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Synthesis and characterization of zeolite Y and ZSM-5 from Nigerian Ahoko Kaolin using a novel, lower temperature, metakaolinization technique
A. S. Kovo, O. Hernandez and S. M. Holmes*
Received 15th April 2009, Accepted 4th June 2009 First published as an Advance Article on the web 8th July 2009 DOI: 10.1039/b907554b Zeolite Y was synthesised, for the rst time, using Nigerian Ahoko kaolin. In addition, a novel metakaolinization technique was used to produce the necessary reactant phase. The rst step involves the rening of the raw kaolin sample, which removes a substantial amount of quartz, a major impurity present in all kaolin including Ahoko kaolin. The second step, metakaolinization, was carried out at a signicantly lower temperature and for a shorter time than in previous studies. The method for the production of metakaolin, based on rapidly exposing a sample of rened kaolin to elevated temperature was investigated in this work. Metakaolin was obtained after 6 min of exposure at 600  C. The metakaolin produced was then used to synthesis zeolite Y and ZSM-5 using conventional hydrothermal treatment and the shortened thermal treatment cycle was shown to be effective for commercial kaolin as demonstrated by the synthesis of zeolite A.

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Introduction
Zeolites are highly crystalline aluminosilicate materials based on fundamental building blocks of tetrahedral SiO4 and AlO4 giving rise to a three dimensional network. The zeolite frameworks are generally open with water and cations located within the channels and cavities. The cation presence is needed in the zeolite framework to balance the negative charge created as a result of isomorphous substitution of Si4+ by Al3+ in the framework. The mobility of this cation is primarily responsible for the unique ion-exchange and catalytic properties of zeolite and zeolite-like materials.1 Zeolite Y is a faujasitic structure in which a sodalite cage is linked with double 6-ring resulting in a super cage with 12 ring pore opening. It has 3-dimensional channel system and can be imagined as stacking layers of sodalite cages.2 Zeolite Y has Si/Al ratio greater than 31,3 and is widely used as a catalyst in the oil industry. ZSM-5 has a narrower pore structure with the MFI structure type and is also extensively used as a catalyst. Utilizing cheap raw materials to synthesise zeolites offers economic advantages over standard synthetic chemicals. Kaolinite minerals are abundant worldwide and have a Si/Al ratio similar to that of zeolites and can be converted into zeolites by hydrothermal action.4 There are two basic steps for obtaining zeolites from kaolinite: i. Thermal treatment of kaolinite to obtain an amorphous material called metakaolin. ii. Hydrothermal reaction of the metakaolin with an aqueous alkali medium to form the zeolite structure.

School of Chemical Engineering and Analytical Science, The University of Manchester, Sackville Street, Manchester, UK M60 1QD. E-mail: Abdulsalami.kovo@postgrad.manchester.ac.uk; oscar.hernandez@ postgrad.manchester.ac.uk; stuart.holmes@manchester.ac.uk; Fax: +44 (0)161 200 4399; Tel: +44 (0)161 200 4376

Metakaolinization of kaolinite, also known as dehydroxylation, is the transformation of kaolinite into an amorphous, but highly reactive, metastable phase that can readily be converted to zeolites. While studies of metakaolinization have been carried out by several research groupings, the variety of compositions of kaolin throughout the world mean that it is important to explore the metakaolinization of Ahoko kaolin before its use in the synthesis of zeolites. There exists a large body of work on the nature of metakaolin511 applied in the synthesis of a variety of zeolites, however, there is disagreement on the conditions required to produce metakaolin. Several workers,1217 agree on the use of 900950  C as the temperature to perform metakaolinization in the synthesis of different zeolites, however, the time of exposure of kaolin at 900  C varies from one group to the other. Chandrasekhar and Pramada18 have studied the effect of calcination temperature on the zeolite synthesis, stating that increasing the temperature of metakaolinization beyond 700  C can ultimately lead to a higher yield of zeolite NaX (a high alumina faujasite). This was in contrast to work on the effect of temperature of calcination on the zeolite products from kaolin by Murat et al.7 In their paper, they concluded that the temperature has an effect on the chemical reactivity of metakaolin only if the natural kaolin is of low crystallinity and contains a high percentage of iron. In the literature4,1924 the lowest reported metakaolinization temperatures are 600650  C for a range of heating times over several hours. This work has studied the method of metakaolinization to produce calcined kaolin that will be used to synthesise zeolite Y and ZSM-5 with the aim of producing a highly crystalline sample under the most economical conditions i.e. lowest temperature and shortest heating time. Other metakaolins used in the synthesis of zeolites are produced by slowly bringing kaolin in a furnace to the required temperature mostly 700900  C which is then held for at least 2 hours.25 In this work we demonstrate a rapid process to produce metakaolin at reduced temperature.
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Here we report the rst recorded use of Ahoko kaolin (ANK) to synthesise zeolite Y and ZSM-5 using a low temperature and reduced contact time, metakaolinization technique. The metakaolinite produced and zeolites synthesised are characterised to demonstrate the efcacy of the process. The rapid metakaolinisation is also demonstrated for a commercially available material and this material is demonstrated to be effective for zeolite synthesis.

Materials and method

A $30kg raw representative sample of kaolin clay (ANK) was collected (by the author) from its site in Ahoko, Kogi State Nigeria. NaOH was obtained from Sigma-Aldrich (99% analytical grade). Renement of the raw ANK was performed by sedimentation in which separation of the samples was achieved as a result of differential settling times of kaolin and the associated impurities. The separation resulted in the production of ne kaolin powder with a kaolin concentration of 75.3% (22.7% in the raw sample) the remainder is made up of quartz and a very small quantity of mica. Chemical composition of both the raw and rened ANK was determined by X-ray Fluorescence (XRF) and is given in Table 1. XRD patterns of the raw kaolin and the rened kaolin sample are given in gures 1 and 2. The conversion of the ANK and a commercially available kaolin (supplied by Sibelco, UK. SiO2 58.8 wt. %, Al2O3 36.4 wt. %) to metakaolin was followed using powder XRD, both in-situ temperature studies and ex-situ time resolved analysis. The aluminosilicate gel used for zeolite Y synthesis was based on the molar ratio26: 15Na2O: Al2O3:15SiO2: 450H2O
Table 1 XRF results of raw and rened Ahoko Kaolin Chemical constituentWeight % in raw sampleWeight % in rened sample SiO2 Al2O3 Na2O K2O Fe2O3 TiO2 MgO MnO LOIa
a

Fig. 2 XRD pattern of rened ANK (quartz and kaolin peaks are identied).

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Sodium hydroxide pellets, 99%w/w, and anhydrous sodium metasilicate which served as an additional source of silica, were both supplied by Sigma-Aldrich. Ahoko Metakaolin (the chemical composition of the metakaolin was measured using XRF and the Si/Al ratio was found to be 3.0) serves as a combined source of alumina and silica. The resulting molar composition of the synthesis mixture is: 2NaOH:1Metakaolin: 7Na2SiO3:245H2O

72.455 18.963 0.021 0.431 1.0471 1.485 0.132 0.004 6.170

60.958 33.832 0.12 0.602 1.871 1.469 0.191 0.002 0.954

Loss on Ignition (organic content).

The deionised water was divided into two equal parts. The sodium hydroxide pellets were dissolved in the rst part of the deionised water, immediately followed by dissolving the Ahoko metakaolin. The anhydrous sodium metasilicate was added to the second part of the deionised water. Both sets of precursors were subsequently mixed together to form a homogenous aluminosilicate gel. The gel was then aged for 48h with continuous stirring at room temperature. Crystallization of the aged sample was performed at 90  C using a Teon-lined autoclave in an oven at varying reaction times. At the end of the hydrothermal treatment, the autoclave was removed from the oven cooled then ltered and washed with deionised water.The washed samples were dried overnight at 60  C. The aluminosilicate gel used for ZSM-5 synthesis was based on the molar ratio27: 23.4Na2O: Al2O3: 83.4SiO2: 4.2(TPA)2O: 3750H2O

Fig. 1 XRD pattern of raw ANK (quartz and kaolin peaks are identied).

A solution of NaOH was prepared by adding 6.59g of NaOH pellet to 11.05g of water. 42.99g of additional silica provided by Ludox AS 40 was added to the above solution and the mixture was stirred continuously for 5 minutes. This was followed by the addition of 15g of (TPA)2O which serves as a template and as before the resulting solution was stirred to ensure complete homogenisation. 1g of metakaolin was then added to the solution containing NaOH, SiO2 and (TPA)2O and the resulting gel was vigorously stirred for 2h. The gel obtained after 2h of stirring was left to age for 48h and was then hydrothermally treated at 170  C using Teon-lined autoclaves at different crystallization times.
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At the end of each run, the reaction was stopped and was allowed to cool in cold water before nally performing washing to reduce the pH to below 8. The ltered samples were then dried in an oven at 60  C overnight. To check the efcacy of the metakalinisation technique a commercially available kaolin was thermally treated and then converted into zeolite A (a straightforward and rapid conversion). The composition of the sodium aluminosilicate solution was based on the work of Chandereskhar13: 5Na2O: Al2O3: 2SiO2: 200H2O.

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The aluminosilicate gel for the synthesis of zeolite A was prepared by adding 1.80g of NaOH pellet to 15.80g of deionised water and was followed by the addition of 1g of Sibelco metakaolin produced at a temperature 600  C and 10 minute exposure time. Ageing of the resulting gel was done for 24h while continuously stirring the mixture. At the end of the ageing phase, hydrothermal reaction was carried out in a preheated oven at a temperature of 100  C and time of 3h using a Teon-lined autoclave. The reaction was quenched in cold water and was washed to reduce the pH to below 8. The zeolite A sample was subsequently dried in oven at 60  C over night.

Fig. 4 Loss of crystallinity with time of (O Ahoko kaolin, - Sibelco kaolin).

Characterization
An ARL- 9400-XP X-rar Fluorescence Spectometer (XRF) was used for the analysis of the kaolinite. The XRD patterns of both the kaolinite and the resulting zeolite product were produced using a Philips Xpert-Pro diffractometer (Cu Ka, g 1.5406, 30 mA and 40 kV). An FEI Quanta 200 Environmental Scanning Electron Microscope (ESEM) was used for the SEM analysis and TEM and electron diffraction analysis was carried out using a Philips CM 200 Microscope.

Results and discussion

The metakaolinization process Temperature programmed XRD was used to monitor the phase change as ANK sample was heated from room temperature to 900  C. The in-situ XRD pattern of the ANK sample (gure 3) shows complete loss of crystallinity at 600  C indicating formation of metakaolin due to dehydroxylation reaction.

To conrm the heating time required at 600  C to produce metakaolin, a mufe furnace was used pre-heated to a temperature of 600 5  C. A set of crucibles containing 5g each of Nigerian Ahoko kaolin were loaded into the furnace. The crucibles were then removed from the furnace after 110 min (1 min intervals), 20 min, 40 min, 50 min, and cooled in air. The product was then characterized to determine the composition of the metakaolin. XRD studies (Fig. 4) indicate that, even after only 6 minutes heating, at 600  C, the metakaolinization process appears to be complete as the sample is X-ray amorphous. This is fundamentally different from other works on the metakaolinization of kaolin26,28,29 where higher temperatures are reported over a longer time. The commercially available kaolin was also demonstrated to be X-ray amorphous after 10 minutes at 600  C. The metakaolin obtained at 50 minute heating time was utilised in the synthesis of zeolite Y as electron diffraction results, generated using the transmission electron microscope, of the sample heated for 10 minutes show the existence of ordering even when the XRD indicates the material is amorphous. The samples heated for 50 minutes are shown to be amorphous using both techniques. Synthesis of zeolite Y The metakaolin produced by thermal treatment at 600  C for 50 minutes was utilized as a starting material for the synthesis of zeolite Y. The synthesis of zeolite Y was carried out at different reaction times to systematically monitor the nature of crystalline material Fig. 5 shows the XRD patterns of zeolite Y samples when the time of crystallization was varied from 3h to 9h. No zeolite

Fig. 3 In-situ XRD pattern of Nigerian Ahoko kaolinite heated from 30900  C (the peaks remaining at 900  C are indicative of residual quartz, the broad peak at $7 is caused by the window on the in situ cell).

Fig. 5 XRD pattern of zeolite Y synthesised at 3,6 and 9 hours crystallisation time with 50 minutes thermal metakaolinisation (the small peak at 8.8 is attributed to mica.)

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formation was noticed after 3h crystallization time indicating that the conversion to zeolite had not begun. Increase in time of reaction to 6 h shows the crystallization of zeolite Y which compared well with standard zeolite Y pattern. This is in contrast with work of Lapides and Heller-Kallai30 which reported the synthesis of zeolite Y after 72h. This difference between the two studies may be attributed to the degree of crystallinity in Ahoko kaolin and the quality of metakaolinization carried out. Further increases in the hydrothermal treatment to 9h leads to an increase in the intensity of the peaks corresponding to zeolite Y, indicating higher crystallinity. After 9 hours synthesis time, the

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Fig. 7 XRD pattern of zeolite Y synthesised at 6 and 9 hours crystallisation time with 10 minutes thermal metakaolinisation.

zeolite Y synthesised from Ahoko kaolin has reached a similar crystallinity to the standard zeolite Y(PQ corporation, Netherland) used for comparison. The SEM images of the sample obtained at different reaction times are shown in gure 6. The SEM shows well dened octahedral crystals as you would expect from highly crystalline zeolite Y,22 EDX analysis gives the Si/Al ratio of the zeolite Y to be 2.8. Repeating the synthesis for metakolin produced by thermal treatment for 10 minutes gives similar XRD results (Fig. 7) although the SEM image of the 9 hour sample (not shown) appears to show less regular crystals.

Synthesis of ZSM-5 The metakoalin from the 50 minute thermal treatment was used to synthesise ZSM-5. Fig. 8 shows the XRD pattern developing with time up to 72 hours and SEM images of the 48 and 72 hour samples are shown in Fig. 8. It is clear that the metakaolin produced is effective in the synthesis of ZSM-5. The very low levels of metakaolin in the synthesis gel of ZSM-5 mean that while it is the only aluminium source it may be that the synthesis of an MFI structure does not require the metakaolin. This hypothesis was tested by removal of the metakaolin from the synthesis mixture. This led to the formation of silicalite as predicted, although the yield was signicantly lower (<25%) than in the synthesis of ZSM-5 under otherwise identical conditions.

Fig. 6 SEM images of zeolite Y samples at different crystallization times a) 3hrs, b) 6hrs, c) 9hrs.

Fig. 8 XRD pattern of ZSM-5 synthesised at 24, 36, 48 and 72 hours crystallisation time with 50 minutes thermal metakaolinisation (peaks additional to pure ZSM-5 are attributed to quartz, mica, and traces of mordenite).

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4 M. Alkan, M. C. Hopa, Z. Yilmaz and H. Guler, The Effect of alkali concentration and solid /liquid ratio on the hydrothermal synthesis of zeolite NaA from natural kaolinite, Microporous and Mesoporous Materials, 2005, 86(13), 176184. 5 G. P. Souza, R. Sanchez and R. N. F. Holanda, Thermal and structural characterization of Brazilian clays, Journal of thermal analysis and calorimetry, 2003, 73, 293305. 6 E. I. Basaldella, A. Kikot and E. Pereira, Synthesis of zeolites from mechanically activated kaolin clays, Reactivity of Solid, 1990, 8(1 2), 169. 7 M. Murat, A. Amokrane, J. P. Bastide and l. Montanaro, Synthesis of zeolite from thermally activated kaolinite: some observations on nucleation and growth, Clay Minerals, 1992, 27(1), 119. 8 W. Kim, Q. Zhang and F. Saito, Synteathesis of zeolite A and zeolite X from kaolinite activated by mechanochemical trment, 2000, 37, 39 42. 9 T. W. Davies and R. M. Hooper, Structural changes in kaolinite caused by rapid dehydroxylation, Journal of Materials science Letters, 1985, 4, 3942. 10 H. Hongping, 29Si,27Al magic-angle spinning nuclear resonance (MAS NMR) studies of kaolinite and its thermal transformation products, Chinese Journal of Geochemistry, 1995, 14(1), 78. 11 A. Madani, A. Aznar, J. Sanz and J. M. Serratosa, 29Si and 27Al NMR study of zeolite formation from alkali-leached kaolinites: Inuence of thermal preactivation, Journal of Physical Chemistry, 1989, 94, 760 765. 12 F. G. Collina and J. Llorens, Study of the dissolution of dealuminated kaolin in sodium-potassium hydroxide during the gel formation step in zeolite X synthesis, Microporous and Mesoporous Material, 2007, 100(13), 30231. 13 S. Chandrasekhar, Inuence of metakaolinization temperature on the formation of zeolite 4A from kaolin, Clay Minerals, 1996, 31(2), 253 261. 14 P. Bosch, P. L. Ortiz and I. Schifter, Synthesis of faujasite type zeolites from calcined kaolin, Industrial and Engineering Chemistry Product Research and Development, 1983, 22(3), 401406. 15 S. Vilma, K. Ursula and R. Cid, Synthesis of molecular sieves from Chilean kaolinites: Synthesis of NaA type zeolite, Journal of Chemical Technology and Biotechnology, 1999, 74, 358363. 16 I. Caballero, F. G. Collina and J. Costa, Synthesis of X-type zeolite from dealuminated kaolin by reaction with sulfuric acid at high temperature, Industrial and Engineering Chemistry Research, 2007, 46(4), 10291038. 17 A. de Lucas, M. A. Uguina, I. Covian and L. Rodriguez, Synthesis of 13X zeolite from calcined kaolin and sodium silicate for use in detergents, Industrial and Engineering Chemistry Research, 1992, 31(9), 21342140. 18 S. Chandrasekhar and P. M. Pramada, investigation on the synthesis of zeolite NaX from Kerala kaolin, Journal of Porous Material, 1999, 6(4), 283297. 19 L. Marcelo, D. I. P. Mignoni, R. C. Nadia, M. Fernandes and B. C. Pergher, Synthesis of mordenite using kaolin as Si and Al source, Applied Clay, 2007, 6. 20 F. E. Imbert, C. Moreno and A. Montero, Venezuelan natural aluminosilicates as a feed stock in the synthesis of zeolite A, Zeolites, 1994, 14, 374378. 21 K. Okada, H. Y. Yoshikazu and A. Nakajima, Effect of the crystallinity of kaolinite precursors on the properties of mesoporous silica, Applied Clay Science, 2007, 10, 1016. 22 H. Youssef, D. Ibrahim and S. Komarneni, Microwave-Assisted Versus Conventional Synthesis A from metakaolinite, Microporous and Mesoporous Materials, 2008, (115), 527534. 23 M. L. Granizo, M. T. Blanco-Varela and A. Palomo, Inuence of the starting kaolin on alkali- activated materials based on metakaolin: study of the reaction parameters by isothermal conduction calorimetry, Journal of Material Science, 2000, 35(1), 63096315. 24 R. Arjita, C. K. D. Gautam and T. K. Pal, Synthesis and Characterization of Detergent-Grade Zeolite from Indian Clay, Chemical Engineering Technology, 2002, 25(1), 9195. 25 L. Heller-Kallai and I. Lapides, Reactions of kaolinites and metakaolinites with NaOH-comparison of different samples (Part 1), Applied Clay Science, 2007, 35(12), 99107. 26 S. Chandrasekhar and P. N. Pramada, Kaolin-based zeolite Y, a precursor for cordierite ceramics, Applied Clay Science, 2004, 27(34), 187198.

Fig. 9 XRD pattern of zeolite A synthesised from metakolin produced from commercial kaolin treated for 10 minutes at 600  C. Commercial samples also contain mica and quartz which is present in the XRD pattern.

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EDX analysis conrmed the presence of aluminium in the ZSM5 sample. Synthesis of zeolite using commercial kaolin To demonstrate the efcacy of the metakaolinisation process a commercially available kaolin sample was treated at 600  C for 10 minutes. The sample was then converted into zeolite A using a previously reported technique.13 Fig. 9 shows the XRD pattern of the synthesised zeolite showing a highly crystalline zeolite A sample after 3 hours synthesis time. This demonstrates that the metakaolinisation technique is effective for samples other than the Nigerian kaolin studied in this work.

Conclusion
It can be concluded that reactive metakaolin can be produced at very short exposure times, of the order of 10 minutes, to a temperature of 600  C. This is a signicant reduction in both time and temperature on previous studies and represents both a reduced energy requirement and the potential for a continuous production process. The method has been demonstrated to be effective for a commercial kaolin as well as a kaolin from a large, as yet unused, natural deposit in Nigeria. In addition, the yields which are achieved with the low temperature metakaolin are comparable with those achieved using the same synthesis but with metakaolinization at higher temperatures. All samples have been shown to produce highly crystalline zeolite materials using the new metakolinisation process.

Acknowledgements
The authors wish to thank the Petroleum Technology Development Fund (PTDF), Federal ministry of petroleum and natural resources, Nigeria for the sponsorship of the work.

References
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27 K. Abdmeziem and B. Siffert, Synthesis of large crystals of ZSM-5 from a smectite type clay material Applied Clay Science, 1994, (8), 437447. 28 S. Chandrasekhar and P. N. Pramada, Microwave assisted synthesis of zeolite A from metakaolin, Microporous and Mesoporous Materials, 2008, 108(13), 152161. 29 G. W. Brindley and M. Nakahira, The Kaolinite-Mullite reaction Series II: Metakaolin, Journal of the American Ceramic Society, 1958, 42(7), 314317. 30 I. Lapides and L. Heller-Kallai, Reactions of metakaolinite with NaOH and colloidal silica - Comparison of different samples (part 2), Applied Clay Science, 2007, 35(12), 9498.

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