Applied Clay Science 90 (2014) 53–60

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Applied Clay Science

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Research paper

Green synthesis of zeolites from a natural aluminosilicate mineral

rectorite: Effects of thermal treatment temperature
Haiyan Liu a,c, Tong Shen a, Tiesen Li b, Pei Yuan c, Gang Shi c, Xiaojun Bao a,c,⁎
a
State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, PR China
b
East China Design Institute, PetroChina Company, No. 21 Huayan Road, Qingdao 266071, Shandong Province, PR China
c
The Key Laboratory of Catalysis, China National Petroleum Corp., China University of Petroleum, Beijing 102249, PR China

a r t i c l e i n f o a b s t r a c t

Article history: This article reports the effects of thermal treatment temperature on the physicochemical properties of a rectorite
Received 4 February 2013 mineral and the chemical reactivity and crystallization behavior of the activated rectorite products for zeolite
Received in revised form 27 December 2013 synthesis purposes. The raw rectorite mineral and its thermal activation products were systematically character-
Accepted 9 January 2014
ized by XRF, XRD, FTIR and 29Si and 27Al MAS NMR techniques and the resultant zeolites were characterized by
Available online 16 February 2014
XRD technique. The results showed that after being thermally treated in the temperature range of 25–1300 °C,
Keywords:
the rectorite experienced the following four stages: dehydration at 150–300 °C, dehydroxylation at 600–
Rectorite 700 °C, structure collapse at 1000 °C, and new phase formation at above 1100 °C. Moreover, it was found that
Thermal treatment after being thermally treated at ca. 1000 °C, the SiO4 tetrahedral units in the rectorite mineral are distorted,
Zeolite P while the AlO6 octahedral units are decomposed and thus the maximum contents of active SiO2 and Al2O3 can
In-situ synthesis be simultaneously achieved, and as a result, zeolite P is obtained when using the rectorite calcined at 1000 °C
as the starting material for fabricating zeolites. Our results further revealed that like kaolin rectorite after thermal
activation at a suitable temperature can be used for zeolite synthesis and thus demonstrates itself a promising
feedstock for the green synthesis of zeolites directly from natural aluminosilicates without experiencing interme-
diate chemicals.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction
Synthetic or man-made zeolites have been widely used as
adsorption materials and heterogeneous catalysts in the chemical
industry for almost 60 years, and now are playing a pivotal role in
the newly emerging green process industry of the new century.
However, the current industrial processes for fabricating zeolites
themselves are not green, because they heavily rely on the use of
chemicals such as sodium silicate and aluminum sulfate whose
manufacture from natural alumina- and/or silica-containing min-
erals is associated with huge discharge of wastes to the environment
and high energy consumption. Therefore, making zeolites directly from
natural aluminosilicate minerals without experiencing those intermedi-
ate chemicals has received extensive attention. Such an attempt is the
use of kaolin, an aluminosilicate mineral, as the starting material to pre-
pare zeolite Y/kaolin composites, a kind of fluid catalytic cracking (FCC)
catalysts for heavy crude oil conversion (Gibson et al., 2004; Haden
et al., 1968, 1970, 1972), via the so-called in-situ crystallization technique.
However, high-quality kaolin that is suitable for preparing FCC catalysts is
now suffering from the supply shortage because of its wide applications
⁎ Corresponding author at: The Key Laboratory of Catalysis, China National Petroleum
Corp., China University of Petroleum, Beijing 102249, PR China. Tel.: +86 10 89734836.
E-mail address: baoxj@cup.edu.cn (X. Bao).
(Wei et al., 2010). Our previous works (Liu et al., 2012; Wei et al., 2010)
have shown that rectorite, a natural aluminosilicate mineral clay having
a regular 1:1 interstratification of non-expandable (dioctahedral mica-
like) and expandable (dioctahedral smectite-like) 2:1 layers (Stixrude
and Peacor, 2002) and with abundant reserves in the earth, can be
taken as an alternative of kaolin to fabricate zeolites, and zeolite/rectorite
composites via the in-situ crystallization technique and ZSM-5/rectorite
composites that can be used as FCC catalyst additives to boost propylene
yield were successfully prepared.
Typically, the in-situ crystallization technique involves two steps
(Gibson et al., 2004; Haden et al., 1970, 1972): (1) the thermal activa-
tion of an aluminosilicate clay to obtain an X-ray amorphous product
that provides part or all of active SiO2 and Al2O3 species that are leach-
able by acidic or basic solutions and can contribute Al- and Si-species for
zeolite synthesis; and (2) the hydrothermal crystallization of the acti-
vated product in an alkaline medium in the presence of makeup Al-
and Si-species to yield a zeolite or a zeolite/clay composite in which
the zeolite is overgrown on the surface or/and in the pores of the
unreacted clay that functions as catalyst matrix.
It has been recognized that the thermal activation significantly im-
pacts the crystallization behavior of the activated product and the prop-
erties of the resulting zeolitic and composite materials such as their
nature, morphology, pore structure, molar SiO2/Al2O3 ratio and hydro-
thermal stability. Haden et al. (1968, 1970) found that using metakaolin

0169-1317/$ – see front matter © 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.clay.2014.01.006
54 H. Liu et al. / Applied Clay Science 90 (2014) 53–60
obtained by calcining a raw kaolin clay at about 600 °C resulted in the
formation of NaA, while adding a substantial amount of kaolin clay cal-
cined at above 980 °C into the synthesis system led to the formation of
zeolite NaX or/and NaY; furthermore, they found that the use of a kaolin
clay calcined at temperature higher than 900 °C as the raw material
yielded a zeolite/kaolin composite with relatively larger pore diameter
and higher molar SiO2/Al2O3 ratio. Rocha and Klinowski (1990) pointed
out that the maximum reactivity for metakaolin was associated with a
minimum content of hexa-coordinated Al species and a maximum con-
tent of tetra- and penta-coordinated Al species, which could be obtained
by calcining the raw kaolin clay at above 700 °C. Chandrasekhar (1996)
found that the calcination temperature also influenced the solubility of
the resulting metakaolin in the solution of sodium hydroxide and a cal-
cination temperature of 950 °C resulted in more zeolite NaP than NaA.
Chandrasekhar and Pramada (1999, 2004) observed that the uncalcined
kaolin was partially converted into hydrosodalite, whereas metakaolins
resulting from calcination at 400, 500 and 600 °C were transformed
into hydrosodalite at a faster rate; moreover, when increasing the
metakaolinization temperature up to 700 °C, zeolite NaX was found to
be the main synthesis product. Several works (Caballero et al., 2007;
Colina and Llorens, 2007) agreed that for synthesizing different zeolites
from kaolin a metakaolinization temperature of 900–950 °C was suitable,
while others (Alkan et al., 2005; Kovo et al., 2009; Mignoni et al., 2008;
Youssef et al., 2008) suggested a relatively lower metakaolinization tem-
perature of 600–650 °C.
When used as the starting material for synthesizing zeolites or
zeolite/rectorite composites, rectorite must be thermally treated. Our
previous work (Wei et al., 2010) had shown that the contents of active
SiO2 and Al2O3 in activated rectorite firstly increased and then de-
creased with the increasing thermal treatment temperature, and their
maxima could be simultaneously achieved at about 900–1000 °C. This
suggests that the thermal activation behavior of rectorite is distinctly
different from that of kaolinite, which is seldom touched to date to the
best of our knowledge. From the perspective of using rectorite to replace
kaolinite, the effects of thermal activation on the physicochemical prop-
erties of the resulting product have to be well understood. Herein, we
present a thorough investigation on the effects of thermal treatment
on the chemical composition, phase structure, silicon and aluminum co-
ordination, and chemical reactivity and crystallization behavior of the
resulting rectorite by using thermogravimetry and differential scanning
calorimetry (TG–DSC), X-ray fluorescence technique (XRF), X-ray pow-
der diffraction (XRD), Fourier transform infrared (FTIR) and solid state
29
Si and 27Al magic angle spinning nuclear magnetic resonance (MAS
NMR) techniques, with the aim of laying a profound background for
the synthesis of zeolites and zeolite/clay composites.
2. Experimental
2.1. Materials
The raw rectorite mineral containing about 90 wt.% rectorite and a
small amount of impurities including quartz, mica and kaolinite used
in the present investigation was purchased from Hubei Celebrities
Rectorite Company (Hubei Province, PR China), designated as REC, and
its chemical composition in terms of oxides is given in Table 1.
Reagent-grade sodium hydroxide and aluminum sulfate were pur-
chased from the market and used without further purification. Water
Table 1
Chemical compositions of REC, R900 and R1100.
Contents (wt.%) Na2O MgO Al2O3 SiO2 P2O5 SO3 K2O CaO TiO2 Fe2O3
REC 1.36 0.29 36.7 43.2 4.04 0.30 0.96 6.79 5.25 0.43
R900 1.59 0.37 38.7 44.5 2.41 0.13 0.99 5.76 4.14 0.69
R1100 1.48 0.38 38.6 44.4 2.35 0.14 0.99 5.78 4.15 0.68
glass (containing 26.3 wt.% SiO2) was purchased from Beijing Aviation
Material Institute (PR China).
2.2. Thermal treatment
To understand the effects of the thermal activation on the properties
of the resulting rectorite products, a series of thermally treated rectorite
samples were obtained by calcining the raw rectorite at temperatures
ranging from room temperature (25 °C) to 1300 °C for 2 h at a constant
ramping rate of 5 °C/min in an oven with air recirculation. The thus ob-
tained samples were designated as RT, where R indicates rectorite and T
stands for the predetermined calcination temperature. The chemical
compositions of R900 and R1100 obtained by calcining the raw rectorite
mineral at 900 and 1100 °C, respectively, are given in Table 1.
2.3. Zeolite synthesis
To investigate the reactivity and the crystallization behavior of the
thermally treated rectorites, using REC and its derived sample RTs as
the starting materials, respectively, a series of zeolites were hydrother-
mally synthesized. In a typical synthesis process, 6.5 g of one rectorite
sample mentioned above was mixed with 6.0 g of solid sodium hydrox-
ide and 55.5 g of water to obtain a synthesis system with a molar ratio of
3.2 Na2O:1 Al2O3:2 SiO2:130 H2O, corresponding to the system for syn-
thesizing zeolite A. After being aged at 60 °C for 12 h, the crystallization
was conducted at 90 ± 2 °C for 4 h. The resultant samples from REC and
RTs were rinsed thoroughly with deionized water until the filtrate pH
reduced to less than 8. The obtained samples were firstly dried in air
at 90 ± 10 °C for 12 h and secondly at 150 °C for 12 h and designated
as REC-Z and RT-Z, respectively.
For comparison purposes, we prepared NaA zeolite using water glass
and aluminum sulfate as the silicon and alumina sources, respectively,
with the same molar ratio of 3.2 Na2O:1 Al2O3:2 SiO2:130 H2O in syn-
thesis system and under the same crystallization conditions.
2.4. Characterizations
The chemical compositions of the rectorite samples were deter-
mined by XRF on a ZSX-100e 4580 spectrometry (Japan). The TG–DSC
analyses of the rectorite were performed on a Netzsch STA409PC ther-
mogravimetric analyzer (Germany) at a ramping rate of 5 °C/min in
air. The FTIR spectra of the rectorites were recorded using a Nicolet
Magna-IR 560 ESP spectrometer (USA) with a resolution of 1 cm−1.
The solid state 29Si and 27Al MAS NMR spectra of the rectorite samples
were obtained on a Varian Unity Inova 300 instrument (USA) operated
at spinning frequencies of 59.59 and 78.17 MHz, respectively, and at a
spinning rate of 6 kHz. The phase structures of the rectorites and zeolites
were characterized by XRD conducted on a Bruker D8 Focus X-ray dif-
fractometer (Germany). The instrument used CuKα radiation and was
operated at 40 kV, 30 mA, and 2θ ranging from 1.3 to 10° and from 5
to 70° for low- and high-angle diffractions for rectorites and from 5 to
50° for the zeolite samples, respectively.
3. Results and discussion
3.1. Effects of thermal treatment on the physicochemical properties of
rectorite
3.1.1. XRF
Table 1 presents the chemical compositions of REC, R900 and R1100
in terms of oxides, with the latter two being the representatives of the
RT series. It can be seen from Table 1 that the natural rectorite mineral
is a Ca-rich clay mineral, i.e., it contains more calcium than other alkaline
metals. It is also noted that the thermally activated products have no ob-
vious changes in their chemical compositions, as shown in Table 1.
 H. Liu et al. / Applied Clay Science 90 (2014) 53–60 55

3.1.2. TG–DSC
Fig. 1 shows the TG–DSC curves of the rectorite mineral. In the tem-
perature range of 25–1300 °C, the DSC curve (the black curve in Fig. 1)
of the rectorite can be divided into the following three stages:
(1). During the first stage from 25 to 300 °C, there are two endother-
mic peaks located at 95 and 160 °C ascribed to the removal of hy-
groscopic and cation-hydrated water, respectively (Fernandez
et al., 2011); the removal of water molecules from smectite-like
interlayers leads to the decreased layer periodicity with the in-
creasing temperature (Benincasa et al., 2001), as indicated by
the decreased values of the d(002) reflection that is considered
as an index of the interlayer distance in Fig. 2: in the temperature
range of 25–300 °C, the d(002) value decreases rapidly from 1.23
to 0.977 nm and remains at this value with the further increasing
temperature, as seen in Fig. 2B. These results suggest that the
rectorite is completely dehydrated at 300 °C. From the corre-
sponding TG curve (the blue curve in Fig. 1), the weight loss of
this stage is estimated about 3 wt.%.
(2). During the second stage from 400 to 700 °C, there are two endo-
thermic peaks occurring at 550 and 700 °C attributed to the dehy-
droxylation of cis-vacant (cv) octahedral layers (i.e. smectite-type
layers) and trans-vacant (tv) octahedral layers (i.e. mica-like
layers) (Drits and Zviagina, 2009; Drits et al., 1998), respectively,
and the weight loss of this stage is about 6.5 wt.%. It is noted that
a tiny exothermic peak appears at about 580 °C which is possibly
attributed to the formation of a metastable intermediate phase
concomitant with the dehydroxylation reaction.
(3). During the third stage from 800 to 1300 °C, two endothermic
peaks occur at 890 and 1090 °C, respectively, with the former
being attributed to the collapse of smectite-like layers and the lat-
ter to that of mica-like layers in the rectorite crystals; furthermore,
two additional exothermic peaks also appear at about 1150 and
1200 °C, indicating the formation of new phases. Fig. 2. Low-angle XRD patterns of the rectorite samples calcined at different temperatures
(A) and varying trends of d(002) values and peak positions vs. calcination temperature (B).
The above analyses lead to the conclusion that during the thermal
treatment from 25 to 1300 °C, the rectorite has experienced structural
changes due to dehydration, dehydroxylation, crystal collapse and shrinkage and distortion due to dehydration (Fernandez et al., 2011);
new phase formation. however, it was also observed that when the calcination temperature
was increased from 300 to 500 °C, no further change was observed in
3.1.3. XRD the values of d(001); (2) dehydroxylation: when the calcination tem-
The d(001) values and peak positions and the high-angle XRD pat- perature was increased to 600 °C, the d(001) value of the resulting
terns of the rectorite samples are given in Figs. 3 and 4, respectively. product R600 only slightly decreased to 1.916 nm, but the XRD pattern
In agreement with the TG–DSC results, the two figures clearly reveal of R600 was distinctly changed compared to those of R300, R400 and
the four kinds of structural changes the rectorite mineral has experi- R500 obtained at lower calcination temperatures: the peak at 2θ =
enced during the thermal treatment: (1) dehydration: calcination 62° corresponding to d(060) disappeared, and those at 2θ = 20°
below 300 °C causes the dehydration of the mineral; correspondingly, and 2θ = 27.6° became sharper and stronger. The above results indicate
the d(001) value of the resulting calcination product decreased from that the dehydroxylation begins at about 600 °C; the d(001) value of
2.148 nm for REC to 1.919 nm for R300 because of the structural R700 decreased further to 1.906 nm and remained unchanged for

Fig. 3. d(001) values and peak positions of the rectorite samples calcined at different
Fig. 1. TG–DSC curves of the rectorite mineral. temperatures.
56 H. Liu et al. / Applied Clay Science 90 (2014) 53–60
Fig. 4. High-angle XRD patterns of the rectorite samples calcined at different temperatures
(M and Cr denote mullite and cristobalite, respectively).
R800 and R900, indicating that the complete dehydroxylation of the
rectorite mineral ends at ca. 700 °C. More importantly, Fig. 4 shows
that a new XRD reflection exactly corresponding to the exothermic
peak at 580 °C in the DSC curve shown in Fig. 1 appeared at 2θ =
13.8° for R600, R700, R800 and R900 and disappeared for R1000, in-
dicating the formation of a metastable intermediate phase concomitant
with dehydroxylation; (3) structure collapse: for the products obtained
by the calcination of the raw rectorite mineral at 1000 °C, almost no re-
flections assigned to the rectorite structure can be identified in its XRD
pattern and its d(001) value further decreased to 1.859 nm, suggesting
the formation of metarectorite (Chandrasekhar and Ramaswamy,
2002): part or all of crystallized AlO4 groups were separated from
the SiO4 tetrahedral sheets and most of the AlO6 octahedra were
depolymerized and transformed into the amorphous alumina species
(Belver et al., 2002; Lambert et al., 1989); (4) new phase formation: in
the XRD patterns of the products obtained at the calcination tempera-
tures of 1100, 1200 and 1300 °C, new diffraction peaks are observed
clearly, as shown in Fig. 4, indicating the formation of new phases in-
cluding mullite and cristobalite following the collapse of rectorite struc-
ture (Dubois et al., 1995).
3.1.4. FTIR
Fig. 5 presents the FTIR bands of the raw rectorite mineral whose
assignments are suggested in Table 2, and Fig. 6 gives the FTIR curves
of the samples obtained by calcination at different temperatures.
Fig. 5. FTIR spectrum of the raw rectorite mineral.
Table 2
Positions and suggested assignments of the FTIR bands of REC shown in Fig. 5 (Benincasa
et al., 2001; Kloprogge et al., 1999; Percival et al., 1974; Steudel et al., 2009).
Band position/cm−1 Suggested assignment
3643, 3431 O\H bond vibration
1022 Si\O\Si stretching vibration (in plane)
937 Al\OH vibration
823 Al\OH out-of-plane vibration
700 Si\O\Al in plane bending/deformation
546 Si\O\Al or Si\O\Mg bending (octahedral stretching)
480 Si\O bending (tetrahedral deformation band)
Fig. 6A and Fig. 6B show that compared with those of REC, the bands
of the H-bonding to Si\O\Si linkage at 3643 cm−1, the Al\OH out-of-
plane vibration at 823 cm−1 and the Si\O\Al in-plane bending/
deformation at 700 cm−1 of R300, R400 and R500 have no significant
change, suggesting that after the complete dehydration at 300 °C, the
rectorite structure remains stable, and even being calcined at 500 °C
no dehydroxylation reaction takes place, as discussed above. Interest-
ingly, the original Al\OH liberation band at ~ 930 cm−1, Si\O\Si in-
plane stretching vibration band at ~1000 cm−1 and Si\O tetrahedral
deformation bending band at ~ 480 cm−1 are all split into twin peaks,
as shown in Fig. 6B, and after being dehydrated the twin-peaks become
single irregular broad ones, being attributed to the structural distortion
and shrinkage and thus evidencing the physical nature of the dehydra-
tion process without substantial structural change (Sarikaya et al.,
2000).
Distinctly different from those of samples R300, R400 and R500, the
FTIR bands of R600 show dramatic changes: the intensity of the
H-bonding to Si\O\Si linkage band decreases significantly (as shown
in Fig. 6A), the Al\OH liberation band (at 931 cm−1) diminishes to a
shoulder one, the Al\OH out-of-plane vibration, Si\O\Al octahedral
stretching and Si\O\Al in-plane bending bands at 823, 546 and
700 cm−1, respectively, disappear completely, meanwhile two new
bands at 676 and 564 cm− 1, respectively, appear and remain stable
for the samples R600, R700, R800 and R900 (see Fig. 6B). These results
indicate again that the dehydroxylation reaction of the rectorite mineral
begins at about 600 °C. In the FTIR spectrum of R700, the above-
mentioned H-bonding to Si\O\Si linkage and Al\OH vibration
bands disappear completely showing the completion of the dehydroxyl-
ation reaction (Madani et al., 1990); the disappearance of the Al\OH
out-of-plane vibration band at 823 cm− 1 and the Al\OH vibration
band at 931 cm−1 indicates the transformation of two Al\OH groups
to a new type of Al\O\Al linkage due to the release of a water molecule
(Kloprogge et al., 1999).
After the complete dehydroxylation at 700 °C, there is a relatively
stable period for the calcination of the rectorite mineral, as reflected
by the only minor difference in the FTIR spectra of R700, R800 and
R900 except for some tiny changes in the fingerprint region including
the shifts of the Si\O bending (tetrahedral deformation) band from
478 to 488 cm−1 and the in-plane Si\O\Si stretching band from
1022 to 1035 cm− 1. These tiny changes should be attributed to the
structural decomposition and reorganization, because the dehydroxyl-
ation is always considered as a chemical reaction invoking crystalline
decomposition (Sarikaya et al., 2000). The above analysis further con-
firms that the dehydroxylation of the rectorite begins at about 600 °C
and ends at 700 °C, and after the complete dehydroxylation the layered
structure of the rectorite remains stable even being further calcined up
to 900 °C.
The thermal behavior of clay minerals such as kaolinite, illite and
montmorillonite has been extensively studied and the results showed
that the dehydroxylation reactions are much different, depending on
the structures, chemical compositions and impurities of different clay
minerals. He et al. (1995) found that the termination temperatures of
dehydroxylation reactions are as follows: 650 °C for kaolinite and illite,
730 °C for Ca-montmorillonite, 740 for Na-montmorillonite, 560 °C for
 H. Liu et al. / Applied Clay Science 90 (2014) 53–60 57

Fig. 6. FTIR spectra of the raw rectorite and calcinated samples at different temperatures (A and B: survey and fingerprint region of b1000 °C; C and D: survey and fingerprint region of
≥1000 °C).

mica–smectite mixed layer clay, and 830 °C for sepiolite; Fernandez 3.1.5. 29Si and 27Al MAS NMR
et al. (2011) reported that for kaolinite the dehydroxylation is complet- Fig. 7 presents the 29Si and 27Al MAS NMR spectra of the rectorite
ed at 600 °C, and for illite not all hydroxyls can be removed at 600 °C, samples before and after the thermal treatment. It is well known that
whereas for montmorillonite most dehydroxylation occurs between the silicon and aluminum sites in the rectorite can be categorized as fol-
600 and 800 °C. lows: (1) silicon atoms that are in tetrahedral coordination located in
Fig. 6C further reveals that the FTIR spectrum of R1000 is significant- structure layers shared three oxygen atoms with other silicon or alumi-
ly different from those of R700, R800 and R900: the band at 3450 cm−1 num tetrahedra; (2) two locations are possible for aluminum atoms: in
assigned to a combination of Si\O\Al linkage became a broad valley. In the tetrahedral sheet substituting silicon atoms and in the octahedral
the low wavenumber region in Fig. 6D, the broad Al\O octahedral sheet, which are surrounded by four oxygen atoms and two hydroxyl
stretching band at 550 cm−1 can be clearly identified, except for that groups. Here, we use the Qm(nAl) notation for the local Si environment,
a rather broad band located between 1000 and 1500 cm−1 consisting in which Q indicates a Si tetrahedron, m is the number of other Si or Al
of the stretching band of Al\O bonds in Al2O3 and Si\O bonds in SiO2
occurred (Demortier et al., 1999). The results are probably associated
with the collapse of the aluminum matrix and the formation of four-
coordinated Al species (Rocha et al., 1991). This suggests that the frame-
work of the rectorite collapses completely when the thermal treatment
temperature is increased to 1000 °C, in good agreement with the XRD
characterization results.
In the FTIR spectra of R1100, R1200 and R1300, the wide valley be-
tween 1000 and 1500 cm− 1 became narrower again, and the new
bands at 445 and 570 cm−1 with lower wavenumbers could be distin-
guished, attributed to the formation of Si\O and Si\O\Al bonds in
the emerging high-temperature phases.
By combining the above results of TG–DSC, XRD and FTIR analy-
ses, we can conclude that the main changes the raw rectorite miner-
al has experienced during the thermal treatment are as follows:
(1) from 25 to 500 °C: dehydration which takes place with the
accompanied structural shrinkage and distortion; (2) from 600 to
900 °C: dehydroxylation of the rectorite with the concomitant
structural distortion and reorganization; (3) at about 1000 °C:
structure collapse and metarectorite formation; (4) at T N 1100 °C: Fig. 7. 29Si (A) and 27Al (B) MAS NMR spectra of the raw rectorite and calcined products at
new phase formation. different temperatures.
58 H. Liu et al. / Applied Clay Science 90 (2014) 53–60

tetrahedra connected, via an oxygen atom, to the Si tetrahedron, and n 30–40 ppm and they assigned this peak to penta-coordinated alumi-
is the number of Al tetrahedra next-nearest neighbors to the Si num (AlV). According to these authors, we speculate that the additional
tetrahedron. resonance at ca. 41 ppm in the spectrum of R1000 should be assigned to
Fig. 7A shows the characteristic 29Si MAS NMR spectrum of REC that the penta-coordinated aluminum. More importantly, in R1000 AlIV and
has a large peak at about −91.8 ppm and a small shoulder one at about AlV are dominant, the AlVI NMR resonance peak at 6.74 ppm decreased
− 76.4 ppm. The former is attributed to Si atoms in Q3(0Al) structure to a shoulder one (Fig. 7B), further suggesting that with the collapse of
(Akolekar et al., 1997; Lippmaa et al., 1980; Madani et al., 1990), and the rectorite layered structure, hexa-coordinated Al atoms were trans-
the latter is ascribed to Q3(3Al) linkage generated by the substitution formed into tetra- and penta-coordinated ones.
of Al for Si in the tetrahedral layer (Jakobsen et al., 1995). The high de- As shown in Fig. 7B, the resonance peak of AlV in the spectrum of
gree of Al substitution reveals an unusual substitution pattern for mica R1200 disappeared again and the two peaks at 4.66 ppm (AlVI) and
tetrahedral sheets in the rectorite. In fact, the substitution of Al for Si 52.9 ppm (AlIV) can be clearly identified, indicating the formation of
in rectorite is a common phenomenon and this substitution can be con- new phases.
firmed by the FTIR and 27Al MAS NMR analyses. The weak band at Based on the above analyses, we can conclude that after being
823 cm−1 in the REC's FTIR spectrum is assigned to an Al\O out-of- calcined at about 1000 °C, the rectorite mineral suffers from complete
plane vibration considered to be generated by the substitution of Al structure collapse, resulting in the distortion of SiO4 tetrahedral sheets
for Si by Benincasa et al. (2001) and Kloprogge et al. (1999). The reso- and the formation of tetra- and penta-coordinated aluminum in the
nance at 65.9 ppm in the REC's 27Al MAS NMR spectrum is ascribed to resulting calcination products and thus endowing the resulting calcina-
the Q3(3Al) reflection (Kinsey et al., 1985). tion rectorite product with outstanding zeolitization reactivity when used
Compared to those of REC, the resonance peaks in the 29Si NMR as a starting material for fabricating zeolites or zeolite/clay composites, as
spectra of R600, R800 and R1000 become broader, with the large one will be discussed below.
originally at − 91.8 ppm gradually shifting to ca. − 100, − 102 and
− 103 ppm, respectively, suggesting that the silicon sites in REC and
the other three samples exist with different bond lengths, bond angles 3.2. Zeolite synthesis from thermally treated rectorites
or cation-oxygen bond strengths. The up-field shifts of the resonance
probably indicate that: (1) the transformation of the lower- The XRD patterns shown in Fig. 8 indicate that when a calcined
polymerized Si species in Q3 linkage into higher-polymerized ones in rectorite alone was used for synthesizing zeolites with relatively lower
Q4 linkage (Mägi et al., 1984); (2) the decondensation of the Al groups SiO2/Al2O3 ratios such as 4A, the nature of the resultant products depends
bonded to SiO4 tetrahedral units, i.e., Al has been separated from the tet- upon the activation temperature namely the chemical reactivity of the ac-
rahedral aluminosilicate framework (Meinhold et al., 1985). The addi- tivated rectorite. When taking the raw rectorite as the starting material,
tional broad resonance of − 78.8 to − 103 ppm in the 29Si NMR neither 4A nor any other kind of zeolites including hydrosodalite can be
spectrum of R1000 can be assigned to the mixture of the Si sites in obtained, significantly different from the situation of kaolinite reported
Q4(0Al), Q3(0Al), Q3(2Al) and Q3(1Al), suggesting that a complete Si by researchers. Many researchers (such as Chandrasekhar and Pramada,
distortion occurs. For the 29Si NMR spectrum of the product R1200 ob-
tained at a further higher calcination temperature, the two peaks origi-
nally existing in the 29Si spectrum of REC merge into a broad peak
between − 92.7 and − 110 ppm, suggesting a new environment of Si
atom because the resonance at ca. −110 ppm is assigned to cristobalite
(Lippmaa et al., 1980), and that with the chemical shifts of − 85 to
− 105 ppm is ascribed to Si associated with mullite phase (Meinhold
et al., 1985).
The 27Al MAS NMR spectrum of REC shown in Fig. 7B exhibits two
peaks at chemical shifts ca. 1.74 and 65.9 ppm, respectively, significantly
different from the results of kaolin minerals reported: the 27Al spectrum
of kaolinite showed only one sharp and strong peak at a chemical shift
of ca. −3 ppm attributed to octahedrally coordinated aluminum (AlVI)
(Chandrasekhar and Pramada, 2004; Liu and Pinnavaia, 2004). The
peak at 1.74 ppm in the spectrum of REC is assigned to AlVI, and that
at 65.9 ppm is attributed to tetrahedrally coordinated aluminum (AlIV)
generated by the substitution of Al for Si in mica tetrahedral sheets
(Jakobsen et al., 1995).
With the increasing calcination temperature, the chemical coordina-
tion of Al in the resultant products changes significantly. For R600, the
peak positions for AlVI and AlIV shift to 2.15 and 62.4 ppm, respectively,
with the peak of AlVI becoming weaker and that of AlIV becoming stron-
ger and broader. This suggests the decrease of the octahedrally coordi-
nated aluminum atoms and the increase of tetrahedrally coordinated
ones. R800 shows the almost similar spectrum as R600 has, indicating
similar chemical environment of Al in the two samples. In the spectrum
of R1000, however, a new 27Al resonance peak at ca. 41 ppm appears in
addition to those of at ca. 6.74 and 57.2 ppm, revealing three types of
coordinated aluminum sites in the sample. In the early studies on the
thermal treatment of kaolin, Meinhold et al. (1985) observed a 27Al
resonance at 35 ppm in a kaolin sample thermally treated at 650 °C in
addition to those originally existing at 65 and 0 ppm for the raw kaolin Fig. 8. XRD patterns of the samples synthesized from the raw rectorite and the calcined
mineral; Gibson (1987), Lambert et al. (1989) and Rocha and Klinowski products at different temperatures (R: rectorite; HS: hydrosodalite; A: zeolite-A;
(1990) also observed the same three peaks with the middle one at ca. P: zeolite-P; and An: anatase TiO2).
 H. Liu et al. / Applied Clay Science 90 (2014) 53–60
1999, 2004; Heller-Kallai and Lapides, 2007; Madani et al., 1990) had
investigated the reactions of raw kaolinite with NaOH and found that
the primary product of hydrothermal synthesis was always the basic
hydrosodalite (Na8[SiAlO4](OH)2·2H2O) and the formation of hydro-
sodalite was independent of the kaolinite used. As known, rectorite is a
natural aluminosilicate clay consisting of non-expandable mica-like
layers and expandable smectite-like layers in a regular 1:1 ratio
(Stixrude and Peacor, 2002), with the mica-like layers endowing
rectorite with exceptional thermal, hydrothermal and chemical stability.
When using R300 and R600 as the starting material, hydrosodalite
was obtained, as seen in Fig. 8, indicating that after being calcined at
300 °C (the termination temperature of dehydration) and 600 °C (the
very beginning temperature of dehydroxylation), the original SiO4
tetrahedral and AlO6 octahedral sheets were distorted due to the dehy-
dration and the distorted SiO4 and AlO6 units were transformed into
hydrosodalite via solid-state rearrangement.
When using R900 that was obtained by calcining rectorite at a tem-
perature beyond the temperature of the complete dehydroxylation at
700 °C as the starting material, except for a large amount of amorphous
products, a small amount of mixture of zeolites P and A was obtained.
Further increasing the calcination temperature to 1000 °C, zeolite P ac-
companied with hydrosodalite becomes the dominant product. Similar
results were obtained using R1100, R1200, and R1300 as the starting
material. These results confirm our conjecture that the chemical reactiv-
ity of metarectorite indeed varies with the thermal treatment tempera-
ture and that the maximum chemical reactivity for rectorite can be
obtained by thermal treatment at ca. 1000 °C, exactly consistent with
the results aforementioned in this article and reported in our previous
work.
As known, when fabricating A, X or Y zeolites from chemicals includ-
ing sodium silicate and aluminum sulfate, the nature and properties of
the resultant products rely heavily on the chemical composition of the
synthesis mixture, such as the molar SiO2/Al2O3 ratio, and the crystalli-
zation conditions, such as crystallization temperature and time.
Crystallization temperature strongly affects the process of nucle-
ation and crystal growth. The higher the temperature, the shorter the
crystallization (Kim and Ahn, 1991). However, when temperature is
higher than ca. 130 °C, zeolite A or X can be converted into hydrosodalite,
a more thermodynamically stable phase (Molina and Poole, 2004; Tounsi
et al., 2009).
The molar SiO2/Al2O3 ratio is another key factor determining the
type of the resultant zeolite. Zhang et al. (2013) found that when the
molar SiO2/Al2O3 ratio was 1.5–4.0, a pure phase NaX could be obtained;
when it was 0.5, a pure phase NaA could be expected; and when it was
1.0, NaA and NaX could be obtained simultaneously.
More detailed observations had been obtained by researchers who
took natural clay minerals, such as kaolin with a molar SiO2/Al2O3
ratio of ca. 2.0, as the starting material for fabricating zeolites.
Chandrasekhar and Pramada (1999, 2004) observed that the uncalcined
kaolin was partially converted into hydrosodalite, whereas metakaolins
resulting from calcination at 400, 500 and 600 °C were transformed into
hydrosodalite at a faster rate; when increasing the metakaolinization
temperature up to 700 °C, zeolite NaX was found to be the main prod-
uct. Chandrasekhar (1996) also found that the calcination temperature
of 950 °C resulted in more zeolite NaP than NaA and this was
interpreted by a high solubility of the resulting metakaolin in the sodi-
um hydroxide solution.
Mezni et al. (2011) found that when using untreated illite as the
starting material, hydrosodalite mixed with quartz and unreacted
clay was formed; whereas using alkaline fused illite as the starting ma-
terial, zeolite X was obtained. Belviso et al. (2013) found that the molar
SiO2/Al2O3 ratio as well as the presence of mineralogical impurities
(mica, illite or quartz) in the starting kaolin materials controlled the
type and the amount of zeolites formed, and they suggested that the
presence of mineralogical impurities was critical for the crystallization
and growth of zeolite X.
59
Haden et al. (1968, 1970) and Heller-Kallai and Lapides (2007) had
obtained pure phase zeolite A with a molar SiO2/Al2O3 ratio of ca. 1.8
when taking metakaolinite obtained by calcining a raw kaolin clay at
about 500–700 °C as the starting material, while adding a substantial
amount of kaolin clay calcined at above 980 °C or supplemental silica-
source into the synthesis system, they obtained zeolite X and Y, respec-
tively. Murat et al. (1992) obtained zeolite P when taking metakaolinite
as the starting material and the formation mechanism of zeolite P had
been interpreted on the basis of a radical change of the zeolite nucle-
ation process due to either the presence of soluble potassium or high sil-
ica content from muscovite (an impurity in the raw kaolinite), or from
“segregation” associated with first step of metakaolinite to mullite
transformation.
From the above analyses, we can conclude that the nature of the
zeolites from natural clay minerals relies not only on the thermal treat-
ment temperature, namely the chemical reactivity that strongly affects
the molar SiO2/Al2O3 ratio of the synthesis mixture, but also on the
presence of mineralogical or chemical impurities in the minerals.
For comparison purposes, we synthesized NaA using chemicals
(water glass and aluminum sulfate) as the silica and alumina sources
under the same crystallization conditions. The XRD pattern shown in
Fig. 9 indicates that when using chemicals as the starting materials,
the same chemical composition of the synthesis system and the same
crystallization conditions lead to NaA exclusively. So we conclude that
when taking rectorite as the starting material to fabricate zeolites, the
actual molar SiO2/Al2O3 ratio of the synthesis system is not exactly
equal to that of the mineral itself. That is to say, the chemical reactivity
of the thermal treated rectorite has much effect on the amounts of active
SiO2 and Al2O3.
As we have noted, rectorite has similar chemical composition as ka-
olinite (as seen in Table 1) and thus the formation of zeolite P encoun-
tered in this investigation can be interpreted by the distinctly different
thermal activation behaviors of rectorite. In our previous work (Wei
et al., 2010), we had shown that the contents of active SiO2 and Al2O3
in activated rectorites firstly increased and then decreased with the
increasing thermal treatment temperature, and their maxima could be
simultaneously achieved at about 900–1000 °C. Therefore, in the syn-
thesis system the SiO2/Al2O3 ratio was remained stable at ca. 2.7 (as
seen in Fig. 4 in Wei et al., 2010), higher than that of the rectorite itself
(2.0), and thus zeolite P whose SiO2/Al2O3 ratio is 2.9 is prone to be ob-
tained. For kaolinite, the maximum contents of active Al2O3 and SiO2 are
achieved at ca. 800 °C and 1000 °C, respectively, and this desynchrony
in the synthesis system leads to the formation of zeolites with different
molar SiO2/Al2O3 ratios: if the value of the molar SiO2/Al2O3 ratio is
lower than 2.0, zeolite A is obtained; if higher than 3.0, zeolite X or Y
is formed; and if between 2.0 and 3.0, zeolite P is prone to be yielded.
Fig. 9. XRD pattern of NaA synthesized using water glass and aluminum sulfate as the
starting materials.
60 H. Liu et al. / Applied Clay Science 90 (2014) 53–60
4. Conclusion
The effects of thermal treatment temperature on the physicochemi-
cal properties and chemical reactivity of the rectorite mineral and the
type of the resulting zeolites were investigated. The results showed
that after being thermally treated in the temperature range of 25–
1300 °C, the rectorite mineral experienced four successive stages: dehy-
dration at 150–300 °C, dehydroxylation at 600–700 °C, crystal collapse
at 1000 °C, and new phase formation at above 1100 °C. After being ther-
mally treated at ca. 1000 °C, the SiO4 tetrahedral units in the rectorite
mineral are distorted, while the AlO6 octahedral units are decomposed
completely and thus a maximum content of active SiO2 and Al2O3 is si-
multaneously achieved, and as a result, zeolite P can be obtained when
using R1000 as the starting material for synthesizing zeolites.
Acknowledgment
The authors gratefully acknowledge the financial support from the
Ministry of Science and Technology of China through the National
Basic Research Program (Grant 2010CB226905), the National Natural
Science Foundation of China (Grants 21276270 and 20825621), and
the Science Foundation of China University of Petroleum, Beijing
(Grant KYJJ2012-03-06).
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