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Powder Technology 145 (2004) 10 19 www.elsevier.

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Crystallization of zeolite L from Na2OK2OAl2O3 SiO2 H2O system


Yong Sig Ko a, Wha Seung Ahn b,*
a

Department of Advanced Material Chemistry, Shinsung College, Dangjin-gun 343-861, South Korea b School of Chemical Science and Engineering, Inha University, Inchon 402-751, South Korea Received 13 June 2003; received in revised form 14 December 2003; accepted 25 March 2004 Available online

Abstract Zeolite L powder was prepared from the substrate mixture of Na2O K2O Al2O3 SiO2 H2O system at temperatures of 373 443 K. In order to investigate the factors which influence the synthesis outcome, a reference system which yields zeolite L in a reproducible manner was chosen and subjected to controlled changes in synthesis parameters. The crystalline zeolite L samples obtained were characterized by elemental chemical analysis, X-ray diffraction (XRD), and scanning electron microscopy (SEM). It was established that phase purity, morphology, and the size of crystals of crystalline product were affected by molar ratios of the substrate, such as SiO2/Al2O3, (K2O + Na2O)/ SiO2, Na2O/(K2O + Na2O), and H2O/(K2O + Na2O). Amorphous silica powder (Zeosil) was the preferred silica source, and the crystallization rate was promoted by introducing gel aging, seeding, and rapid heating rate. D 2004 Elsevier B.V. All rights reserved.
Keywords: Zeolite L; Crystallization; Synthesis parameters; Seed; Gel aging; Heating rate

1. Introduction Zeolites and related materials play an important role in many commercial applications, such as adsorption, separation, and particularly in the field of heterogeneous catalysis. The uniform pore size and the specific adsorption characteristics of zeolites are the main reasons for the development of adsorptive separation and catalytic reaction processes, and much works have been carried out in adjusting the properties to the requirement of the different applications. The crystal structure of zeolite L was determined initially by Barrer and Villiger [1], which has one-dimensional pores of about 0.71 nm aperture leading to cavities of about 0.48 1.24 1.07 nm with a Si/Al ratio of typically 3.0 [2]. Due to its unique structural features, zeolite L is known as a good support for noble metal catalysts used in aromatization of the C6-hydrocarbons of normal structure and is being used commercially in the Chevron Aromax cyclization process [3]. Some investigations have been conducted on the properties of L-type zeolite with regards to its structure [1,2], adsorptive properties [4,5], and catalytic properties [6].
* Corresponding author. Tel.: +82-32-8607466; fax: +82-32-8720959. E-mail address: whasahn@inha.ac.kr (W. Seung Ahn). 0032-5910/$ - see front matter D 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.powtec.2004.03.016

Preparation of the zeolite L with or without using organic templates was reported mostly as patents by various investigators [7 13] claiming different particle morphologies. According to Wortel [10], zeolite L, having a cylindrical morphology comprised of crystallites with a mean diameter of at least 0.5 to 1 Am, is particularly valuable as a catalyst support. Verduijn [12,13] reported that zeolite L with flat basal planes and smaller crystallite size was prepared from the synthesis gel modified by the addition of small amounts of copper, magnesium, calcium, barium, cobalt, zinc, chromium, manganese, or nickel. The addition of these metals was reported to suppress unwanted zeolite W formation. Joshi et al. [14] reported the effects of substrate compositions on the crystallization kinetics of the zeolite L, and Meng et al. [15] synthesized an ultrafine zeolite L with a crystal size of f 30 nm in diameter. Isomorphous substitution of Fe3 + in zeolite L was reported recently by us [16]. Although a considerable amount of information is available in the literature describing various synthesis routes and crystallization kinetics of zeolite L, the effects of synthesis parameters on L-type zeolite were never systematically investigated. Studies of zeolite crystallization are important both in order to optimize industrial production of zeolites and to obtain information concerning the mechanisms involved

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during nucleation and crystal growth. The starting point for zeolite synthesis is crystallization from an inhomogeneous gel, created from a silica source and an alumina source, combined with water under high pH conditions generated by OH ion concentration. Factors influencing zeolite crystallization are gross composition, time, temperature, and other history-dependent factors, but how the available parameters can be manipulated to create a particular zeolite structure is a complex problem not yet fully understood [17]. In this study, the effects of starting raw materials, substrate composition, reaction temperature, reaction time, gel aging, seeding, heating rate, and mixing sequence upon the crystallization rate of zeolite L were reported. For this purpose, these synthesis parameters were systematically varied in a Na2O K2OAl2O3 SiO2 H2O substrate system of fixed composition, which was implemented by us earlier for preliminary synthesis and catalytic application studies [18].

2. Experimental 2.1. Synthesis of zeolite L Zeolite L was prepared from substrates having the following composition range expressed as oxide mole ratios: SiO2/Al2O3 = 10 35, (K2O + Na2O)/SiO2 = 0.30 0.55, Na2O/(K2O + Na2O) = 0.20 0.68, H2O/ (K2O + Na2O) = 30 60. The silica sources used were colloidal silica sol (Ludox HS-40 from Dupont, 40% SiO2), fine silica powder of Zeosil 77 (KoFran, 91.8% SiO2), and aqueous sodium silicate solution (KoFran, 25.3% SiO2, 6.6% Na2O). Sodium aluminate (Junsei, 32.6% Na2O, 35.7% Al2O3) was used as alumina source. Potassium hydroxide (Tedia, 85%) and sodium hydroxide (Tedia,

Fig. 2. XRD patterns of zeolite L samples obtained with different SiO2/ Al2O3 ratios at 443 K (T and W denotes the peaks for zeolite T and W, respectively). Gel composition: (K 2 O + Na 2 O)/SiO 2 = 0.37, H 2 O/ (K2O + Na2O) = 45, Na2O/(K2O + Na2O) = 0.5; 24h synthesis. (a) 20, (b) 25, (c) 30, and (d) 35.

98%) were used for alkali metal cations. Sodium hydroxide, potassium hydroxide, and alumina source were added to the deionized water in a Teflon vessel (100 ml) and stirred until the alumina source was completely dissolved. This solution was then added slowly to the aqueous silica solution, and the whole mixture was stirred vigorously for further 30 min for homogenization. The reaction mixture was transferred to a series of 100-ml Teflon-lined stainless steel vessels and kept in a convection oven maintained at 373 443 K. In some cases, crystallization was also performed with stirring using a magnetic bar, or an aging treatment at room temperature was conducted prior to the hydrothermal reaction. Reaction vessels were removed from the oven at the scheduled time intervals and were quenched immediately in cold water. The solid products were separated by filtration and washed with deionized water repeatedly until the pH of the washed liquid was 9. Finally, the products were dried in an oven at 393 K for 12 h before characterization. 2.2. Characterization

Fig. 1. Effect of reaction temperature on the crystallization of zeolite L, and variation of pH from the substrate composition of 5.4K2O 5.7Na2O Al2O3 30SiO2 500H2O.

The samples prepared were analyzed by X-ray diffraction (XRD) for phase identification. The unit used was a powder

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X-ray diffractometer (Philips, PW-1700) with a scintillation counter and a graphite monochromator attachment, utilizing Ni-filtered CuKa radiation. The pure sample with the most intense peaks was taken as reference assigning 100% crystallinity, and the percentage crystallinity of the other samples was calculated relative to the reference. A quantitative measure of the crystallinity of a zeolite is made by using the summed areas of selected peaks in the X-ray diffraction pattern. To calculate crystallinity, peaks located at 2h = 5.5, 19.4, 22.7, 28.0, 29.1, and 30.7 were used to avoid the possible interference of the coexisting phases, such as zeolite W or T for a given sample. The morphology of the crystalline phase was examined using a scanning electron microscope (Hitachi, X-650) after coating with an Au Pd evaporated film. The chemical analysis of crystal-

line samples was performed using ICP (Jobin Yuon JY-38 VHR) and XRF (Rigaku, 3070).

3. Results and discussion In this work, effects of various synthesis parameters which can influence the crystallization sequence mentioned on zeolite L were examined in detail. 3.1. Influence of temperature Fig. 1 shows the crystallization curves of zeolite L synthesized at different reaction temperatures from a substrate composition of 5.4K2O 5.7Na2OAl2O3 30SiO2

Fig. 3. SEM photographs of zeolite L crystals obtained with different SiO2/Al2O3 ratios in the synthesis mixture. (a) 25, (b) 28, (c) 30, and (d) 33.

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500H2O. It was observed that the increase in reaction temperature caused a decrease in induction period and resulted in reduction of crystallization time. For the zeolite L sample obtained at 373 K, the maximum crystallinity of the zeolite reached only 48% even after 7 days. On the other hand, highly crystalline zeolite L crystals were obtained in 24 h at 443 K. Fig. 1 also shows the pH variation of the mother liquor with synthesis time during the crystallization of zeolite L from the synthesis mixture at 373 K. Crystallization of zeolites from the synthesis gels is usually accompanied by a noticeable change in pH, and pH measurement can be used as a convenient method for examining the course of the crystallization. As can be seen, the crystallization of zeolite L is accompanied by a sharp decrease in pH, which coincides with an increase in crystallinity. 3.2. Influence of SiO2/Al2O3 ratio Fig. 2 shows the change in X-ray diffraction patterns of zeolite L samples prepared with different SiO2/Al2O3 ratios. It was found that zeolite L could be obtained as a pure phase and with good crystallinity at the SiO2/Al2O3 ratio around 30. If the SiO2/Al2O3 ratio is too high or low, the system forms zeolite T or W, respectively, which appears to be the more stable phase. Such a phase transformation seems to be in accordance with the fact that all these zeolites are crystallized in K+/Na+-mixed alkali systems, and all of them possess cancrinite cages as the major secondary building units in their frameworks. Fig. 3 shows the SEM photographs of the As-synthesized zeolite L samples with various SiO2/Al2O3 ratios at constant (K 2 O + Na 2 O)/SiO 2 , Na 2 O/(K 2 O + Na 2 O), and H 2 O/ (K2O + Na2O) ratios. The shape of zeolite L crystals was

Fig. 5. XRD patterns of zeolite L samples obtained with different (K2O + Na2O)/SiO2 ratios at 443 K (T denotes the peaks for zeolite T). Gel composition: SiO2 /Al2 O3 = 30, H2 O/(K2 O + Na2 O) = 45, Na2 O/ (K2O + Na2O) = 0.5; 24 h synthesis. (a) 0.33, (b) 0.37, (c) 0.40, and (d) 0.43.

Fig. 4. The relationship of SiO2/Al2O3 ratio of synthesis mixture and zeolite L products.

dependent on SiO2/Al2O3 ratio of synthesis mixture. Most of the crystals were produced as a typical clam-shaped crystal of domed basal plane, whereas highly siliceous gel at SiO2/Al2O3 ratio of 33 produced crystals having basal planes of more flatness. The higher SiO2/Al2O3 ratio led to the larger zeolite L crystals; the samples in the case of SiO2/ Al2O3 ratios of 28, 30, and 33 had average crystal sizes of 0.8, 1.5, and 2.3 Am, respectively. It is also worth noting that only a small change in SiO2/Al2O3 ratio of synthesis mixture from 35 (Fig. 2d) to 33(Fig. 3d) resulted in pure L crystals without phase impurities. Fig. 4 shows the relationship of SiO2/Al2O3 ratios in the synthesis mixture and those of the zeolite L crystals obtained. It can be seen from the figure that there is a pronounced general trend towards proportional growth of SiO2/Al2O3 ratio in the crystals with increase in the SiO2/ Al2O3 ratio in the substrate. For catalytic applications, such as catalytic cracking and isomerization, zeolites become more useful as the SiO2/Al2O3 is increased. Acid strength and thermal stability, which is critical for the success of a zeolite as a catalyst for these applications, are both improved with increasing SiO2/Al2O3 ratio. In this experiment, highly siliceous zeolite L of SiO2/Al2O3 = 6.8 could be obtained with the SiO2/Al2O3 ratio of 33 of the substrate mixture.

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3.3. Influence of (K2O+Na2O)/SiO2 ratio Fig. 5 shows the change in X-ray diffraction patterns of zeolite L samples with different (K2O + Na2O)/SiO2 ratios. For (K2O + Na2O)/SiO2 ratio of 0.33, zeolite L was found to coexist with zeolite T, whereas no other crystalline phase was formed from the synthesis mixture with the ratio higher than 0.33. In (K2O + Na2O)/SiO2 ratios lower than 0.37, the increase of (K2O + Na2O)/SiO2 ratio led to a gradual increase in the content of zeolite L phase. It seemed that the increase in alkalinity effectively induced the dissolution of the amorphous aluminosilicate gel in the reaction mixture to form soluble active species, and therefore, the crystallization rate has been increased with increasing (K2O + Na2O)/SiO2 ratio. However, at higher (K2O + Na2O)/SiO2 ratios above 0.37, the degree of crystallization for the zeolite L decreased as the

ratios increased. This indicates that the polycondensation of hydroxoaluminate and silicate ions is restricted by excess alkalinity. These results suggest the existence of an optimum alkalinity for nucleation in the synthesis of zeolite L. Results obtained from these series of experiments show that the optimum ratio of the (K2O + Na2O)/SiO2 is around 0.37. Fig. 6 shows the SEM photographs of the zeolite L samples with various (K2O + Na2O)/SiO2 ratios at constant SiO2/Al2O3, Na2O/(K2O + Na2O), and H2O/(K2O + Na2O) ratios. Morphology appeared sensitive to the (K2O + Na2O)/ SiO2 ratio of the synthesis mixture; a distinctive characteristic in morphology was the formation of ice hockey puckshaped crystals at the ratio of 0.37, accompanied by a decrease in crystal size as the (K2O + Na2O)/SiO2 ratios increased. The samples in the case of (K2O + Na2O)/SiO2 ratios of 0.37, 0.40, and 0.43 had average crystal sizes of

Fig. 6. SEM photographs of zeolite L crystals obtained with different (K2O + Na2O)/SiO2 ratios in the synthesis mixture. (a) 0.35, (b) 0.37, (c) 0.40, and (d) 0.43.

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Fig. 7. The relationship of SiO2/Al2O3 ratio of the zeolite L crystals and (K2O + Na2O)/SiO2 ratio in the synthesis mixture.

1.0, 0.7, and 0.4 Am, respectively. It is noteworthy in that Verduijn [19] demonstrated that a Pt-loaded zeolite L catalyst with ice hockey puck morphology showed significantly improved selectivity and stability over typical clamshaped zeolite L for the aromatization of light aliphatic hydrocarbons. It has been claimed that the SiO2/Al2O3 ratio in the zeolite product is highly sensitive to the alkalinity in the synthesis mixture [20], and the SiO2/Al2O3 ratio of the final product is primarily determined by alkalinity [21,22]. Fig. 7 shows the relationship of SiO2/Al2O3 ratio of the zeolite L crystals and (K2O + Na2O)/SiO2 ratio in the synthesis mixture. The SiO2/ Al2O3 ratio of the solid product decreased with an increase of the (K2O + Na2O)/SiO2 ratio in the synthesis mixture. In accordance with this, high-silica zeolite L samples should be prepared from aluminosilicate mixtures with lower ratios of the alkali metal oxides to silica. 3.4. Influence of H2O/(K2O+Na2O) ratio Fig. 8 shows the change in X-ray diffraction patterns of zeolite L samples with different H2O/(K2O + Na2O) ratios. It was observed that with the synthesis temperature, time, and the other three substrate ratios being kept constant, the product formed in the sequence of zeolite L to zeolite L/ zeolite T with increasing H2O/(K2O + Na2O) ratio. The zeolite L samples were obtained when the H 2 O/ (K2O + Na2O) ratio varied between 30 and 50. However, for H2O/(K2O + Na2O) ratio higher than 50, coprecipitates of zeolites L and T were obtained with a decreasing proportion of zeolite L as the H2O/(K2O + Na2O) ratio increases. A strong influence of water contents on the zeolite phase obtained was also observed in mordenite synthesis [23,24]. In fact, the ratio of H2O/(K2O + Na2O)

determines the concentration of the gel if the other threesubstrate mole ratios are kept constant, and the viscosity of the synthesis gel changes with changing water content. Therefore, it may influence the rates of nucleation and crystal growth. The H2O/(K2O + Na2O) ratio in the synthesis mixture represents the inverse of the alkalinity, and the phenomenon can also be explained as a consequence of the alkalinity variation [25] rather than the overall changes in gel concentration. As is shown, pure zeolite L was formed at the H2O/(K2O + Na2O) ratio of around 45. Fig. 9 shows the SEM photographs of the zeolite L samples with various H2O/(K2O + Na2O) ratios at constant SiO2/Al2O3, (K2O + Na2O)/SiO2, and Na2O/(K2O + Na2O) ratios. The H2O/(K2O + Na2O) ratio in the synthesis mixture influenced the crystal size and shape of zeolite L samples synthesized at 443 K. The average crystal size of zeolite L became larger as the concentration decreases with an increase of water content in the synthesis mixture, which can be a consequence of facile diffusion or interaction of the substrate with decreasing viscosity of aluminosilicate gel. A distinctive characteristic in crystal shape was the formation of ice hockey puck-shaped crystals at the ratio of 50, desired for the catalytic applications, and unwanted zeolite T appeared while the H2O/(K2O + Na2O) ratios were more than 55.

Fig. 8. XRD diffraction patterns of zeolite L samples obtained with different H2O/(K2O + Na2O) ratios at 443 K (T denotes the peaks for zeolite T). Gel composition: SiO 2 /Al 2 O 3 = 30, (K 2 O + Na 2 O)/SiO 2 = 0.37, Na 2 O/ (K2O + Na2O) = 0.5; 24 h synthesis. (a) 35, (b) 45, (c) 55, and (d) 60.

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(a)

(b)

(c)

(d)

Fig. 9. SEM photographs of zeolite L crystals obtained with different H2O/(K2O + Na2O) ratios in the synthesis mixture. (a) 35, (b) 40, (c) 43, and (d) 50.

3.5. Influence of Na2O/(K2O+Na2O) ratio Fig. 10 shows the change in X-ray diffraction patterns of zeolite L samples with different Na2O/(K2O + Na2O) ratios. Amorphous gels in the composition ranges of 0.4 < Na2O/ (K2O + Na2O) ratio < 0.6 were converted to the zeolite L phase. For the ratio around 0.5, zeolite L was crystallized as a pure phase with 100% crystallinity; whereas, zeolite W was found at higher ratio of 0.66. The chemical compositions of zeolite L samples synthesized with different SiO2/Al2O3 ratios at a constant ratio of Na2O/(K2O + Na2O) = 0.5 are shown in Table 1. It was found that although the zeolite L could be synthesized from synthesis mixtures containing Na+ ions in the ratio of Na2O/ (K2O + Na2O) = 0.5, the cations in the crystal structure of the zeolite L crystals were mostly potassium. This also

indicates that the zeolite L structure preferentially incorporates K+ ions. It is known that the K+ ion is necessary for the crystallization of pure zeolite L, because its framework structure is based on the cancrinite cage occupied by K+ ion [22]. On the other hand, it was also observed that an increase in the potassium contents of the zeolite L crystals was accompanied by an increase of the aluminum contents, which suggests that the K+ ions may regulate the initial concentration of aluminum in synthesis mixture [26]. 3.6. Influence of silica source and aging time The effects of silica source and aging treatment on the zeolite L crystallization are shown in Fig. 11. The crystallization rate of zeolite L obtained from amorphous fine silica powder (Zeosil) was significantly faster in comparison with

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Fig. 11. Effects of silica source and aging treatment on crystallization rates of zeolite L from the substrate composition of 5.4K2O 5.7Na2O Al2O3 30SiO2 500H2O, using Ludox, Zeosil, and sodium silicate solution (55% of silica) in conjunction with Zeosil (45% of silica) as a silica source at 443 K.

Fig. 10. XRD patterns of zeolite L samples obtained with different Na2O/ (K2O + Na2O) ratios at 443 K (W denotes the peaks for zeolite W). Gel composition: SiO 2 /Al 2 O 3 = 30, (K 2 O + Na 2 O)/SiO 2 = 0.37, H 2 O/ (K2O + Na2O) = 45; 24 h synthesis. (a) 0.4, (b) 0.5, (c) 0.6, and (d) 0.66.

treatment at room temperature for 1 day substantially improved the crystallization rates of zeolite L irrespective of the silica source. It is believed that the aging treatment offers the time required to achieve the formation of nuclei with dissolution of silica sources [27 31]. 3.7. The influence of using seeds

the case of using colloidal silica sol (Ludox HS-40). When the Zeosil was added to the sodium silicate solution to satisfy the required silica contents of the starting substrate, the crystallization rate of zeolite L was also faster than that of the zeolite L prepared using Ludox HS-40. The best silica source was found to be Zeosil, which produced good yields of the zeolite L within a short period. These results indicate that the fine silica particles promote the nucleation of zeolite L better than do the dissolved silicates or aluminosilicate ions. The use of amorphous silica powder (Zeosil) in the synthesis of zeolite L may also provide real cost advantages over more expensive Ludox HS-40. Fig. 11 also shows the effect of aging treatment of the synthesis mixture at room temperature on the crystallization rates of zeolite L. Aging
Table 1 Chemical composition of zeolite L crystals obtained from synthesis gels with different SiO2/Al2O3 ratios SiO2/Al2O3 (in gel) 25 28 30 33 Chemical composition (wt.%) Si 53.59 57.64 57.75 58.15 Al 18.01 18.21 17.39 16.46 K 16.15 16.22 15.16 14.54 Na 0.5 0.4 0.49 0.52 Na2O/(K2O + Na2O) 0.05 0.04 0.05 0.06

Fig. 12 shows the influence of the addition of seed crystals to synthesis mixture on the crystallization rates of

Gel composition: Na2O/(K2O + Na2O) = 0.5, (K2O + Na2O)/SiO2 = 0.37, H2O/(K2O + Na2O) = 45.

Fig. 12. Effect of seed crystal addition on the crystallization rates of zeolite L from the substrate composition of 5.4K2O 5.7Na2O Al2O3 30SiO2 500H2O at 443 K. Silica source: Ludox HS-40; no aging.

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zeolite L. Seeding of zeolite L crystals of size 1 Am in the reaction batch substantially improved the crystallization rates with increasing amount of seed crystals up to 5 wt.%. However, the size of zeolite L crystals formed was inversely related to the quantity of seed crystals added to the synthesis mixture. Gulfaz and Sand [32] observed a similar result for mordenite. Apparently, the added seed crystals provide a higher surface area available for the assimilation of reactants from synthesis gel accelerating the nucleation and shorten the time required for the crystallization [33]. The gel in these cases serves merely as a source of nutrients for crystal formation from nuclei originating from the seeds. 3.8. Influence of heating rate Fig. 13 shows the effect of different heating rates on the crystallization of zeolite L. In this study, the heating rate was varied in the range of 10 50 K/h using an external heating band controlled by a temperature programmer. The temperature of the reaction mixture in a synthesis vessel was elevated from room temperature to 443 K, with a constant heating rate with or without stirring and was maintained at this temperature for 24 h. The faster the heating rate to 443 K before subsequent isothermal crystallization, the more promoted was the crystallization rate of zeolite L. In addition, when stirring was used in conjunction with the heating rate control, the crystallization rate of zeolite L was faster than that synthesized with the control of heating rate alone under static condition. The sharp increase of crystallization rate of zeolite L with an increase of heating rate may be connected to the enhancement of uniform gel nucleation rate, which produced zeolite L crystals with narrow size distribution.

Fig. 14. Effect of mixing sequence on the crystallization rates of zeolite L from the substrate composition of 5.4K2O 5.7Na2O Al2O3 30SiO2 500H2O at 443 K (no aging). (A) [H2O + Na2O + K2O + Al2O3] ! Ludox HS-40; (B) Ludox HS-40 ! [H2O + Na2O + K2O + Al2O3].

3.9. Influence in order of mixing substrates The order of mixing of substrates is important to obtain a homogeneous gel mixture [34]. To study the influence of mixing sequence of reactants on the crystallization of zeolite L, two methods of the addition sequences were used to prepare the initial synthesis gel. Zeolite L samples with method (a) were synthesized following the procedure described in the experimental section. The method (a) involves a preparation sequence that all of the substrates except for Ludox HS-40 were mixed initially and then the resulting mixture was finally added to colloidal silica Ludox HS-40. For comparison, zeolite L samples were also prepared with method (b), which was based on the last addition of colloidal silica Ludox HS-40 to the solution containing other substrates. Fig. 14 shows the effect of the mixing sequence on crystallization rates of zeolite L. The mixing sequence of the reactants, indeed, influenced the crystallization of zeolite L despite having identical starting compositions; the crystallization rate of zeolite L with method (a) was observed to be faster than that obtained with method (b). It is interpreted that the rapid crystallization of method (a) compared with method (b) may be attributed to the increase in viscosity of the synthesis gel for the former, which encourages supersaturation and hence promotes crystallization of zeolite L.

4. Conclusions A systematic study was carried out to investigate the effects of various synthesis parameters on the crystallization of zeolite L. The concentration of substrates has to be carefully controlled in order to obtain pure zeolite L. In

Fig. 13. Effect of different heating rates on the crystallization of zeolite L from the substrate composition of 5.4K2O 5.7Na2O Al2O3 30SiO2 500H2O at 443 K. Silica source: Ludox HS-40; no aging; reaction time: 24 h.

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particular, SiO2/Al2O3 ratio must be kept within the range of 25 33 in the synthesis mixture, otherwise zeolite T or W crystallize simultaneously. On the other hand, the samples became contaminated by zeolite T when each ratio of (K2O + Na2O)/SiO2 and H2O/(K2O + Na2O) is less than 0.33 and more than 55, respectively. Alkalinity, the water content, and the ratio of the cations also greatly influenced the crystallization process and the morphology of the zeolite L crystals. It was found that the SiO2/Al2O3 ratio of zeolite L product correlated with SiO2/Al2O3 and (K2O + Na2O)/ SiO2 ratios of the gel, and could be adjusted by controlling these ratios in the preparation of the synthesis mixtures before the crystallization. The relative rate of crystallization to zeolite L increased in the order of colloidal silica (Ludox HS-40) < sodium silicate solution < silica powder (Zeosil). It was established that the crystallization rate could be promoted by introducing such modifications as gel aging, seeding, and rapid heating rate. For the crystallization of zeolite L, it was believed that the precursors of the zeolite were formed during the aging step. Increasing the heating rate to 443 K before subsequent isothermal crystallization was very effective for rapid crystallization.

[5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15]

[16] [17] [18] [19] [20]

[21] [22] [23] [24] [25] [26] [27] [28] [29] [30]

Acknowledgements This work was supported by Clean Technology Institute at the School of Chemical Science and Engineering, Inha University.

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