Selective Dehydration of Glycerol to Acrolein: Development of

Ecient and Robust Solid Acid Catalyst MUICaT5

Ganapati D. Yadav,* Rajesh V. Sharma, and Suraj O. Katole
Department of Chemical Engineering, Institute of Chemical Technology, Nathalal Parekh Marg, Matunga, Mumbai, 400019 India
*S Supporting Information
ABSTRACT: Valorization of bioglycerol to industrially relevant products has been targeted worldwide to make biodiesel
production cost competitive. Among several bulk chemicals derived from glycerol, synthesis of acrolein/acrylic acid is one route
which is favored for which several catalysts and processes have been proposed in the literature. The present work reports on gas
phase dehydration of glycerol to acrolein by using several catalysts and supports. Dodecatungstophosphoric acid supported
(DTP) on hexagonal mesoporous silica (HMS) showed promise. It was observed that HMS acted as a better support for acrolein
selectivity as compared to K-10 clay and octahedral molecular sieves (OMS). 20% w/w DTP/HMS catalyst resulted in 94% of
glycerol conversion and 80% of acrolein selectivity at 225 C. However, it suered with severe deactivation due to coke
deposition. Various techniques such as NH
3
-TPD, BET-surface area, SEM image and EDX analysis were used for catalyst
deactivation study. Then a new robust catalyst, MUICaT-5, was then synthesized by using deactivation data of 20% w/w DTP/
HMS catalyst. MUICaT-5 catalyst gave 86% of glycerol conversion and 60% of acrolein selectivity. The stability and activity of
the MUICaT-5 catalyst were evaluated by time on stream (TOS) studies up to 100 h at 275 C. After regeneration, reusability of
MUICaT-5 catalyst was carried out up to six times, without aecting acrolein selectivity and glycerol conversion. Catalyst
reusability was also supported by characterization using NH
3
-TPD, BET-surface area measurements, SEM, and EDX techniques.
1. INTRODUCTION
The spectacular rise in demand for clean fuels and chemicals
from renewable resources has led to intensive research to
develop industrial applications of biomass of all sorts. A lot of
emphasis on biodiesel production is a result of such demand.
1
Glycerol is a main coproduct of biodiesel production with 10%
w/w mass. Glycerol is a very promising low-cost feedstock for
producing a range of value-added specialty and ne
chemicals.
13
The chemistry of glycerol shows that with its
three hydroxyl groups it can undergo dehydration, reforming,
oxidation, hydrogenolysis, etherication, and esterication
reactions to produce several commodity chemicals.
46
Use of
catalysis in these processes will be helpful in developing
sustainable chemical production processes. Dehydration of
glycerol produces two important bulk chemicals, namely, 3-
hydroxypropionaldehyde and acrolein. Catalytic conversion of
glycerol could oer a cost-eective and sustainable alternative
route for the present acrolein production technology which is
based on petroleum-derived propylene. Acrolein is an
important and versatile chemical. It nds direct applications
in a spectrum of areas ranging from medicine to water
treatment, petroleum industry, and formulations industry as
biocide. For instance, acrolein is used for the synthesis of
agrochemicals like methionine, fragrances, and dyes. It also acts
act as a precursor for the production of acrylic acid, acrylic acid
esters, super absorber polymers, and detergents.
2,79
Acrolein is commercially produced by gas phase oxidation of
propylene in the presence of BiMo mixed oxide catalyst. The
second route is the oxidation of propane to acrolein/acrylic
acid.
1012
It is a vapor phase oxidation reaction using
molybdenum and vanadium based catalysts.
13
The production
of acrolein by dehydration of glycerol is not yet commercial-
ized. Various reports are available for glycerol dehydration
reaction.
Solid acid catalysts such as sulfates, phosphates, and zeolites
have been used either in gaseous or liquid phase reactions.
1417
Acidic ZSM-5 or HY zeolites give 75% of acrolein yield with
complete conversion of glycerol at 250340 C, but they suer
from a sharp deactivation. Dehydration of glycerol is also
reported in supercritical water (T > 374 C, P > 221 atm) with
liquid acid H
2
SO
4
to get acrolein selectivity of 84% at 40% of
glycerol conversion or with zinc sulfate salt as catalyst with 75%
of acrolein selectivity at 50% of glycerol conversion.
17
Acrolein
selectivity up to 80% at 90% of conversion was reported with
H
2
SO
4
as a catalyst at 400 C,
18
which is polluting. Sulfated
zirconia
19
and Nb
2
O
5
20
were also used, but these catalysts also
gave poor results.
Keggin type heteropoly acid (HPA) catalysts are strong
Bronsted acids.
21
Supported HPAs have excellent superacidic
prpoerties.
22,23
Clays and hexagonal mesporous silica (HMS)
are some of the most widely used supports for a variety of
catalysts including HPAs.
23,24
HMS possesses high surface area
vis-a -vis clays and regular hexagonal porous structure and has
been used in a number of processes.
25
Our lab demonstrated
that clay supported HPAs such as H
3
PW
12
O
40
(dodecatung-
stophoshoric acids, DTP)
23
and its partially substituted
nanoform Cs
2.5
H
0.5
PW
12
O
40
(Cs-DTP)
24
are superior catalysts
in several acid catalyzed reactions including dehydration,
alkylation, acylation, etc. DTP supported on HMS is a very
Received: April 7, 2013
Revised: June 28, 2013
Accepted: June 28, 2013
Published: June 28, 2013
Article
pubs.acs.org/IECR
2013 American Chemical Society 10133 dx.doi.org/10.1021/ie401098n | Ind. Eng. Chem. Res. 2013, 52, 1013310144
good catalyst.
26
A few researchers have reported that supported
HPAs are eective for the glycerol dehydration reaction
27
and
gives better selectivity to acrolein and these catalysts included
silica-supported silicotungstic acid,
28,29
activated carbon-sup-
ported silicotungstic acids,
30
modied molecular sieve zeolite
(HY > H > Mordenite > SBA-15 > ZSM-23),
31
and zirconium
and niobium mixed oxides.
32
Dierent silica-, alumina-, and
aluminosilicate-supported heteropolyacid catalysts were pre-
pared by Atia et al.
33
using phosphomolybdic acid,
phosphotungstic acid, silicotungstic acid, and ammonium
phosphomolybdate as precursors. Alumina was found to be
superior to silica as support with regard to catalyst activity and
selectivity. In their studies, tungsten based heteropolyacids
showed outstanding performance and stability whereas
molybdenum-containing HPAs tend to decompose partly
close to 400 C into molybdates and MoO
3
whereas
tungsten-containing catalysts were stable. This suggested that
tungsten-based materials are interesting acid catalysts for the
dehydration of glycerol in the gas phase.
33
Metal oxide
supported HPAs are stable up to 400 C without any
decomposition
33,34
and in certain metal oxide supported
catalysts heteropolyacids are shown to be stable even at higher
temperature; for instance, zirconia supported HPAs are stable
at 600 C and beyond.
35
The most of the heteropoly acid based
glycerol dehydration reactions were reported at 270325
C.
2735
HMS has more silanol (SiOH) groups on the surface which
makes the support more hydrophilic, which can increase the
interaction between glycerol hydroxyl group and support
hydroxyl group and may increase the selectivity of the acrolein.
Hence, the principal objectives of the present work was based
on preparation of HMS based catalysts and evaluation of their
eects on glycerol dehydration reaction. The two dierent set
of catalysts were prepared: (i) heteropoly acid supported on
HMS, and (ii) other solid acids supported on HMS. The
sencondary objective of the present work was to screen a large
number of catalysts (heteropoly acid and solid acid supported
on HMS) and arrive at optimum conditions for dehydration of
glycerol to acrolein. If the chosen catalyst was deactivated,
either due to use of severe conditions or due to any other
process parameter inuence, then it could be the basis for
developing a new catalyst. This work also discusses a systematic
evaluation of the various catalysts including the characterization
of the most active, used and reused catalyst to understand the
process parameters which will help in further research. In the
current investigation, a new catalytic material (MUICaT-5)
based on HMS as support has been prepared, and used as solid
acid for the dehydration of glycerol to acrolein in vapor phase.
This catalyst has good recyclability and delineates the novelties
of the process. MUICaT is an acronym for Mumbai University
Institute of Chemical Technology by which this institute was
formerly known (now it is a separate deemed university called
ICT). The catalyst activity was evaluated using 20% w/w
glycerol solutions. The purpose was to reduce reactor size and
possible scale-up for commercial use of the process to improve
economics.
2. EXPERIMENTAL SECTION
2.1. Materials. The following chemicals were procured
from rms of repute and used without further purication:
glycerol (LR), dodecatungstophosphoric acid (AR), methanol
(s.d. Fine Chem., Mumbai, India), aluminum nitrate (s.d. Fine
Chem., Mumbai, India), tungstic acid (s.d. Fine Chem.,
Mumbai, India), ethanol (s.d. Fine Chem., Mumbai, India),
zirconium oxychloride (LR) (s.d. Fine Chem., Mumbai, India),
tetraethyl orthosilicate (TEOS) (Fluka, Germany), hexadecyl
amine (Spectrochem Ltd., Mumbai, India).
2.2. Catalyst Preparation. Hexagonal mesoporous silica
(HMS) was synthesized by neutral S
o
I
o
templating route.
25a,26a
The process is briey described here. The synthesis mechanism
is based on hydrogen bonding and self-assembly between
neutral primary amine surfactants (S
0
) and neutral inorganic
precursor (I
0
). In a typical preparation, tetraethyl orthosilicate
(TEOS) was added under vigorous stirring to a solution of
dodecyl amine (DDA) in ethanol and deionised water to obtain
a gel of composition 1.0 TEOS/0.27 DDA/9.09 EtOH/50.8
H
2
O. After aging for 18 h at ambient temperature, template
silica with short-range hexagonal morphology was recovered.
Template removal was achieved by calcination at 550 C in the
air. 20% w/w dodecatnugstophosphoric acid (DTP)/HMS was
prepared by incipient wetness technique, as descried earlier by
us,
27
for which 2 g of dry dodecatungsto phosphoric acid was
weighed accurately. It was dissolved in 8 mL of methanol. The
solution was added in small aliquots of 1 mL each time to the
silica molecular sieve with constant stirring with a glass rod or
kneading it properly. The solution was added at time intervals
of 2 min. Initially on the addition of the DTP solution, HMS
was in powdery form but in complete addition it formed a
paste. The paste on further kneading for 10 min resulted in a
free-owing powder. The performed catalyst was dried at 120
C for removal of water and other occluded volatiles and
subsequently calcined at 300 C temperature for 3 h. 20% w/w
DTP/HMS,
26
20% w/w DTP/K-10,
23
20% Cs-DTP/K-10,
24
and 20% w/w DTP/OMS (octahedral molecular sieves) were
prepared as per the methods reported in literature.
36
20% w/w
NiO/HMS, 20% w/w CoO/HMS, 20% w/w CuO/HMS, and
20% w/w Fe
2
O
3
/HMS were prepared by adding nitrate
solution of respective metal precursor to HMS by wet incipient
technique and further calcination was done at 650 C for 3 h.
MUICaT-5 was synthesized as follows: 2.39 g of zirconium
oxychloride and 0.11 g of aluminum nitrate were dissolved in
aqueous solution and added to 5 g of precalcined HMS by
incipient wetness technique. After addition, the solid was dried
in an oven at 110 C for 3 h. The ammonia gas was passed
through dried material for 2 h, and then material was washed
with deionized water until a neutral ltrate which was detected
by phenolphthalein, and the absence of chlorine ion is detected
by silver nitrate tests. A material balance on chlorine before and
after precipitation was done, and the washing showed no
retention of chlorine on the solid. It was then dried in an oven
for 24 h at 110 C. The generation of acidic centers into this
material was made possible by grinding tungstic acid (0.1078 g)
with 0.9 g of zirconium hydroxide and aluminum hydroxide on
HMS followed by hydrothermal treatment and then it was
calcined at 750 C for 3 h.
37
The various HMS based solid acid
catalysts such as UDCaT-1,
38
UDCaT-4,
39
and UDCaT-6
40
were prepared by the reported methods from our laboratory.
2.3. Characterization of Catalyst. 2.3.1. NH
3
-TPD. Acidic
sites of the catalyst were determined with temperature
programmed desorption (TPD) analysis by using Autochem
II 2910 (Micromeritics, USA) with ammonia as probe
molecule. A quantity of 30 mg of the catalyst was taken in a
quartz tube and degassed up to 300 C under the ow of
nitrogen. Then, ammonia gas was passed for 30 min to adsorb
the ammonia over the surface of the catalysts at room
temperature. Physisorbed gas was removed by passing inert
Industrial & Engineering Chemistry Research Article
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nitrogen at room temperature. Chemisorbed ammonia was
desorbed by using temperature programmed desorption and
detected by TCD.
2.3.2. Surface Area, Pore Volume, and Pore Diameter
Analysis. The surface properties of fresh and used catalysts
were measured by the BrunauerEmmettTeller (BET)
method using ASAP 2010 (Micromeritics, USA) instrument.
The catalyst samples were degassed under vacuum at 200 C
for 4 h. The measurements were made using N
2
gas as the
adsorbent and with a multipoint method. Isotherms were
measured at liquid nitrogen temperature.
2.3.3. SEM and EDX Analysis. External surface morphology
of the catalyst sample was captured by scanning electron
microscope (SEM) (Camera SU 30 microscope, JEOL, Japan).
The dried samples were mounted on specimen studs and
sputter coated with a thin lm of gold to prevent charring. The
gold coated surface was then scanned at various magnications
by using scanning electron microscope. Elemental analysis of
fresh, used and regenerated catalysts was determined by energy
dispersive X-ray spectroscopy (EDXS) (KEVEX X-ray
spectrometer JED-2300, JEOL, Japan). However, to avoid the
error in quantication of bulk composition, X-ray beam was
focused at three spot in the catalyst, and the average value of
each metal is presented.
2.4. Apparatus and Reaction Procedure. Vapor phase
dehydration of glycerol was carried out in a xed bed stainless
steel reactor (17.2 mm diameter (ID) and 250 mm height;
Chemito). The bed was packed with a known quantity of dry
catalyst. Inert glass bead packing was placed above the catalyst
bed. The stainless steel reactor was equipped with liquid feed
pump (HPLC grade, Knauer, USA), preheater, gas ow
arrangement with mass ow controller and condenser. The
role of N
2
in the feed is to carry out the reaction in inert
atmosphere, and also to avoid the further decomposition of
acrolein to other byproducts by decreasing the residence time
of acrolein in the catalyst. Under standard reaction condition:
the temperature of the bed was maintained at 225 1 C of
accuracy. The ow rate of the nitrogen gas was measured and
controlled by mass ow controllers at 10.2 mL/h. WHSV was
kept at 10.74 h
1
with the residence time of 35 s. Reaction
samples were collected from the bottom of the condenser. The
catalyst was activated under the ow of nitrogen for 2 h at the
reaction temperature.
2.5. Method of Analysis. Analysis of reaction mixture was
performed by GC on a Chemito 1000 model. A 30 m 0.15
mm internal diameter capillary column (BPX-50) was used for
analysis in conjunction with a ame ionization detector. The
quantication of collected data was done through a calibration
procedure by using synthetic mixtures. Dodecane was used as
an internal standard to correct the volumetric changes during
the reaction by taking the ratio of glycerol and dodecane
concentrations. The amount of acrolein and hydroxyacetone
obtained was calculated through calibration curve and product
yields were calculated. Product selectivity was calculated by the
eq 3 as reported by Gu et al.
41
The gaseous byproduct and coke
deposited on the catalyst were not analyzed quantitatively and
its percentage was mentioned as others by keeping an account
of the material balance. The products were conrmed by GC-
MS and authentic samples. Commonly used terms for
calculation of conversion, product yield, product selectivity
and weight hourly space velocity (WHSV) are as follows:
=

glycerol conversion, %
glycerol conc. in feed glycerol conc. in product
glycerol conc. in feed
100
(1)
=
product yield, mol %
mol of carbon in defined product
mol of carbon in glycerol in feed
100
(2)
= product selectivity, mol %
product yield
glycerol conversion
100
(3)
=
F
W
WHSV
(4)
Scheme 1. Dehydration of Glycerol over Solid Acid
Industrial & Engineering Chemistry Research Article
dx.doi.org/10.1021/ie401098n | Ind. Eng. Chem. Res. 2013, 52, 1013310144 10135
where WHSV = Weight hourly space velocity, h
1
, F = Total
mass ow of liquid feed (glycerol solution), g/h, and W =
Weight of catalyst, g.
3. RESULTS AND DISCUSSION
Scheme 1 shows the mechanism for the glycerol dehydration
reaction. Glycerol dehydration over a heterogeneous catalyst
follows two parallel paths a and b leading to three products
which are all interesting, which are temperature dependent
reactions. By dehydration path a it produces 3-hydroxypropanal
(A
1
) which is further dehydrated to give acrolein (A
2
) which is
the desired product. There could be break-up of A
1
by path aa
to acetaldehyde (A
11
) and formaldehyde (A
12
). On the
contrary, path b leads hydroxyacetone (B
2
), which is also
industrially important. It has been reported that hydroxyace-
tone is obtained at high temperature, and also acrolein
undergoes cracking and produces acetaldehyde and form-
aldehyde at higher temperature.
42
Preliminary analysis had
suggested that type of acidity, its distribution and temperature
would play dominant roles in selectivity to acrolein.
3.1. Catalyst Charecterizations of 20%(w/w) DTP
Supported on K10, HMS, and OMS. The three dierent
support K10, HMS and OMS were used to incorporate
dodecatungstophosphoric acid. The total acidity measurement
of K10 and HMS were carried using NH
3
-TPD were found to
0.139 mmol/g and 0.021 mmol/g, respectevely while basicity
measurement of OMS carried out by CO
2
-TPD was measured
to be 4.76 mmol/g. 20% (w/w) DTP/K10 and 20% (w/w)
DTP/HMS are completely characterized again during this work
for both virgin and used catalysts by NH
3
-TPD, FTIR, XRD,
SEM, and BET surface area, and some characterization was
published by our group.
23,24,39
20% (w/w) DTP/OMS was
characterized similarly. Only a few salient features are reported
here. The acidity of 20% w/w DTP/K-10 catalyst was measured
by NH
3
-TPD and found to be 0.423 mmol/g. The IR spectrum
of 20% (w/w) DTP/K10, 20% (w/w) DTP/HMS and 20%
(w/w) DTP/OMS catalyst exhibits bands at 3450, 1652, 1092,
990.7, 893, 817, and 466 cm
1
. The XRD analysis conrmed
that 20% w/w DTP/K-10 is crystalline in nature. The BET
surface area of 20% w/w DTP/K-10 was found to be 135 m
2
/g.
The preparation of 20% w/w DTP/HMS and its application is
also reported by our group.
26
The acidity of 20% w/w DTP/
HMS was measured by NH
3
-TPD and found to be 0.130
mmol/g. 20% w/w DTP/HMS was characterized by XRD and
no crystalline phase was detected which indicates uniform
distribution of DTP in HMS. Hence, these materials are
completely amorphous in nature. The BET surface area of 20%
w/w DTP/HMS was found to be 299.6 m
2
/g and is a type-IV
isotherm which indicates mesoporosity is retained after DTP
loading. The OMS-2 catalyst has a one-dimensional tunnel
structure formed by 2 2 edge shared MnO
6
octahedral chains.
X-ray diraction patterns show d-spacing values which match
with the reported data of OMS-2 and the corresponding (h k l)
values are (1 0 1), (0 0 2), (3 0 1), (2 1 1), (3 1 0), (1 1 4), and
(6 0 0) at 2q values of 12.7, 18.0, 28.7, 37.4, 41.8, 50.0, and
55.3. When DTP is dispersed in OMS-2, there is a linear
decrease in surface area from 69.4 to 42.4 m
2
/g.
Keggin type heteropoly acid (HPA) catalysts are strong
Bronsted acids. HMS is neutral. The active species in DTP/
HMS are Bronsted acids arising from the doedcatungstophos-
phoric acid as reported by us earlier
26
and Bardin et al.
43
There
are abundant silanol groups (#SiOH) on the surface of
mesoporous silica owing to its amorphous wall structure. With
these reactive silanol groups, one can eectively immobilize
organic functional groups onto a silica surface through either
covalent bonding or hydrogen bonding.
44
On silica, only H-
bond formation occurs indicating a rather weak acidity of the
silanol groups, quantitatively characterized by pK
a
= 7.
45
Hexagonal mesoporous silica is neutral and does not create
acidity by steam generated in situ during dehydration.
particularly at the reaction temperature of 225 C.
3.2. Ecacies of Dierent Support and Catalyst
Screening. 20% w/w DTP was loaded on dierent support
like K-10 (acidic), HMS (neutral)
8
and OMS (basic) to
evaluate the eect of support on glycerol conversion and
acrolein selectivity. Although, all the catalyst had the same 20%
w/w DTP loading, it was observed that neutral support (HMS)
showed better selectivity for acrolein as compared with other
supports (Table 1). The increase in selectivity also can be due
the presence of free hydoxy group which make the catalyst
more hydrophilic in nature. Therefore, various HMS supported
catalysts such as 20% w/w CoO/HMS, 20% w/w CuO/HMS,
20% w/w NiO/HMS, 20% w/w Fe
2
O
3
/HMS, 20% w/w
CsDTP/HMS, and 20% w/w DTP/HMS were prepared and
screened for vapor phase glycerol dehydration reaction (see
Figure 1).Recently, the redox active metals such as copper, iron
and nickel were used in the catalyst composition for
dehydration of glycerol to acrolein.
16,41,46
Therefore, copper,
iron, nickel and cobalt were supported on HMS and their
activity for acrolein preparation was evaluated. However, it was
Table 1. Ecacy of Dierent Support: 20% (w/w) Glycerol
Solution, 1.0 g of Catalyst Weight, 225 C, 1.5 L/h of N
2
Flow Rate, 10.2 mL/h of Glycerol Flow Rate, 10.74 h
1
of
WHSV, and 4 h
% selectivity
catalyst
% conversion
(glycerol) acrolein hydroxyacetone others
a
20% w/w
DTP/K-10
89 50 10 40
20% w/w
DTP/HMS
94 80 9 11
20% w/w
DTP/OMS
62 45 14 41
a
Acetaldehyde, propionaldehyde, acetone, and allyl alcohol.
Figure 1. Ecacy of various catalysts: 20% (w/w) glycerol solution,
1.0 g of catalyst weight, 225 C, 1.5 L/h of N
2
ow rate, 10.2 mL/h of
feed ow rate, and 10.74 h
1
of WHSV, 4 h.
Industrial & Engineering Chemistry Research Article
dx.doi.org/10.1021/ie401098n | Ind. Eng. Chem. Res. 2013, 52, 1013310144 10136
observed that HMS suppored copper, iron, nickel and cobalt
catalysts showed poor acrolein selectivity as compared to
heteropoly acid based catalysts such as 20% w/w CsDTP/HMS
and 20% w/w DTP/HMS, which can be due to redox
properties of these metals.
Typical reaction condition were as follows: 1.0 g of catalyst
loading, 225 C of reactor bed temperature, 225 C of
preheator temperature, 20% (w/w) glycerol solution, 10.2 mL/
h of feed ow rate (glycerol solution), 1.5 lit/h of N
2
ow rate,
4 h reaction duration and 10.74 h
1
of WHSV. 20% w/w DTP/
HMS was found a better catalyst as compared to other catalysts.
The increase in activity can be due to the synergistic eect of
DTP and hydrophilic nature of HMS support which has high
surface area and mesoporosity. Hence, further, reactions were
carried out by using 20% w/w DTP/HMS catalyst.
3.3. Eect of Temperature (20% w/w DTP/HMS). Most
of the literature on HPA catalyzed glycerol dehydration
reaction was reported at 270325 C. Hence, catalytic activity
of 20% w/w DTP/HMS was tested at 325 C. Thermogravi-
metric analysis of 20% w/w DTP/HMS revealed that catalyst is
stable at 325 C.
23,26
In all the cases, catalyst was preheated for
2 h at a desired reaction temperature to activate the catalyst
which also ensured the stability of the catalyst. A series of
experiments were performed at 200, 225, 275, and 325 C to
investigate the eects of temperature on glycerol conversion
and acrolein selectivity by using 20%w/w DTP/HMS catalyst
(see Figure 2). 20% w/w DTP/HMS showed 94% of glycerol
conversion and 80% of acrolein selectivity at 225 C.
Temperature below 225 C was not sucient to vaporize
glycerol and hence conversion of glycerol and selectivity of
acrolein was decreased. It was also observed that beyond 225
C of temperature the conversion of glycerol was almost the
same but selectivity of acrolein decreased.
This anomalous result indicates that 225 C is sucient for
complete conversion of glycerol which could be due the
synergistic eect of the hydrophilic of HMS and Bronsted
acidic of DTP. However, selectivity of acrolein was decreased
with increase in the temperature from 225 to 325 C which
could be due to the cracking of acrolein at higher temperature
and also due to deposition of coking on the support.
42
Therefore, we can conclude that the synergistic eect of DTP
and HMS favors the acrolein selectivity at low temperature, i.e.,
225 C as compared to 275300 C. Hence, further
experiments were performed at 225 C.
3.4. Eect of DTP Loading on HMS. Time on stream data
for DTP loading on HMS was recorded for 25 h. It was found
that increase in DTP loading from 20% to 50% leads to increase
in life of the catalyst without aecting acrolein selectivity. This
increased in the life of catalyst with increase in DTP loading
may be due to proportional increase in catalyst active sites. It
was also found that 20%, 30%, 40%, and 50% DTP/HMS
catalyst undergoes deactivation after 10, 13, 15, and 19 h (see
Figure 3). 50% w/w DTP/HMS has more catalytic active sites
and hence it takes longer time to deactive as compared to 20%
w/w DTP/HMS. The deactivation of 20% w/w DTP/HMS
catalyst is further studies by NH
3
-TPD, BET-surface area, SEM
and EDX analysis for better understanding and design of new
catalyst.
3.5. Regeneration and Reusability of 20% w/w DTP/
HMS Catalyst. The spent catalyst was collected from the
reactor and washed with methanol to remove adsorbed
polymeric material from pores of the catalyst. Then the catalyst
was subjected to calcination at 300 C for 3 h in owing air. A
10% loss of catalyst during regeneration process was made up
with the fresh catalyst, and catalyst reusability study was carried
out at standard reaction conditions. It was observed that
catalyst underwent severe deactivation after rst run (see Table
2). The cause of catalyst deactivation was investigated by NH
3
-
TPD analysis, BET surface area, BJH pore volume, SEM image
and EDX elemental analysis.
Figure 2. Eect of temperature: 20% (w/w) glycerol solution, 1.0 g of
catalyst weight, 325200 C, 1.5 L/h of N
2
ow rate, 10.2 mL/h of
feed ow rate, 10.74 h
1
of WHSV, and 4 h.
Figure 3. Eect of DTP loading on HMS: 20% (w/w) glycerol
solution, 1.0 g of catalyst weight, 225 C, 1.5 L/h N
2
of ow rate, 10.2
mL/h of feed ow rate, and 10.74 h
1
of WHSV.
Industrial & Engineering Chemistry Research Article
dx.doi.org/10.1021/ie401098n | Ind. Eng. Chem. Res. 2013, 52, 1013310144 10137
3.6. Activity and Selectivity of Virgin and Used 20%
w/w DTP/HMS Catalysts. NH
3
-TPD prole of fresh and used
20% DTP/HMS are shown in Figure 4a,b. The acidity of the
used catalyst was found completely decreased. This was because
of deposition of the coke during the reaction which is in
agreement with the literature.
40,41
Also, DTP was leached out
during washing of the used catalyst which was conrmed by
EDX data by tugsten content in the regenerated catalyst (see
Table 3). The surface properties of fresh and used and
regenerated 20% DTP/HMS are given in Table 4. BET surface
area of regenerated catalyst had decreased from 299.7 to 119.21
m
2
/g, pore volume from 0.203 to 0.082 cm
3
, and pore diameter
from 27.16 to 13.01 nm. The decrease in BET surface area,
pore volume and pore diameter is due to the coke deposition
inside the pore of the catalyst which is conrmed by EDX data
of regenerated catalyst, and also responsible for the decrease in
the activity of the catalyst. Figures S1 show SEM image of fresh
and regenerated 20% w/w DTP/HMS catalyst. It was observed
that both the catalysts had marginal dierence in the SEM
image because deposited coke was present in the pore space of
the catalyst. Elemental analysis of fresh, used and regenerated
catalyst was done by EDX (see Table 3). It was found that the
regenerated catalyst contained 5.01 mass% of carbon which was
due to coke deposition inside the catalyst during the reaction.
Also, the tungsten (W) mass percentage of regenerated catalyst
decreased from 11.42 to 1.04 mass %, which was due to
leaching of DTP from the catalyst during washing step. Hence,
it can be concluded that 20% w/w DTP/HMS which is
Bronsted acid catalyst gave the good results for rst run and
after that it underwent severe deactivation due to coke
deposition and leaching of DTP from HMS support. Thus,
part (II) of this work is devoted to preparation of HMS
supported moderate Lewis acid site based catalyst because
strong Lewis acid also leads to severe deactivation as mentioned
in the literature report.
32
3.7. Selection of Lewis Acid Based Catalyst Supported
on HMS. In our laboratory, we have been working in the area
of preparation on supported solid acid catalysts. In part (I)
study we observed that hexagonal mesoporous silica (HMS)
acted as better support for acrolein selectivity. In part (II)
investigation, a new MUICaT-5 catalyst based on HMS as
support was prepared, and used as moderate Lewis acid catalyst
for the dehydration of glycerol to acrolein in vapor phase under
milder conditions in comparison with other reported catalysts.
The moderate acid strength was conrmed by NH
3
-TPD
prole. MUICaT-5 catalyst has WZrAl/HMS catalyst
composition and the elemental composition is mentioned in
Table 8. It was reported that zirconium and tungsten based
catalyst has more Lewis acid character.
4749
The exact catalytic
reaction mechanism of MUICaT-5 to convert glycerol to
acrolein is not known; however, some reports mentioned that
tungsten oxide is converted into tungsten hydroxide at elevated
temperature in presence of steam, which could provide
Bronsted acidity.
49
Typical reaction conditions were: 1.0 g of
catalyst loading, 275 C of reactor bed temperature, 275 C of
preheater temperature, 20% (w/w) of glycerol solution, 10.2
mL/h of feed ow rate (glycerol solution), 1.5 L/h of N
2
ow
rate, 4 h, and 10.74 h
1
of WHSV. The various solid acid
catalysts such as UDCaT-1, UDCaT-4, UDCaT-6, and
MUICaT-5 were screened for glycerol dehydration reaction.
The catalyst composition, percentage conversion of glycerol
and acrolein selectivity are given in Table 5. It was observed
that MUICaT-5 catalyst showed the highest glycerol conversion
and highest acrolein selectivity as compared to other studied
HMS based catalysts. It can be due the presence of moderate
acid site on MUICaT-5 catalyst which is conrmed by NH
3
-
TPD prole. Hence, further studies have been carried out by
using MUICaT-5 catalyst. This enhanced activity of MUCaT-5
catalyst was further corelated to NH
3
-TPD prole, BET surface
area, pore volume, and EDX elemental analysis for better
understanding.
3.8. Time on Stream Data (MUICaT-5 Catalyst). The
stability and activity of the MUICaT-5 catalyst were evaluated
by time on stream (TOS) data up to 100 h. Figure 5 shows that
catalyst MUICaT-5 was stable and active up to 15 h without
any appreciable loss in activity, and selectivity of acrolein. After
that it undergoes gradual deactivation which is also in
accordance with the literature report that the solid acid catalyst
undergoes deactivation due to coke formation during the
reaction.
19,32
The coke deposition on the active site of the
catalyst was conrmed by BET and EDX analysis data.
3.9. Regeneration and Reusability of MUICaT-5
Catalyst. The spent catalyst was removed from the reactor
and washed with methanol to remove the adsorbed
polymerized material from the catalyst. Then, catalyst was
subjected to calcination at 750 C for 3 h in owing air to burn
o coke present on the catalyst. There was an inevitable loss of
catalyst particles during these operations. Hence, the actual
amount of catalyst used in the next batch was almost 10% less
than the previous batch. The loss of the catalyst was made up
with fresh catalyst. Catalyst reusability was veried by
performing the reaction under standard condition for 10 h.
The catalyst was activated under the ow of N
2
at 275 C for 2
h. Table 6 shows that there was no appreciable decrease in the
activity of the catalyst even after sixth run of the catalyst.
MUICaT-5 catalyst shows good reusability without aecting
acrolein selectivity; hence ex-situ regeneration of the catalyst
process can be a cost-eective process. The fresh and
regenerated catalysts were subjected to characterization to
correlate the activity and reusability of the catalyst for glycerol
dehydration reaction.
4. MUICAT-5 CATALYST CHARACTERIZATION
Acidic sites of the catalyst were determined by temperature
programmed desorption (TPD) analysis with ammonia as
probe molecules. Figure 6a,b show NH
3
-TPD data of fresh and
regenerated MUICaT-5 which conrmed that MUICaT-5
catalyst has moderate acid strength, and the acidity of the
used catalyst was regained after calcination at 750 C in owing
air. At 750 C of temperature the coke which was deposited on
active site of used catalyst is burnt o completely which makes
the catalyst active for further reaction.
Surface area and pore volume of fresh, used, and regenerated
catalyst were calculated from N
2
-adsorptiondesorption
Table 2. Catalyst Reusability Study (20% w/w DTP/HMS):
20% (w/w) Glycerol Solution, 1.0 g of Catalyst Weight, 225
C, 1.5 L/h of N
2
Flow Rate, 10.2 mL/h of Feed Flow Rate
10.74 h
1
WHSV, and 4 h
% selectivity
no. % conversion (glycerol) acrolein hydroxyacetone others
a
rst run 94 80 9 11
second run 35 73 13 14
third run 20 65 14 21
a
Acetaldehyde, propionaldehyde, acetone, and allyl alcohol.
Industrial & Engineering Chemistry Research Article
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isotherms using conventional BET and BJH methods and are
presented in Table 7. The surface area of the fresh and
regenerated catalyst was decreased from 143.93 to 138.01 m
2
/g,
pore volume from 0.144 to 0.140 cm
2
/g, and pore diameter
from 40.13 to 40.09 nm. Hence it can be concluded that coke
was completely removed from pore space of the used catalyst
and made the catalyst active. It is also in accordance with the
reusability data of MUICaT-5 catalyst.
Figure S2 (a), (b) and (c) represents the external
morphology of the fresh, used and regenerated MUICaT-5
catalyst. The external morphology of fresh and regenerated
Figure 4. NH
3
-TPD result of (a) fresh and (b) used 20% w/w DTP/HMS.
Table 3. Energy Dispersive X-ray Spectroscopy (EDXS)
Analysis of 20% w/w DTP/HMS (Fresh, Used, and
Regenerated Catalyst)
element
fresh catalyst
(% mass)
used catalyst
(% mass)
regenerated
catalyst
C 6.87 5.01
O 50.14 49.76 52.20
Si 38.44 36.25 41.75
W 11.42 7.12 1.04
total 100 100 100
Industrial & Engineering Chemistry Research Article
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catalyst were quite similar; however, used catalyst shows some
agglomerated particles on the catalyst surface which could be
due to coke deposition. The elemental analysis of fresh, used
and regenerated catalyst was represented in the Table 8. It was
observed that used catalyst has carbon elemental mass
percentage is 4.19%; however, regenerated catalyst has no
carbon elemental mass percentage. Hence we can conclude that
calcination at 750 C for 3 h, removed the coke deposited in
the pores of used catalyst. Therefore, NH
3
-TPD data, BET
surface area, BJH pore volume, SEM image and EDX elemental
analysis provided enough evidence for reusability of MUICaT-5
catalyst.
5. PROCESS OTIMIZATION
5.1. Eect of Temperature (MUICaT-5 Catalyst). The
glycerol dehydration reaction was carried out at four dierent
temperatures of 325, 300, 275, and 250 C under otherwise
similar reaction conditions. Figure 7 shows that with increasing
the temperature from 275 to 325 C, the selectivity of the
acrolein was decreased. However, glycerol conversion increased
from 86 to 98%. The decrease in acrolein selectivity can be due
to the side reaction at higher temperature in the presence of
solid acid catalyst.
19
However, at 250 C of temperature, it gave
the poor glycerol conversion and acrolein selectivity. At 275 C,
MUICaT-5 catalyst gave 86% glycerol conversion and 60% of
acrolein selectivity. Hence, 275 C was chosen for further
reaction parameter optimization.
5.2. Eect of Glycerol Concentration. Glycerol is a
coproduct of biodiesel process which is obtained in dierent
concentrations depending on the workup procedure used.
Hence, dierent concentrations of glycerol such as 10%, 20%
and 50% (w/w) were used to evaluate the activity of the
catalyst. It was observed that 10% and 20% (w/w) of glycerol
solution gave almost similar results. However, 50% (w/w) of
glycerol solution resulted into a decrease in glycerol conversion
as well as acrolein selectivity (see Figure S3). This is a complex
reaction network strongly depedent on reaction temperature
and concentration (partial pressure). As the concentration of
glycerol increases on sites, it leads to cracking and coking. Some
pore channels become inaccessible due to deposition of
carboneous (viscous) material. Even if a few junctions are
blocked, the number of networks become less reducing the
number of active sites. Hence there is decrease in selectivity and
conversion. Hence, 20% w/w of glycerol solution was used for
further optimization.
5.3. Nature of Active Sites. Since HMS is the support in
MUICaT-5 catalyst, it is important to throw light on nature of
acidity.
5.4. Eect of Glycerol Flow Rate. Glycerol ow rate was
optimized by conducting the reaction at four dierent glycerol
ow rate 5.1, 10.2, 20.4, and 40.8 mL/h with WHSV of 5.37,
10.74, 21.48, and 42.96 h
1
, respectively. It was observed that,
with increasing glycerol ow rate from 10.2 to 40.8 mL/h, the
conversion and selectivity both decreased (see Figure S4). The
Table 4. Surface Area, Pore Volume, and Pore Diameter
Analysis of 20% w/w DTP/HMS (Fresh, Used, and
Regenerated Catalyst)
catalyst
BET surface area
(m
2
/g)
pore volume
(cm
2
/g)
pore
diameter
(nm)
fresh 20% w/w
DTP/HMS
299.6 0.203 27.16
used 20% w/w
DTP/HMS
13.1 0.019 2.11
regenerated 20% w/w
DTP/HMS
119.2 0.082 13.01
Table 5. Lewis Acid Based Catalyst Screening (Catalyst Composition, Percentage Conversion of Glycerol, and Acrolein
Selectivity): 20% (w/w) Glycerol Solution, 1.0 g of Catalyst Weight, 275 C, 1.5 L/h of N
2
Flow Rate, 10.2 mL/h of Feed Flow
Rate 10.74 h
1
WHSV, and 10 h
% selectivity
catalyst catalyst composition % conv. (glycerol) acrolein hydroxyacetone others
a
UDCaT-1 sulfuric acid treated Zr/HMS 60 28 15 57
UDCaT-4 persulfated ZrAl/HMS 68 38 16 46
UDCaT-6 chlorosulfonic acid treated Zr/HMS 71 29 14 57
MUICaT-5 WZrAl/HMS 86 60 10 30
a
Acetaldehyde, propionaldehyde, acetone, and allyl alcohol.
Figure 5. Time on stream data: 20% (w/w) glycerol solution, 1.0 g of
catalyst weight, 275 C, 1.5 L/h of N
2
ow rate, 10.2 mL/h of feed
ow rate (glycerol solution), 10.74 h
1
WHSV, and 100 h.
Table 6. MUICaT-5 Catalyst Reusability Study: 20% (w/w)
Glycerol Solution, 1.0 g of Catalyst Weight, 275 C, 1.5 L/h
of N
2
Flow Rate, 10.2 mL/h of Feed Flow Rate 10.74 h
1
WHSV, and 10 h
% selectivity
catalyst run % conversion (glycerol) acrolein hydroxyacetone others
a
rst run 86 59 11 30
second run 84 58 10 32
third run 83 57 12 31
fourth run 81 56 11 33
fth run 78 56 10 34
sixth run 76 55 12 33
a
Acetaldehyde, propionaldehyde, acetone, and allyl alcohol.
Industrial & Engineering Chemistry Research Article
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decrease in catalyst activity is due to increase in WHSV values
hence; the residence time of glycerol is decreased. Also, the
catalyst to substrate weight ratio is decreased with an increase
in feed ow rate so fewer number of catalyst active sites is
available to convert glycerol to acrolein. Therefore, 10.2 mL/h
of glycerol ow rate was chosen for further reaction parameter
optimization.
5.5. Eect of N
2
Flow Rate. N
2
ow rates of 0.72, 1.5, and
3.0 L/h were selected to establish its eect on reaction. It was
observed that with increase in N
2
ow rate from 0.72 to 3.0 L/
h, selectivity of acrolein has decreased. This is because at higher
N
2
ow rate, acrolein was carried away by N
2
gas, and did not
get enough time to get condensed (see Figure S5). The escaped
gas was collected by bubbling it through 250 mL of distilled
water which conrmed the presence of acrolein in outgoing gas.
The total carbon balance was obtained in the range of 8993%
for all liquid products by on line GC analysis. The remaining
was gaseous phase and carbon deposited on the catalyst pores.
5.6. Eect of Catalyst Loading (MUICaT-5 Catalyst). It
was anticipated that with increase in catalyst loading, the life of
catalyst can also be increased due to propotional increase in
catalyst active sites. Hence, the eect of catalyst loading on the
conversion of glycerol was evaluated by loading the reactor with
0.5, 1.0, and 2.0 g of MUICaT-5 catalyst with WHSV value
5.37, 10.74, and 21.48, respectively, by using 20% w/w of
glycerol solution. Figure 8 shows that with increase in catalyst
loading from 0.5 to 2.0 g, catalyst life increased from 6 to 15 h
without aecting the selectivity of acrolein.
6. CONCLUSIONS
Three dierent supports (acidic, neutral and basic) were used
for catalyst development for selective dehydration of glycerol to
acrolein in a continuous xed bed catalytic reactor using various
catalysts. The work was divided in two parts. In part I,
heteropoly acids were used initially as suitable catalysts. Among
hexagonal mesoporous silica (HMS) as a netural support, two
dierent sets of catalysts were prepared: (i) heteropoly acids
supported on HMS and (ii) dierent metal oxides supported
on HMS. It can be concluded that HMS as support increased
the selectivity of acrolein due to presence of free hydroxyl
group, hydrophilicity, and neutral nature. With 20% w/w
dodecatungstophopshoric acid (DTP)/HMS as catalyst, which
has Bronsted acidic characteristics, good results were obtained
at low temperature (225 C). However, the catalyst underwent
severe deactivation due to coke deposition in the pore space of
the catalyst which was conrmed by BET-surface area, and
EDX elemental analysis. It was also observed that the
regenerated DTP/HMS catalyst has very low activity for
glycerol conversion, which was due to leaching of DTP from
catalyst support. Although 20% w/w DTP/HMS showed
promise for glycerol conversion and acrolein selectivity, it is not
Figure 6. NH
3
-TPD of (a) fresh and (b) regenerated MUICaT-5
catalystt.
Table 7. Surface Area, Pore Volume, and Pore Diameter
Analysis of MUICaT-5 Catalyst (Fresh, Used, and
Regenerated)
catalyst
BET surface area
(m
2
/g)
pore volume
(cm
2
/g)
pore diameter
(nm)
fresh MUICaT-5 143.9 0.144 40.13
used MUICaT-5 25.2 0.055 85.72
regenerated
MUICaT-5
138.0 0.140 40.09
Table 8. Energy Dispersive X-ray Spectroscopy (EDXS)
Analysis of MUICaT-5 Catalyst (Fresh, Used, and
Regenerated Catalyst)
element % mass (fresh) % mass (used) % mass (regenerated)
C 4.19
O 45.26 43.51 44.67
Al 0.20 0.20 0.19
Si 34.12 32.68 33.08
Zr 9.79 11.43 11.73
W 10.63 7.98 10.32
total 100 100 100
Figure 7. Eect of temperature: 20% (w/w) glycerol solution, 1.0 g of
catalyst weight, 250325 C, 1.5 L/h of N
2
ow rate, 10.2 mL/h feed
ow rate 10.74 h
1
WHSV, and 10 h.
Industrial & Engineering Chemistry Research Article
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a reusable catalyst. Thus, more rigorous studies were done in
part II work which dealt with selection and preparation of
moderate Lewis acid based catalysts supported on HMS, and its
eects on glycerol dehydration and acrolein selectivity. It was
found that MUICaT-5 catalyst also underwent deactivation due
to coke deposition inside the pore space of the catalyst.
However, the used catalyst regains its activity after calcination
at 750 C. The catalytic activity of regenerated catalyst was
conrmed by NH
3
-TPD data, BET surface area, BJH pore
volume, SEM image, and EDX elemental analysis. Hence,
MUCaT-5 catalyst which has moderate acid site, conrmed by
NH
3
-TPD analysis, has good activity and reusability for glycerol
dehydration reaction to get acrolein in good yield. At optimized
reaction conditions it gave 86% of glycerol conversion and 60%
of acrolein selectivity at 275 C, which is lower than
temperatures used by others. The catalyst was recycled up to
6 times without aecting the activity of catalyst and selectivity
of acrolein.
The global market for biodiesel is estimated to reach 180
million tons by 2016 and to grow at the rate of 42% per year.
6
which will make huge amount of glycerol available as a cheap
feedfstock to produce several chemicals. Glycerol can also be
chemically converted to acrylic acid by dehydration to acrolein
followed by oxidation to acrylic acid which is an important
chemical building block, and used in production of
polyacrylates and commodity acrylates. The global market for
acrylic acid was worth US$8 billion in 2011 and growing at 3 to
4 percentage per year. Hence, the proposed route can also be
useful to meet the acylic acid market demand.
50
Overall this work has added useful new knowledge to
dehydration of glycerol to acrolein.

ASSOCIATED CONTENT
*S Supporting Information
Figures S1S5 as discussed in the text. This material is available
free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION
Corresponding Author
*E-mail: gd.yadav@ictmumbai.edu.in; gdyadav@yahoo.com.
Notes
The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
This research was supported by CSIR-NMITLI program under
the project on Bioglycerol based chemicals. G.D.Y. received
support from R.T. Mody Distinguished Professor Endowment,
and J.C. Bose National Fellowship of DST, Government of
India. R.V.S. and S.O.K. received JRF under this project.

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