Fuel 89 (2010) 3853–3859

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Fuel
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Fly ash-supported cerium triflate as an active recyclable solid acid

catalyst for Friedel–Crafts acylation reaction
Chitralekha Khatri, Deepti Jain, Ashu Rani *
Department of Pure and Applied Chemistry, University of Kota, 2-m-1, Rangbari Scheme, Rajasthan 324005, India

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

Article history: An efficient solid Lewis acid, has been synthesized by loading cerium triflate (7 wt%) on the acid activated
Received 16 January 2009 fly ash with high silica content (81%). The physico-chemical properties of synthesized fly ash-supported
Received in revised form 2 July 2010 cerium triflate catalyst (CFT) were monitored by XRD, FT-IR spectroscopy, FT-IR spectroscopy of the
Accepted 7 July 2010
ammonia adsorbed catalyst, SEM-EDAX, TEM, Flame Atomic Absorption Spectrophotometer and
Available online 14 August 2010
TG-DTA study. The increased concentration of silica surface hydroxyl groups on activated fly ash have
a major influence on the loading of cerium triflate. The catalytic activity of the catalyst CFT was tested
Keywords:
in the acylation of veratrole using acetic anhydride as the acylating agent. The proposed model structure
Solid acid
Fly ash
of CFT shows that the triflate species withdraws the electron density from the surface cerium making it
Cerium triflate electron deficit and generate Lewis acidity on the surface of fly ash as confirmed by NH3 adsorbed FT-IR
Friedel–Crafts acylation spectrum. The activity data indicate that this heterogeneous catalyst is very active, corresponding to high
conversion (88%) of veratrole to 3,4-dimethoxyacetophenone. The catalyst could be easily recovered and
reused giving similar conversion up to three reaction cycles indicating its stability under experimental
conditions. Thus fly ash-supported cerium triflate is a novel and efficient catalyst and is a promising
way of bulk utilization of waste fly ash by developing cost effective catalyst system for industrially
important Friedel–Crafts acylation reactions.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction
Fly ash, a byproduct of power generation plants, consisting of
unique, property stable, non-toxic, nonmetallic hollow micro-par-
ticles, is mainly used as cement and concrete materials [1–4]. Due
to environmental regulations, new ways of utilizing fly ash have to
be explored in order to safeguard the environment and provide
cost effective ways for its bulk utilization. Nevertheless the search
of new application of the fly ash as either catalyst or catalyst sup-
port material is still ongoing. Fly ash cenospheres (SiO2, Al2O3,
Fe2O3, CaO), with the appropriate treatment could be converted
into catalytic support material similar to that of other commercial
silica materials. Literature reports the use of fly ash as catalyst for
different oxidation [5,6], chlorination [7] and condensation [8]
reactions and as solid support in the synthesis of 2-mercaptoben-
zothiazole derivatives under microwave irradiation [9]. Fly ash
activated by thermal method has also been investigated to catalyze
reactions such as Knoevenagel condensation, ‘One-Pot’ conversions
of ketones to amides via, Beckmann rearrangement, Schiff Bases
formation, Biginelli and Hantzsch reactions [10]. In our previous
* Corresponding author. Tel.: +91 9352619059.
E-mail addresses: chitra_cool81@yahoo.com (C. Khatri), deepti_skjain@yahoo.
com (D. Jain), ashu.uok@gmail.com (A. Rani).
work fly ash is successfully used for the synthesis of highly efficient
catalysts with Brönsted acidity for benzylation and esterification
reactions [11–13].
The Friedel–Crafts acylation of aromatics is a Lewis acid cata-
lyzed reaction for synthesizing aromatic ketones as reactive inter-
mediates for the production of fine chemicals, to be used in
pharmaceuticals, cosmetics, agrochemicals, dyes, and special
chemicals [14]. Several Lewis acids (AlCl3, FeCl3, BF3, ZnCl2, TiCl4,
ZrCl4) or (polyphosphoric acid, HF) are being applied as catalyst
in homogeneous system of Friedel–Crafts acylation. For this pur-
pose, few solid acid catalysts were also employed as they can be
easily separated from the product with no residual inorganic con-
tamination [15]. The solid acids such as zeolites [16], clays [17],
modified metal oxides [18], ion-exchange resins [19], silica sup-
ported heteropoly acid [20], supported ionic liquids [21], proton
or Lewis acids on a support [22] and Nafion or Nafion like compos-
ites [23] have been reported to be good catalysts for acylation or
important organic transformations. Silica supported metal triflates
have draw attention in recent years for catalyzing various organic
reactions [24–26]. Silica supported Cu triflate [27], Bi or Sc triflate
[28] and La triflate [29] have been used efficiently for Friedel–
Crafts acylation reactions [30]. However Ce triflate is being ignored
for the purpose with only limited use for acylation of benzene
along with co-catalyst [31].

0016-2361/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2010.07.007
3854 C. Khatri et al. / Fuel 89 (2010) 3853–3859
Thus in the present study Ce triflate has been supported over
activated fly ash to prepare an innovative catalyst for acyla-
tion reaction. The catalyst possessed stable Lewis acid sites for
catalyzing acylation of veratrole by acetic anhydride to synthesize
3,4-dimethoxy acetophenone, a chemical widely used as antineo-
plastic. The work reports structural, textural and surficial proper-
ties of fly ash-supported triflate catalyst (CFT), its catalytic
performance and reuse etc. Activated fly ash rich in silica is
presented as an efficient support material to synthesize noble,
recyclable, cost effective, solid Lewis acid catalysts for industrially
important synthetic organic chemistry.
2. Experimental
2.1. Reagents
Fly ash [Class F type (SiO2 + Al2O3) > 70%], collected from Kota
Thermal Power Plant (Rajasthan, India) was used as support for
the preparation of the heterogeneous catalyst. Concentrated
H2SO4 (98%), methanol (99.99%), veratrole (98%) and acetic anhy-
dride (96%) were purchased from S.D. Fine Chem. Ltd., India and
cerium triflate (98%) from Sigma Aldrich.
2.2. Catalyst preparation
Synthesis of fly ash-supported Ce(OTf)3 catalyst (CFT) was car-
ried out by loading cerium triflate (7 wt%) on the activated fly
ash. The activation of fly ash was carried out in a stirred reactor
taking fly ash and concentrated H2SO4 acid in the ratio of 1:2 fol-
lowed by drying at 110 °C and calcination at 450 °C for 4 h. The
activated fly ash (6 g) was heated at 400 °C for 4 h prior to being
introduced in a 100 ml two-neck round bottom flask containing
solution of 0.42 g-cerium trifluoromethanesulfonate (7 wt%) dis-
solved in 100 ml methanol. The flask was equipped with a reflux
condenser and a magnetic stirrer bar. The slurry was refluxed at
110 °C for 24 h then filtered and washed with cold methanol to re-
move unloaded triflate from the fly ash surface. The resulting solid
product (CFT) was further dried at 110 °C for 24 h and calcined at
150 °C for 4 h under static condition.
2.3. Catalyst characterization
Powder X-ray diffraction studies were carried out by using
(Philips X’pert) analytical diffractometer with monochromatic
CuKa radiation (k = 1.54056 Å) in a 2h range of 0–80°. The FT-IR
spectrum of the synthesized material was recorded using IR Pres-
tige-21, Shimadzu in DRS by mixing the sample with KBr in 1:20
weight ratio in the range 400–4000 cm1 with a resolution of
4 cm1. The chemical components present in the fly ash sample
were analyzed by atomic absorption spectrophotometer
(AA-6300, Shimadzu). The detailed imaging information about
the morphology and surface texture of the sample was provided
Scheme 1. Acylation of veratrole with acetic anhydride over CFT.
by SEM-EDAX (Philips XL30 ESEM TMP). The loading of cerium tri-
flate on fly ash particles was confirmed by TEM analysis (Tecnai 20
G2 (FEI make), Resolution: Line-1.4 A, Point 2.04 A).
2.4. Catalytic activity of (CFT): acylation of veratrole with acetic
anhydride
The acylation of veratrole with acetic anhydride (Scheme 1) was
performed in liquid phase batch reactor consisting of 25 ml round
bottom flask with condenser in a constant temperature oil bath
with magnetic stirring. A mixture of veratrole (1.38 g) and acetic
anhydride (2.04 g) was taken in round bottom flask. The catalyst
(substrate to catalyst ratio = 10), activated at 150 °C for 2 h was
added in the reaction mixture. The reaction was carried out at dif-
ferent molar ratio of substrate and acetic anhydride and at differ-
ent temperatures in the range of 90–150 °C for time ranging
from 2 min to 4 h. After completion of the reaction the catalyst
was filtered and the product was analyzed by Gas Chromatograph
(Dani Master GC) having a flame ionization detector and HP-5 cap-
illary column of 30 m length and 0.25 mm diameter, programmed
oven temperature of 50–280 °C and N2 (1.5 ml/min) as a carrier
gas. The conversion of veratrole was calculated by using weight
percent method [12].
Conversion (wt%) = 100  [Initial wt%  Final wt%]/Initial wt%.
2.5. Catalyst regeneration
The spent catalyst was washed with acetone, dried in oven at
110 °C for 12 h followed by calcination at 150 °C for 2 h and reused
for next reaction cycle under similar reaction conditions as earlier.
3. Result
3.1. Catalyst characterization
After chemical activation the silica content in fly ash is greatly
increased from 54% to 81%, which is evident from SEM-EDAX
Fig. 1. SEM-EDAX of activated fly ash.
 C. Khatri et al. / Fuel 89 (2010) 3853–3859
Fig. 2. X-ray diffraction pattern of (a) pure fly ash (FA), (b) activated fly ash (CFA)
and (c) fly ash-supported cerium triflate catalyst (CFT).
spectrum of CFA as shown in Fig. 1. Silica content of as received fly
ash (FA) was analyzed by AAS.
X-ray diffraction patterns of pure fly ash, FA (Fig. 2A), activated
fly ash, CFA (Fig. 2B) and supported cerium triflate catalyst CFT
(Fig. 2C) show the presence of crystalline and amorphous phases.
The amorphous phase of fly ash is increased by chemical activation
which results in decreased crystallite size up to 12 nm [12]. The
activation of fly ash prior to the loading of cerium triflate removes
some of the crystalline components present in the fly ash sample
thus lowering the crystallinity and increases the amorphous con-
tent suitable for proper loading. In CFT (Fig. 2C) the loading of cer-
ium triflate on previously activated fly ash has increased the
crystallinity and crystallite size from 12 to 80 nm.
The FT-IR spectra of pure fly ash (FA) and activated fly ash (CFA)
evidence a broad band in –OH region (3800–2700 cm1), which is
attributed to surface –OH groups, particularly of silica and the
water molecules adsorbed on the surface (Fig. 3A and B). The
broadness of the band reflects strong hydrogen bonding between
3855
(a)
(b) 3495
%T
3016 1097
(c) 3348
1074
3541
1402
3163
3500 3000 2500 2000 1500 1000 500
-1
cm
Fig. 3. FT-IR spectra of (a) pure fly ash (FA), (b) activated fly ash catalyst (AFAC) and
(c) fly ash-supported cerium triflate catalyst (CFT).
the hydroxyl groups as reported earlier [11,12]. The increased
amorphous silica in the activated fly ash can be characterized by
an intense band in the range 1000–1300 cm1, corresponding to
the valence vibrations of the silicate oxygen skeleton. The main
absorption band of the valence oscillations of the groups Si–O–Si
in quartz appears with a main absorption maximum at
1100 cm1 [12]. The FT-IR spectrum of CFT (Fig. 3C) shows a very
intense peak at 1410 cm1 of asymmetric stretching frequency of
S@O bond i.e., mS@O), which is attributed to the sulfonate group
[32] of cerium triflate loaded on the activated fly ash. A small
shoulder present at 1000 cm1 is due to stretching frequency
(mas) of C–F bond of triflate.
FT-IR spectrum (Fig. 4) of the ammonia adsorbed sample
(after evacuation at 150 °C for 30 min.) indicates the presence
of significant amount of Lewis acid sites, as inferred from the
bands at 1603 cm1 (dasym of NH3 adsorbed on Lewis sites)
and 1198 cm1 (dsym of NH3 adsorbed on Lewis sites). However,
the presence of Brønsted acid sites which are characterized by
the bands in the range of 1460–1490 cm1 for bending modes
of NHþ 4 formed by protonation of ammonia on Brønsted sites
were not observed in the sample. The cerium triflate combines
Fig. 4. FT-IR spectrum of ammonia adsorbed CFT after evacuation at 150 °C.
3856 C. Khatri et al. / Fuel 89 (2010) 3853–3859
Scheme 2. The model of the active site in fly ash-supported cerium triflate catalyst
(CFT).
with –OH groups of the silica present in the activated fly ash and
retain the Lewis acidity (Scheme 2).
TEM images of cerium triflet loaded and unloaded spherical alu-
minosilicate cenospheres of fly ash are given in Fig. 5(A) and (B).
Dark crystalline spots on the spherical surface of aluminosilicate
(Fig. 5B) are probably the loaded cerium triflet.
Fig. 5. TEM of aluminosilicate cenospheres of fly ash (a) unloaded and (b) cerium
triflet loaded.
Fig. 6. TGA-DTA of fly ash-supported cerium triflate catalyst.
Thermogravimetric analysis of the prepared catalyst results into
total 70% weight loss from 50 to 800 °C. The endotherm centered at
90 °C, accompanied by a weight loss corresponds to the loss of
water and solvent (methanol). The curve presented in Fig. 6, shows
major weight loss of 15 wt% between 200 and 400 °C due to ther-
mal decomposition of triflate species loaded on the surface of fly
ash as decomposition temperature of triflate is 450 °C [33]. After
450 °C weight loss is attributed due to decomposition of sulfur spe-
cies present in the catalyst. In the present case, the reaction of
highly dispersed Lewis acid with silica surface silanol groups,
hydrolyze the Ce(OTf) bond to form CeO and triflic acid (CF3SO3H)
which causes the thermal decomposition of triflate groups [33,34].
3.2. Catalytic activity
Fly ash-supported cerium triflate shows high catalytic activity
for acylation of veratrole with acetic anhydride resulting 88% con-
version to 3,4-dimethoxyacetophenone, where as FA and CFA due
to absence of Lewis acidity on the surface do not catalyze the acyl-
ation. The reaction conditions such as reaction temperature, time,
molar ratio of reactants and substrate to catalyst ratio were opti-
mized in order to achieve maximum conversion of veratrole.
Optimization of reaction temperature to give maximum conver-
sion of veratrole was studied at temperature ranging from 90 to
Fig. 7. Variation of conversion (%) with temperature after 1 h.
 C. Khatri et al. / Fuel 89 (2010) 3853–3859
Fig. 8. Variation of conversion (%) with time at 130 °C.
Fig. 9. FT-IR spectra of (i) fresh CFT catalyst and (ii) regenerated CFT catalyst.
150 °C for 1 h taking veratrole to acetic anhydride molar ratio of
1:2 with substrate/catalyst ratio of 10. The results showed that
Scheme 3. Mechanistic pathway of acylation of veratrole over fly ash-supported cerium triflate catalyst (CFT).
3857
the conversion of veratrole gradually increases with increase in
temperature from 90 to 130 °C. The maximum conversion (88%)
was obtained at 130 °C, which decreased (83%) at higher reaction
temperature (150 °C) as shown in Fig. 7.
The optimization of reaction time required to achieve maxi-
mum conversion was carried out at 130 °C taking veratrole to ace-
tic anhydride molar ratio of 1:2 with substrate/catalyst ratio of 10
for different reaction times ranging from 2 min to 4 h as shown in
Fig. 8. It was found that in the first 1 h of the reaction period the
conversion increases linearly up to 88%, which remained constant
till 4 h.
The effect of veratrole to acetic anhydride molar ratio on con-
version was also monitored at different molar ratios ranging from
1:1 to 1:5 at temperature 130 °C, time 1 h and substrate to catalyst
ratio 10. The conversion was found maximum at 1:2 M ratio with
88% conversion, which further decreased up to 63% on increasing
the molar ratio up to 1:5.
The substrate to catalyst weight ratio was varied from 5 to 20.
The maximum 88% conversion was obtained at weight ratio 10,
which remained constant on increasing the weight ratio up to 5.
3.3. Catalyst regeneration
The used CFT catalyst from the reaction mixture was filtered,
washed with acetone and regenerated by heating at 150 °C for
1 h. The regenerated catalyst was used for the next reaction cy-
cles under similar reaction conditions to first cycle. The catalyst
was found efficient up to four cycles giving conversion in the
range of 88–81%. The FT-IR spectra of regenerated catalyst after
second cycle in Fig. 9 shows similarity with that of fresh cata-
lyst indicating the presence of triflate species and with no
change in chemical composition of catalyst surface. The signifi-
cant decrease in conversion after fourth cycle is due to the
deposition of carbonaceous material on the external surface of
the used catalyst that may block the active sites present on
the catalyst [11].
3858 C. Khatri et al. / Fuel 89 (2010) 3853–3859
4. Discussion
Fly ash due to the presence of sufficient crystalline phases
(quartz, mullite and calcite) possessed crystallite size up to
33 nm, which after acid activation decreased to 12 nm in CFA.
Treatment with H2SO4 dissolved some of the crystalline phases
resulting in decrease in crystallite size [12]. After cerium triflate
loading on CFA, the crystallite size of CFT was increased up to
80 nm due to presence of highly crystalline cerium with crystallite
size in the range 38–60 nm [35]. The chemical activation increases
the silica content in the activated fly ash, which possesses signifi-
cantly higher surface hydroxyl groups and helps in loading of the
triflate species. The interaction of triflates with surface –OH groups
of silica binds triflates on the silica surface without diminishing its
Lewis acidity [33]. It is well reported that the silica supported tri-
flates as solid acid catalysts mainly contain Lewis acidity, origi-
nated from the loaded metal triflates [33,36,37]. Therefore, from
NH3 adsorbed FT-IR study it is confirmed that the increased Si–
OH in the activated fly ash helps in loading of the triflate species
only but not generate acidity.
The TGA of fly ash-supported cerium triflate catalyst (CFT) was
carried out to determine the thermal stability of the catalyst The
decomposition of CFT at lower temperature (below 400 °C) may
be ascribed to the decomposition of triflate species, which is
loaded on the surface by reaction of triflate ion and surface hydro-
xyl groups as in case of silica supported Zn triflate and Cu triflate
[33,34]. In the present case, the reaction of highly dispersed Lewis
acid with silica surface silanol groups hydrolyzes the Ce(OTf) bond
to form CeO and triflic acid which causes the thermal decomposi-
tion of triflate groups.
The catalytic activity of CFT as determined by acylation of verat-
role with acetic anhydride showed maximum conversion (88%) at
130 °C for 1 h with veratrole to acetic anhydride molar ratio 1:2
and substrate/catalyst ratio of 10. At temperatures above the boil-
ing temperature of acetic anhydride (140 °C), conversion was de-
creased due to decrease in the contact time of acetic anhydride
with veratrole, as former mostly remained in the vapour phase
during the reaction. The catalyst was efficiently reused for the next
three cycles which indicates that the acid sites are not lixiviated in
the reaction mixture. The decrease in conversion after the third cy-
cle is attributed to the blocking of active sites by the deposition of
organic residues of reactants and product. The proposed model
(Scheme 2) of the CFT catalyst shows lewis acid site on cerium me-
tal attached to activated fly ash surface. The triflate species with-
draw the electronic density from the surface metal atom making
it electron deficit and generate Lewis acidity. The Lewis sites on
CFT catalyst are able to generate acylium ion intermediate from
acetic anhydride, which attack on the p-electron system of verat-
role. The possible pathway for the production of 3,4-dimethoxy-
acetophenone in the acylation of veratrole with acetic anhydride
catalyzed by CFT is shown in Scheme 3.
5. Conclusion
The chemical activation of fly ash by acid leaching results in in-
creased silica content and surface hydroxyl content, giving a better
solid support for loading of conventional Lewis acid. CFT catalyst
possessed significant amount of Lewis acidity comparable with
other silica supported triflates. The catalyst is recyclable suggest-
ing stability of the active sites in the reaction system. The novelty
of the present work is the utilization of the abundant residue of fly
ash as solid support for the synthesis of highly selective solid Lewis
acid catalyst (CFT), overcoming the problems of conventional
homogeneous Lewis acids. The industrial scale use of the catalyst
will not only give an effective partial solution of bulk utilization
of waste fly ash but will also provide a low cost solvent free pro-
duction process.
Acknowledgements
The authors are thankful to Vice-Chancellor Prof. B.M. Sharma
for providing laboratory and analytical facilities. Analytical support
was provided by Dr. Manish Kumar Mishra from Dharmsinh Desai
University, Nadiad, Gujarat and at Sardar Patel University Vallabh
Vidhyanagar Gujarat. TEM analysis was conducted by Dr. N.P. Lalla
at DAU-CAE, Indore. The financial support was provided by Univer-
sity grants Commission and Fly Ash Mission, Department of Sci-
ence and Technology, Ministry of Science and Technology, Govt.
of India, New Delhi, India.
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