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1. Journal : Large 11696 Article No : 3088 Pages : 9 MS Code : 3088 Dispatch : 28-9-2023
Vol.:(0123456789)
1 3
Chemical Papers
https://doi.org/10.1007/s11696-023-03088-5
ORIGINAL PAPER
Sustainable synthesis of automobile fuel additive from glycerol
and acetone and catalyst reusability studies
Lakshmana Rao Jeeru1
· Narayan C. Pradhan2
· Paul Naveen1
· Ramesh Kumar Guduru3
· B. V. S. Praveen4
Received: 14 April 2023 / Accepted: 13 September 2023
© The Author(s), under exclusive licence to the Institute of Chemistry, Slovak Academy of Sciences 2023
Abstract
The present study examined the production of Solketal, a gasoline additive, using glycerol and acetone. For the ketalization
experiments, a potential cation exchange resin Ceralite IR-120 was utilized. The effect of agitation speed, temperature, cata-
lyst dosage, and feed composition on the rate of glycerol conversion was studied. For a molar ratio of 1:16 between glycerol
and acetone, the experimental results indicated a conversion rate greater than 90%. The experimental studies indicate low
mass transfer resistances. The activation energy for the chemical reaction was calculated to be 54.34 kJ/mol, indicating that
kinetics rather than thermodynamics dominates this process. A pseudo-homogeneous reaction model that characterizes the
acetalization process over the catalyst also concurred with the experimentally determined conversion rate. Catalyst reusability
studies showed catalytic activity for up to six recycles.
Keywords Heterogeneous catalyst · Biodiesel · Glycerol · Acetone · Solketal · Acetalization · Reusability
Introduction
Increasing greenhouse gas emissions in the atmosphere has
become a major concern throughout the world, and hence,
reduction in fossil fuel usage has become very important. At
this juncture, biofuels and gasoline additives have received
a great deal of attention due to their ability to cut down
emissions (Alalwan et al. 2019; Okolie et al. 2022). Bio-
mass is a renewable resource and may be used to produce
bioenergy/biofuels without increasing greenhouse gas
emissions (Thornley et al. 2015). Biofuels are great alterna-
tives to fossil fuels. Fischer–Tropsch synthesis produces a
wide range of biofuels, including bio-methanol, bioethanol,
biodiesel, and synthetic diesel, from biomass (Ahorsu et al.
2018; Manikandan et al. 2022). Current international inter-
est in biodiesel is due to several advantages over petroleum
diesel. Biodiesel is a non-toxic and biodegradable alterna-
tive and can be used in conventional diesel engines without
any modifications (Riaz et al. 2022; Aljaafari et al. 2022).
Its superiority over petroleum-based diesel reflects better
lubricity, lack of sulfur, and aromatics, along with reduced
carbon emissions (Singh et al. 2018). Hence, it garnered
great attention in the recent past. It is usually produced along
with glycerol, which is a by-product, via the transesterifi-
cation of triglycerides in vegetable oils/animal fats while
using alcohol in an acid or alkali catalyst. Glycerol/glycerine
is also called 1, 2, 3-propanetriol and is generated almost
10% (by volume) during the production of biodiesel (Reza-
nia et al. 2019). With the increasing production of biofuels
(biodiesel and bioethanol) throughout the world, the simul-
taneous production of large amounts of glycerol has also
seen a large spike, and it is expected to reach 4 million tons
by 2027 (Bhatt et al. 2018). Large-scale manufacturers can
easily refine the glycerol economically but for small-scale
manufacturers, it is always challenging with refining costs,
and on top, they must pay to get rid of glycerol from their
plants. Thus, the price of glycerol is expected to come down
quite rapidly as the production of biodiesel keeps increas-
ing. Therefore, it is worthwhile to consider the efficacy of
* B. V. S. Praveen
bvspraveen@gmail.com
1
Department of Petroleum Engineering, School of Energy
Technology, Pandit Deendayal Energy University,
Gandhinagar 382426, India
2
Department of Chemical Engineering, Indian Institute
of Technology, Kharagpur 721302, India
3
Department of Mechanical Engineering, School
of Technology, Pandit Deendayal Energy University,
Gandhinagar 382426, India
4
Department of Chemical Engineering, Chaitanya Bharathi
Institute of Technology (CBIT), Hyderabad 500075, India
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glycerol in producing value-added products on an industrial
scale to enhance the sustainability of the biodiesel industry
(Ayoub and Abdullah 2012; De Corato et al. 2018; Gutiér-
rez Ortiz 2020).
Early research on glycerol showed the possibility of pro-
duction of 1,3-propanediol through hydrogenolysis (Wang
et al. 2020), glycolic acid dihydroxyacetone and glyceralde-
hyde via oxidation (Zhang et al. 2012), and form acrolein
by dehydration processes (Sung and Cheng 2017), which,
in turn, can result in acrylic acid upon oxidation, and then,
polyglycerol and polyglycerol esters when polymerized.
However, glycerol is unsuitable for fuel applications to the
hydroxyl groups but is an excellent source for making oxy-
genated compounds, e.g., acetals and ketals, which can be
used as additives in the fuels for the reduction of carbon
emissions. On top, glycerol-based acetals are used as sur-
factants, disinfectants, and flavors (Kaur et al. 2020; Checa
et al. 2020). The acetalization of glycerol with acetone
results in 2,2-dimethyl-1,3-dioxane-5-ol and 2,2-dime-
thyl-1,3-dioxolane-4-methanol (Solketal), which are two-
branched oxygenated compounds, shown in the scheme used
in the acetalization of glycerol with. Among these, Solketal
is a good fuel and helps improve the flow properties of liquid
fuels at low temperatures in the transportation sector. Also,
it helps improve the oxidation stability and octane number
of gasoline while reducing gum formation (Ilgen et al. 2016;
Corrêa et al. 2021). It is also used as a solvent in the polymer
industry for plasticizing polymers. It is used in pharmaceuti-
cal preparations also as solubilizing and suspending agent
(Vannucci et al. 2021) (Fig. 1).
Various catalysts were used for the conversion of glycerol
to Solketal. These catalysts include iron complex, Purolite,
Amberlyst-35, Indion, nitric acid-modified montmorillonite
clay, heteropolyacids (HPAs), and many more (Corrêa et al.
2021). In general, the acetalization of glycerol is done using
homogeneous acid catalysts, such as mineral acids (H2SO4,
HF, and HCl) and p-toluene sulfonic acid (Poly et al. 2019).
Esposito et al. (2017) and Da Silva et al. (2020) used iron-
based homogeneous catalyst with glycerol-to-acetone molar
ratio ranging between 1:4 and 1:20. In both cases, the con-
version and selectivity were reported to be more than 95%.
However, the catalyst was reported to lose its activity after
four recycles. However, this approach suffers from corro-
sion of process equipment along with difficulty in separating
the catalyst from the product stream. In addition, it also has
environmental concerns regarding effluent disposal. Never-
theless, these challenges can be overcome while using het-
erogeneous catalysts. Zeolites used as catalysts by various
researchers showed selectivity of 85% for glycerol acetone
molar ratio ranging between 1:2 and 1:10. However, the
catalyst showed very little or no reusability (Manjunathan
et al. 2015; Kowalska-Kus et al. 2017). Different studies
were reported on the acetalization of glycerol using solid
acid catalysts such as Amberlyst-36, Amberlyst-15, mont-
morillonite K-10, niobic acid, HZSM-5, HUSY, amorphous
and mesoporous silica, sulfated zirconia, and zeolites such
as H-BEA, H-MOR, H-MFI, and H-FER (Gonçalves et al.
2008; Testa et al. 2013; Rossa et al. 2019). Ion-exchange
type catalyst consisting of Indion 225 Na led glycerol con-
version of 35% (Sulistyo et al. 2020), and Amberlyst-35
showed conversion of 70% (Moreira et al. 2019). Deutsch
et al. (2007) investigated the activity of various heterogene-
ous catalysts for the generation of cyclic acetals via glycerol
condensation reaction with aldehydes. A high molar ratio
of acetone to glycerol (6:1) resulted in a high yield of more
than 90% of Solketal with high selectivity in a batch reactor
(Vicente et al. 2010). Although different researchers showed
the potential conversion of glycerol into fuel additives or
value-added products through the acetalization process,
none of them had reported any detailed kinetic studies with
acetone over the solid acid catalysts (Deutsch et al. 2007;
Vicente et al. 2010; Smirnov et al. 2018; Zahid et al. 2020).
Other catalysts, including clays, metal oxides, and ionic liq-
uids, showed good catalytic conversion but very poor recy-
clability. The literature reported that the global market of
Solketal is expected to account for around $108.4 billion by
2028 (Ao and Rokhum 2022).
This information is very critical from the practical imple-
mentation point of view for the utilization of glycerol in
producing value-added fuel additives. Therefore, consider-
ing the great importance of the above in the long term, here,
we have done detailed kinetic studies of the acetalization of
Fig. 1 The scheme used in the acetalization of glycerol with acetone
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glycerol with acetone. The primary objective of this work
was to explore the kinetics of the acetalization reaction of
glycerol with acetone in a batch mode over a solid acid cata-
lyst, Ceralite IR-120. We have studied the effect of various
parameters to shed light on the practical viability of the
adapted approach. The outcome of these studies could easily
help propose a suitable reaction mechanism and a rate equa-
tion with the kinetic parameters measured experimentally.
Experimental methods
Materials
Both glycerol and acetone (>99.5 wt. % purity) were pro-
cured from Merck Specialty Pvt. Ltd. Commercial grade
N, N-dimethyl formamide (DMF) (>99.5 wt. % purity) was
obtained from SD Fine Chem Pvt. Ltd., Mumbai, India.
Solketal (1, 2-Isopropylideneglycerol, 99 wt. %) was pur-
chased from Sigma-Aldrich, India, as a calibration standard
for gas chromatography (GC) analysis. The strong cation
exchange resin, Ceralite IR-120 (20–50 mesh, ionic form H+
with ion-exchange capacity min. 4.5 meq/g) (equivalent to
Amberlite IR-120) from Central Drug House (P) Ltd., was
used as the catalyst.
Experimental procedure
The glycerol acetalization reactions were performed in a
20 cm3
fully baffled three-necked glass reactor equipped
with a glass turbine impeller connected to a high-speed
motor and a vertical condenser. The reactor's temperature
was controlled precisely with an accuracy of ± 0.03 K
using an external thermostat containing an external ther-
mocouple inserted inside the reaction mixture, and a sche-
matic for the setup used in our experiments is shown in
Fig. 2.
The acetalization experiments were conducted using
a predetermined amount of reactant mixture comprising
glycerol and acetone, taken in a standard volumetric flask,
following the required mole ratios, and then diluted with
DMF solvent to achieve a total volume of 100 cm3
. The
resulting mixture was then introduced into the reactor and
maintained at a constant temperature using a water bath.
Fig. 2 A schematic diagram for
the batch reactor assembly
Fig. 3 Effect of agitation speed on reaction rate [Conditions: temper-
ature=303 K; feed mole ratio (glycerol:acetone)=1:10; catalyst load-
ing=10% (W/V); and matching glycerol conversion=5.0%]
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Once the temperature was set, the catalyst solution was
added to the reactor simultaneously. To improve the solu-
bility of glycerol in acetone, DMF was used as a suitable
solvent, leading to the formation of a single phase, indicat-
ing proper homogenization. Liquid samples of approxi-
mately 0.2 ml were extracted at regular intervals once the
two phases (liquid and solid) separated clearly without
agitation. The samples were then stored in an ice bath
until analysis through gas chromatography (GC 8610). The
samples from the organic phase were collected at vari-
ous time intervals and analyzed in a gas chromatograph
(GC) (Thermo Scientific Trace 800 Model) equipped with
a capillary column measuring 30 m in length, 0.25 mm in
inner diameter, and a 0.25‐μm film with 5% phenyl methyl
polysiloxane as a stationary phase. Nitrogen was employed
as the carrier gas, and the GC used a flame ionization
detector. The composition of the samples was analyzed by
comparing peak areas against a pre-calibrated curve, and
the actual glycerol conversions and the moles of products
were measured from the calibration file prepared in GC
using various standards made from pure compounds.
Results and discussion
Effect of agitation speed
Initially, the effect of agitation speed was examined to deter-
mine the role of mass transfer resistances on the reaction
system, as it is very important before performing the kinetic
studies of any reaction. The experiments were conducted at
various agitation (stirring) speeds in the range of 1000–3000
rev/min under otherwise identical experimental conditions
to investigate the effect of mass transfer on the reaction's
kinetics. The reaction rates at matching 5% glycerol conver-
sion were compared in this stirring speed range, and it was
observed to increase with the increase in speed up to 2000
rev/min, as shown in Fig. 3. Above 2000 rev/min, the effect
of speed on reaction rate is negligible, and it could be con-
cluded that the mass transfer effect is unimportant at speeds
above 2000 rev/min. Therefore, all other experiments were
Fig. 4 Effect of feed mole ratio
on glycerol conversion [Condi-
tions: temperature=298 K; the
speed of agitation=2500 rev/
min; and catalyst loading=10%
(W/V)]
Fig. 5 Effect of feed mole ratio on reaction rate [Conditions: tem-
perature=298 K; the speed of agitation=2500 rev/min; catalyst load-
ing=10% (W/V); and matching glycerol conversion=5.0%]
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conducted at a constant 2500 rev/min speed to eliminate the
mass transfer effects, and the reactions were kinetically con-
trolled. In this study, the reactants could quickly diffuse into
the pores without any significant resistance in a macroscopic
ion-exchange resin used as a catalyst. Hence, internal mass
transfer resistance was expected to be negligible.
Effect of initial composition of reaction mixture
Experiments are carried out to analyze the influence of
the initial molar concentration of reactants on conversion
and the reaction rate at 298 K with 10% (W/V) loading of
the catalyst and at a constant stirring speed of 2500 rev/
min while varying the initial acetone-to-glycerol molar
ratio from 2 to 16. Increasing the acetone-to-glycerol
molar ratio increased glycerol conversion, as shown in
Fig. 4. The rates of reaction of glycerol were calculated
at a 5% conversion level for various feed compositions.
From Fig. 5, it can be observed that the rate of reaction of
glycerol increases with an increase in the concentration of
acetone in the reaction mixture. Therefore, the reactants'
initial mole ratio strongly affects the reaction kinetics: A
higher mole ratio results in a higher reaction rate and more
extensive conversion. The experimental outcomes demon-
strate that the excess of acetone in the composition leads
to enhancing the reaction in the forward direction thermo-
dynamically to escalate the glycerol conversion. Increased
reactant concentrations would result in a greater reaction
rate, thereby tending to further product yield.
Effect of temperature
The effect of reaction temperature on the acetalization reac-
tion of glycerol was explored at different temperatures rang-
ing from 303 to 333 K with the fixed conditions of acetone/
glycerol mole ratio of 6 and catalyst loading of 5% (W/V),
and the variation of glycerol conversion with temperature
is shown in Table 1 and Fig. 6. Based on the equilibrium
conversion data obtained, higher temperatures reduce the
equilibrium product yield, consistent with thermodynamic
studies showing exothermic behavior. Furthermore, the ini-
tial rate of the ketalization process increases with increasing
temperature, similar to that shown in the literature (Nanda
et al. 2014). From the conversion values, it was inferred that
high conversions were achieved at low temperatures due to
exothermic reaction; however, this was compensated with
longer reaction times (Moreira et al. 2019). The reaction rate
was also calculated at a matching glycerol conversion of 5%,
as shown in Fig. 7. The Arrhenius plot of logarithmic initial
rates (calculated from the best polynomial fit curve with con-
version–time data) versus the inverse reaction temperature
Table 1 Effect of reaction
temperature on conversion
at different temperatures
[Conditions: feed mole ratio
(glycerol:acetone)=1:6; catalyst
loading=5% (w/V); and the
speed of agitation=2500 rpm]
Time (min) Conversion of glycerol (%)
Reaction temperature (K)
303 308 313 318 323 328 333
5 2.8 3.4 5.9 8.7 10.6 14.0 17.2
10 4.3 7.1 10.2 12.9 16.2 22.2 29.0
15 6.0 9.5 14.5 17.8 23.0 27.5 34.8
30 10.8 17.5 21.9 27.1 33.0 40.4 48.0
45 15.3 22.8 27.6 35.9 41.0 48.7 54.2
60 20.0 30.4 33.5 40.3 46.9 54.4 58.7
120 31.5 43.4 46.5 54.6 60.5 63.9 65.4
240 47.2 52.4 60.7 62.7 66.5 70.4 66.7
360 56.7 60.5 66.0 68.9 69.9 71.4 67.3
480 61.4 65.7 69.4 71.9 73.6 71.4 67.3
Equilibrium conversion 93.3 87.4 84.1 78.2 74.8 71.4 67.3
Fig. 6 Effect of temperature on conversion [Conditions: feed mole
ratio (glycerol:acetone)=1:6; the speed of agitation=2500 rev/
min; catalyst loading=10% (W/V); and matching glycerol conver-
sion=5.0%]
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was made, as shown in Fig. 8. The slope of the best-fit line
determined the apparent activation energy as 54.34 kJ/mol.
The equilibrium constant values at different temperatures
were calculated based on the equations considered from the
literature (Nanda et al. 2014) and are shown in Table 2. The
equilibrium values were evaluated by keeping the reaction
times very long until two consecutive values were similar.
From Table 2, it was inferred that high conversions were
achieved at low temperatures due to exothermic reaction
(Moreira et al. 2019); however, this was compensated with
longer reaction times.
The equilibrium constant is calculated using the follow-
ing formula:
A graph plotted between the lnKc vs 1∕T showed a linear
correlation. This plot is used to calculate the thermodynamic
properties such as enthalpy and entropy which is given by
the expression:
whereΔHo
and ΔSo
are the standard enthalpy and entropy
at 298 K (kJ/mol K). The linear fitting of the experimental
data obtained the following equation:
Kc =
[solketal]∗[water]
[acetone]∗
[
glycerol
]
ln Kc =
ΔSo
R
−
ΔHo
R
1
T
3.0x10
-3
3.1x10
-3
3.2x10
-3
3.3x10
-3
-10
-9
-8
-7
ln(Initial
reaction
rate,
kmol/m
3
.s)
1/T(K
-1
)
Experimental
Linear Fit,R
2
=0.988
Fig. 8 Arrhenius plot of ln (initial rates) versus 1/T [Conditions:
temperature=303 K; feed mole ratio (glycerol:acetone)=1:10; the
speed of agitation=2500 rev/min; and matching glycerol conver-
sion=5.0%]
Table 2 XXX
Temperature (K) Equilibrium conversion, XE Equilibrium
constant, Kc
303 93.3 1.56
308 87.4 0.89
313 84.1 0.72
318 78.2 0.51
323 74.8 0.39
328 71.4 0.34
333 67.3 0.26
Fig. 7 Effect of tempera-
ture on reaction rate [Con-
ditions: feed mole ratio
(glycerol:acetone)=1:6; the
speed of agitation=2500 rev/
min; catalyst loading=10%
(W/V); and matching glycerol
conversion=5.0%]
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Comparing the above two equations, we get
ΔHo = −154.67 kJ/mol K and ΔSo = −47.61kJ/mol K. The
negative values suggest that the reaction is exothermic, simi-
lar to that reported in the literature (Ribeiro et al. 2022).
ln Kc = 5729.1
1
T
− 18.613
Recycling (reusability) of the catalyst
The catalyst was reused for five additional cycles to evaluate
the stability of the ion-exchange resin in the glycerol and
acetone reaction. Each cycle was conducted at 313 K with
a glycerol-to-acetone molar ratio of 1:6 and a reaction time
of up to 8 h. Following an 8-h reaction time, the catalyst
was recovered through filtration, thoroughly washed with
distilled water to remove any entrapped glycerol, acetone,
Solketal, and solvent, and then air-dried overnight at 308 K.
The dried catalyst was subsequently reloaded into the reac-
tor. The glycerol conversions for each reaction cycle were
very similar, and no significant catalyst deactivation was
observed in the analyses conducted (Fig. 9).
Kinetic studies
The acetalization of glycerol with acetone was performed in
the presence of a solid acid catalyst. Solketal was identified
as the only product of the cation exchange resin-catalyzed
acetalization reaction. From the conversion versus time data
at diverse temperatures, plots of – ln(1-XG) (where XG is
conversion of glycerol) versus reaction time were made, and
the plots were observed to be well fitted with linear relation
having origin as slope, as shown in Fig. 10. The pseudo-first-
order rate constants are obtained from the slopes of straight
lines at different reaction temperatures in the selected
range. The results show as the temperature increased from
303 to 333 K for the glycerol-to-acetone molar ratio of 1:6
and catalyst loading of 5% (w/V), the apparent rate con-
stant increased from 7.18 × 105
to 51.35 × 105
s−1
. The
plot (Fig. 10) shows a less than linear fit for temperature
1 2 3 4 5 6
8
10
12
14
Reaction
rate
X
10
5
,
kmol/
m
3
.s
Catalyst run cycles
Fig. 9 Variation of reaction rate with reuse time [Conditions: reac-
tion temperature=313 K; feed mole ratio (glycerol:acetone)=1:6; the
speed of agitation=2500 rev/min; catalyst loading=5% (W/V); and
matching glycerol conversion=5.0%]
Fig. 10 The plot of the pseudo-
homogenous first-order inte-
grated kinetic model
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333 K. This is attributed to the fact that as the temperature
increases, the reaction rate increases, making the curve non-
linear, as reported by Moreira et al. (2019). However, we
have considered a linear pseudo-first-order reaction to meas-
ure the apparent rate constant used to evaluate the activation
energy at all the temperatures.
In a graph plotted between the logarithmic values of the
apparent rate constant and the inverse of reaction tempera-
ture, a reasonably good straight-line fit was observed and is
shown in Fig. 11. The apparent activation energy and the
frequency factor are calculated from the slope and intercept
as 54.88 kJ/mol and 13.05 ×104
s−1
, respectively.
Conclusions
Glycerol, a by-product of the biodiesel industry, was con-
verted into a valuable product, Solketal, ketalization with
acetone, another low-cost by-product of the cumene process
phenol. A heterogeneous catalysis approach was employed
to synthesize Solketal using an acidic ion-exchange resin
(Amberlite IR120) as a solid acid catalyst. The reaction
mixture's intense agitation was kinetically controlled with
an apparent activation energy of about 54.34 kJ/mol. A
pseudo-homogeneous reaction model was developed for the
acetalization reaction over the heterogeneous catalyst. The
model could fit the experimental conversion–time data rea-
sonably well. As a heterogeneous catalyst, the ion-exchange
resin was recovered and then reused without reactivation six
times. This is an eco-friendly process, and the catalyst can
be recycled without regenerating.
Declarations
Conflict of interest On behalf of all authors, the corresponding author
states that there is no conflict of interest.
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