecular Sieves: Studies of Microporous Materials, van Nostrand, Reinhold, New York, 1992 Szostak, R. Molecular Sieves: Principles of Synthesis and Identifkation, van Nostrand, Reinhold, New York, 1989 van Bekkum, H., Flanigen, E.M. and Jansen, C. (Eds.) Introduction to Zeolite Science and Practice, Elsevier, Amsterdam, 1989 Olson, D. and Bisio, A. (Eds.) Proceedings of the Sixth International Zeolite Conference, Butterworth, Guildford, 1984 Murakami, Y., lijima. A. and Ward, J.W. (Eds.), New Developments in Zeolite Science and Technology, Kodansha, Elsevier, Amsterdam, 1986 Jacobs, P.A. and van Santen, R.A. (Eds.), Zeolites: facts, Figures, Future, Studies in Surface Science and Catalysis, Vol 49, Elsevier, Amsterdam, 1989 von Ballmoos, R., Higgins, J.B. and Treaty, M.M.J. (Eds.) Proceedings from the Ninth International Zeolite Conference, Butt&worth, Boston, 1992 Weitkamp, J., Karge, H.G., Pfeifer, H. and Hoolderich, W. (Eds.) Zeolites and Related Microporous Materials Studies in Surface Science and Catalysis, Vol 84, Amsterdam, 1994 Kacirek, H. and Lecher?, H. J. Phys. Chem. 1975, 79, 1589 Kacirek, H. and Lechert, H. J. Phys. Chem. 1976, 80, 1291 Kacirek, H. PhD Thesis, University of Hamburg, 1974 Lechert, H., Kacirek, H. and Weyda, H. in Zeolite Synthesis (Eds. M.L. Occelli and H.E. Robson), ACS Symp. Ser. 398, Am. Chem. Sot., Washington, DC, 1989, p. 494 Lechert, H. and Kacirek, H. Zeolites 1991, 11,720 Lechert, H. and Kacirek, H. Zeolites 1993, 13,192 Lecher-t, H. in Studies in Surface Science and Cata/ysis, Vol. 18, Structure and Reactivity of Modified Solids (Ed. P.A. Jacobs) Elsevier, Amsterdam, 1984, p. 107 Wienecke, J. PhD Thesis, University of Hamburg, 1985 Weitkamp, J., Karge, H.G., Pfeifer, H. and Hoolderich, W. (Eds.) Zeolites and Related Microporous Materials Studies in Surface Science and Catalysis 1994, 84A, 147 Staelin, P. PhD Thesis, University of Hamburg, Hamburg, Germany, 1991 Elliott, C.H. and McDaniel, C.V. US Pat. 3,639,099 (1972) McDaniel, C.V., Maher, P.K. and Pilato, J.M. US Pat. 4,166,099 (1979) Kasahara, S., Itabashi, K. and Igawa, K. in New Developments in Zeolite Science and Technology (Eds. Y. Murakami, A. lijima, and J.W. Ward), Elsevier, Amsterdam, 1986 p. 185 Ginter, D.M., Radke, C.J. and Bell, A.T. in Molecular Sieves: Studies of Microporous Materials (Eds. M.L. Occelli and H.E. Robson), van Nostrand, Reinhold, New York, 1992, D. 6 McCormick, A.V., Bell, A.T. and Radke; C.J. Zeolites 1987, 7, 183 McCormick, A.V., Bell, A.T. and Radke, C.J. J. Phys. Chem. 1989, 93, 1741 Ginter, D.M., Radke, C.J. and Bell, A.T. in Studies in Surface Science and Catalvsis. Vol 49. Zeolites: Facts, Fiaures. Future (Eds. P.A. Jacobs. and R.A. van Santen), Els&ier, Amsterdam, 1989, p. 161 Mortlock, R.F., Bell, A.T. and Radke, C.J., J. Phys. Chem. 1991,95,372

It can be seen that Equations (lo), (13), (15), and (16) allow the calculation of the %/Al ratio of different zeolites from the composition of the solution phase or the batch composition with good accuracy. Refinements of the theory will be necessary to explain the dependence of the Si/Al ratio on the water content of the batch. In the present theory, the water content is eliminated in Equations (10) and (11) because the formation of the ratio is in terms of the silicate and the OH- content of the batch. This does not disturb the description of the system as long as the assumptions of our theory are valid. One of these assumptions is that the aluminate concentration in the solution is low and that there is enough water in the batch so that all of the silicate given by Equation (6) is present in the solution phase. If, on the other hand, for large amounts of water the gel phase is partially hydrolyzed, corrections will be neccessary. Practically, these conditions are fulfilled in a range of the parameter p between about 100 and 500. Changes in the solubility of the gel phase may be also present if complexing agents are added to the batch. Thus it can be assumed that one effect of the templates is an influence on the silicate concentration and the kind of silicate species in the solution phase. Refined considerations for extreme water contents will be discussed in a separate paper.

5 6

10

11

CONCLUSIONS
The Si/Al ratio of faujasites correlates with the concentrations of the silicate and the OH- in the solution phase with very good accuracy by the Equation (10) (Si/W prod = 1 + b . ISiO,l,,,/IOH-I that can be taken from simplifying assumptions n. m) the experit can be

12 13 14 15

16 17 18

where b is a constant iments. With some concluded that W/N with

19 20

prod = (b+ m) . n/(b+ ratio

21 22 23 24

the Si/Al

n and the excess alkalinity /SiO,

m = (NaOH

- NaAlO,)

in the batch. With b = 2 a wide range of batch compositions can be related to the Si/Al ratio of the final product with very good accuracy. The constant b is certainly dependent on temperature and may have different values for other zeolites such as ZSM-5. Deviations at low Si/Al ratios can be corrected empirically, obtaining Equation (16) W/W prod = (2+m).n/(2+n.m)+0.3/n-0.3.

25

26 27 28

The exactness of the fit is a good guideline for further discussions of a more detailed common mechanism for the crystallization process of zeolites.

29

Zeolites

16:149-156,

1996

155

.Si/AI 30 31 32

ratio

of different

zeolites:

H. Lechert

et al. 43 44 45 46 47 48 49 50 51 Guth, J.L., Caullet, P., Jacques, P. and Wey, R. Bull. Sot. Chim. France, 1980, 314. 121 Caullet, P. PhD Thesis, University of Mulhouse, 1983 Harris, R.K. and Knight, G.T.G. J. Chem. Sot. Farad. Trans. I/1983,79,1525 Harris, R.K. and Knight, G.T.G. J. Chem. Sot. Farad. Trans. // 1983, 79, 1525 Ingri, N. Acta Chim. Stand. 1959, 13, 775 Lagerstrtim, G. Acta Chim. Stand. 1959, 13, 722 Aveston, J. J. Chem. Sot. 1965,4444 Ingri, N., Lagerstrhm, G., Frydman, M. and Sillen, L. Acta Chim. Stand. 1957, 11, 1034 Lechert, H. and Weyda, H. in Molecular Sieves: Synthesis of Microporous Materials (Eds. M.L. Occelli and H.E. Robson), van Nostrand, Reinhold, New York, 1992, 77 Bornholdt, K. Diplome Work, University of Hamburg, 1993 Zhdanov, S.P. Adv. Chem. Ser. 1971,101,20 Zhdanov, S.P. Molecular Sieves, Society of Chemical Industry, London, 1968, p. 70 Senderov, E.E. and Khitarov, N.I. Adv. Chem. Ser. 1971,101, 149 Colella, C., de Gennaro, M. and lorio, V. in New Developments in Zeolite Science and Technology (Eds. Y. Murakami, A. lijima, and J.W. Ward), Elsevier, Amsterdam, 1986, p. 263

33 34 35 36 37 38 39 40 41

42

Ginter, D.M., Went, G.R.T., Bell, A.T. and Radke, C.J. J. Magn. Reson. 1989, 81, 217 McCormick, A.V. and Bell, A.T. Catal. Rev. Sci. Eng. 1989, 31.97 Bell, A.T. in Zeolite Synthesis (Eds. M.L. Occelli and H.E. Robson) ACS Symp. Ser. 398, Am. Chem. Sot., Washington, DC, 1989, p. 66 Fahlke, B., Starke, P., Seefeld, V., Wieker, W. and Wendland, K.-P. Zeolites 1987, 7, 209 Fahlke B. and Wieker, W. Zeolites 1983, 3, 195 Polak, F. and Stobiecka, E. Bull. Acad. PO/on. Sci., Ser. SC;. Chim. 1978, 26, 899 Engelhardt, G., Zeigan, D., Jancke, H., Hoebbel, D. and Wieker, W. Z. Anorg. A//g. Chem. 1975, 418, 17 Hoebbel, D., Vargha, A., Fahlke, B. and Engelhardt, G. Z. Anorg. A//g. Chem. 1985, 521, 61 Fahlke, B., MDller, D. and Wieker, W. Z. Anorg. A//g. Chem. 1988,562,141 Engelhardt, G., Fahlke, B., Mlgi, M. and Lippmaa, E. Zeolites 1985, 5, 49 Thangaraj, A. and Kumar, R. Zeolites 1990, 10, 117 Harvey, G. and Dent Glasser, L.S.D. in Zeolite Synthesis (Eds. M.L. Occelli and H.E. Robson) ACS Symp. Ser. 398, Am. Chem. Sot., Washington, DC, 1989, p. 49 Caullet, P. and Guth, J.L. Zeolite Synthesis (Eds. M.L. Occelli and H.E. Robson) ACS Symp. Ser. 398, Am. Chem. Sot., Washington, DC, 1989, p. 83

52 53 54 55 56

156

Zeolites

16:149-156.1996