Article

pubs.acs.org/IECR

Glycerol Valorization as Biofuel Additives by Employing a Carbon-

Based Solid Acid Catalyst Derived from Glycerol
Ummadisetti Chandrakala, Rachapudi B. N. Prasad, and Bethala L. A. Prabhavathi Devi*
Centre for Lipid Research, CSIR - Indian Institute of Chemical Technology, Tarnaka, Hyderabad-500007, India
*
S Supporting Information

ABSTRACT: A two-step process was developed for the preparation of triacetylglycerol (TAG), a biofuel additive employing a
solid acid catalyst derived from glycerol. The first step involves esterification of glycerol with acetic acid (1:4 mol) at 115 °C for 1
h in the presence of catalyst (5 wt %) to obtain 100% conversion of glycerol with 22, 67, and 11% MAG, DAG, and TAG,
respectively. In the second step, the esterified product mixture after removal of excess acetic acid and moisture was acetylated
with acetic anhydride (1 mol with respect to glycerol) at 115 °C for 30 min to obtain 100% TAG. The recovered catalyst was
reused for five cycles without any significant loss of its initial activity. The protocol is cost-effective due to the use of highly stable
and recyclable SO3H-carbon catalyst for the production of TAG with minimum moles of acetic acid and acetic anhydride in
shorter reaction time.

1. INTRODUCTION gasoline.15 The acetylated glycerols can be produced by

In recent years, the commercial use of biodiesel has been
rapidly expanding throughout the world as a potential
substitute for the petroleum based fuels because it is one of
the renewable, biodegradable, and biocompatible new energy
sources. The rapid growth of the biodiesel industry resulted in
oversupply of glycerol which has become a burden to the
biodiesel industry until new markets are created for glycerol by
way of new product development.1,2 Glycerol is a highly
fascinating molecule for the preparation of a variety of chemical
intermediates, and also it is a platform chemical for the
production of biofuel additives. Several groups are working for
the conversion of glycerol into value added products through
different strategies and/or approaches such as hydrogenolysis,
esterification/acetylation, reforming, etherification, etc.3−13
Most of these reactions are reported to be favored in the
presence of Brønsted acid catalysts, especially for the
production of oxygenated compounds like fuel additives from
biodiesel byproduct glycerol. Valorization of glycerol as fuel
additives can not only improve the engine performance by
reducing the diesel fuel particulate emissions, pour point, and
viscosity of biodiesel on blending but also reduce the cost and
increase the quality of biofuel.14
Acetylated glycerol derivatives, namely, monoacetylglycerol
(MAG), diacetylglycerol (DAG), and triacetylglycerol (TAG),
have gained potential interest to find applications for the better
utilization of excess glycerol produced from the biodiesel
process. The industrial production of acetylglycerols is known
since decades ago, and all of them have several applications in
the chemical industry. MAG is used in the manufacture of
explosives, as tanning agent, and as solvent for dyes. DAG is
used as a plasticizer and softening agent and solvent. TAG is
used as a solvent for dissolving or diluting drugs and organic
compounds. In addition, DAG and TAG are valuable additives
that cause improved properties with respect to viscosity, flash
point, and oxidation stability when used as a supplement to
diesel fuel and also as antiknocking agent when added to
esterification/acetylation of glycerol with acetic acid/acetic
anhydride with or without homogeneous or heterogeneous
catalysts. Homogeneous acid catalysts such as HCl, H3PO4, and
p-TSA have been employed for the acetylation of glycerol.
However, homogeneous catalysts generate several problems at
the end of the reactions, including difficulty in separation of the
catalysts, production of toxic pollutants, and corrosion of the
reactor. To overcome these drawbacks, research attention has
been mainly impelled to discover ecofriendly and highly stable
heterogeneous catalysts, such as solid acid or base catalysts.
In the last few years, several studies were reported by using
different solid acid catalysts such as Amberlyst-15, zirconia,
niobic acid, HPAs, and zeolites for the preparation of glycerol
acetates from glycerol and acetic acid.16−18 Acidic mesoporous
silica catalyst was reported for 90% glycerol conversion with
over 85% of combined selectivity toward DAG and TAG.15
When sulfuric acid treated activated carbon was used as catalyst,
91% glycerol conversion with selectivity of 38, 28, and 34% for
mono-, di-, and triacetyl glycerols, respectively, was achieved at
120 °C and 3 h of reaction time.5 When Amberlyst-15 acid
resin was used as a catalyst, a selectivity of 54 and 13% toward
DAG and TAG, respectively, was achieved.4 Dodecatungsto-
phosphoric acid immobilized onto a silica matrix as a
heterogeneous catalyst achieved 65% combined selectivity (62
and 3% for DAG and TAG, respectively) to DAG and TAG.19
Whereas in the presence of niobic acid-supported tungstophos-
phoric acid (TPA) as catalyst, a relatively high combined
selectivity of 77% (57 and 20% of DAG and TAG, respectively)
to DAG and TAG was recorded.7 When MoOx/TiO2−ZrO2
catalyst was used, 100% conversion with selectivity of 53, 40,
and 7% of MAG, DAG, and TAG, respectively, was reported.8
Received: August 1, 2014
Revised: September 30, 2014
Accepted: September 30, 2014

© XXXX American Chemical Society A dx.doi.org/10.1021/ie503079m | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
Sulfated zirconia catalysts were considerably less active.20 Most
recently, sulfated zircon-based mixed oxides (SO42−/CeO2−
ZrO2) solid acid catalyst was reported with 100% conversion
with 25, 59, and 16% selectivity for MAG, DAG, and TAG,
respectively.10 However, some of these catalysts cannot be
applied industrially because HPAs are soluble in polar media,
some silicate-based catalysts are difficult to functionalize,
zeolites have low thermal stability, and some materials are
too expensive.5 Moreover, water also affects the catalytic
behavior of the catalyst because of the hygroscopic nature of
some of these catalysts. Even though there are many studies for
the preparation of acetylated glycerol derivatives with acetic
acid in a single step using different solid acid catalysts, none of
them showed 100% selectivity to TAG even with high amounts
of acetic acid: glycerol ratio (>6:1 mmol) and after longer
reaction periods (>4 h) at higher temperatures (>120 °C). As
the rate of acetylation reaction is higher than esterification,
acetic anhydride as an acylating reagent can achieve 100%
selectivity for TAG either through esterification followed by
acetylation with the acid resin Amberlyst-35 as a catalyst in the
presence of a high excess of acetic acid or by direct acetylation
with acetic anhydride with K-10 Montmorillonite as
catalyst.21,17 According to Liao et al.,21 first step of esterification
was carried out with 9 equiv of acetic acid (with respect to
glycerol) for 4 h at 105 °C, and in the second step acetic
anhydride was added to complete the reaction with 100%
selectivity to TAG in 15 min. But the main disadvantage of this
method is use of high moles of acetic acid for the esterification
step and longer reaction time with less selectivity to TAG.
Recently, carbon-based solid acid catalysts have gained
significant attraction over homogeneous catalysts as they are
highly efficient, sustainable, and eco-friendly and can be reused
several times without appreciable loss of activity.22 In this
context, we have demonstrated that sulfonic acid functionalized
heterogeneous carbon catalysts derived from glycerol (biodiesel
byproduct)/glycerol pitch (waste from fat splitting industry)
are promising catalysts for the esterification of fatty acids,
tetrahydropyranyl protection and deprotection of alcohols and
phenols, simultaneous esterification and transesterification of
nonedible oils, acetylation of alcohols, phenols, and amines, and
also the regioselective azidolysis of epoxides.23−28 In con-
tinuation of our efforts toward exploring the applications of the
carbon acid catalyst having 1.6 mmol/g acid density with
surface area of 0.21 m2/g, we herein report a simple and highly
efficient two-step process for the production of TAG, a biofuel
additive by esterification of glycerol with acetic acid followed by
acetylation of glycerol acetates with acetic anhydride at 115 °C
within 1.5 h with high selectivity and reusability.
2. EXPERIMENTAL SECTION
2.1. Catalyst Preparation.28 A mixture of glycerol (10 g)
and concentrated sulfuric acid (30 g) were taken in a 500 mL
glass beaker and gently heated on hot plate from ambient
temperature to 220 °C to facilitate in situ partial carbonization
and sulfonation. The contents of the reaction were left at that
temperature for about 20 min until the foaming ceased. The
resultant black crystalline product was cooled to ambient
temperature and washed with hot water under agitation until
the wash water became neutral to pH. The product was filtered
using filter cloth (90 μ pore size) under vacuum and dried in
the oven for 2 h at 120 °C in order to ensure that it was free of
moisture to obtain glycerol based carbon acid catalyst (5.60 g).
The catalyst was fully characterized by CHN analysis, XRD,
B dx.doi.org/10.1021/ie503079m | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Article
XPS, IR, 13C MAS, and Raman spectroscopy. The methods are
discussed in Supporting Information.
2.2. Two-Step Methodology for the Preparation of
Triacetylglycerol (TAG). In the first step, glycerol was reacted
with acetic acid followed by acetic anhydride in the second step
to achieve 100% TAG in quantitative yields.
2.2.1. First Step: Esterification of Glycerol with Acetic Acid.
A mixture of glycerol (9.2 g, 0.1 mol), acetic acid (23 mL, 0.4
mol), and catalyst (0.46 g, 5 wt % of glycerol) were heated at
115 °C for 1 to 4 h under stirring. The reaction was monitored
by TLC and GC. After complete conversion of glycerol the
catalyst was separated from the reaction mixture by filtration,
washed with methanol, and dried at 110 °C for reuse. The
product mixture was concentrated and dried by distilling out
the unreacted acetic acid and moisture formed during the
reaction in a rotary evaporator under reduced pressure.
Optimization of reaction conditions for the complete
conversion of glycerol to glycerol acetates was conducted by
varying the catalyst loading from 5 to 20 wt % (with respect to
glycerol) and mole ratio of glycerol:acetic acid (1:4 to 1:10) for
different reaction periods (1 to 4 h) at 115 °C. The
composition of the reaction mixture for the formation of
MAG, DAG, and TAG was determined at regular intervals by
GC. There is a possibility of the formation of the isomers of
MAG (1-MAG and 2-MAG) and DAG (1,3-DAG and 1,2-
DAG) during esterification reaction. However, separation of the
isomers of MAG and DAG was not observed in the GC analysis
and hence it was reported as MAG and DAG.
2.2.2. Second Step: Acetylation of Glycerol Ester Mixture
with Acetic Anhydride. The dried esterified products mixture
obtained after 1 h and the recovered carbon acid catalyst from
the first step were treated with acetic anhydride (9.56 mL, 0.1
mol, 1:1 with respect to glycerol used in the first step) at 115
°C for 30 min to get 100% TAG. The reaction was monitored
by TLC and GC. After completion of the reaction, catalyst was
separated by filtration, and the unreacted acetic anhydride and
acetic acid formed during the reaction were distilled out under
vacuum in a rotary evaporator to obtain 100% TAG in
quantitative yield. In another protocol the reaction mixture
from the first step (without separation of catalyst and drying)
after 1 h was treated with acetic anhydride (0.1 mol, 1:1 with
respect to glycerol) at 115 °C for 4 h. The effect of drying of
the esterified product and catalyst in the acetylation reaction for
the preparation of TAG was also studied by conducting the
reactions with and without catalyst and also by varying the
acetic anhydride concentration and reaction period.
2.3. Analysis of Reaction Products. The reaction samples
were collected at 1 h intervals and were qualitatively analyzed
using gas chromatography (GC) for conversion percentages.
The reaction sample (100 μL) was diluted in CHCl3:MeOH
(1:1, 2 mL), and 1 μL of the liquid was injected into a capillary
nonpolar GC column HP-1 (30 m × 0.32 mm × 0.10 μm)
mounted in a gas chromatograph GC 6850 system (Agilent
Technologies, USA). The analysis was performed in a
temperature-programmed mode of 80 °C (0 min)−10 °C/
min−300 °C (5 min). The typical retention times (tR) of the
components were 4.04, 5.03, and 5.93 min for MAG, DAG, and
TAG, respectively.
3. RESULTS AND DISCUSSION
Generally, the synthesis of biofuel additives by acetylation of
glycerol using acetic anhydride proceeds with higher reaction
rates and is more difficult to handle than that of esterification.
Industrial & Engineering Chemistry Research Article

Scheme 1. Carbon Acid Catalyzed Two-Step Process for the Preparation of Triacetylglycerol

However, if only acetic acid was used for esterification reaction Table 1. Effect of Acetic Acid Mole Ratio and Time on the
with glycerol, MAG and DAG were found to be major Esterification of Glycerola
components restricting TAG to not more than 20%. So there is
glycerol:AcOH (mole ratio) control
a need to use acetic anhydride for completing the reaction to
prepare TAG in high yields. But the price of the acetic 1:4 1:6 1:8 1:10 1:4 1:10
anhydride is as high as four times that of acetic acid, and hence time (h) product [composition (wt %) of the product by GC]
it is not commercially feasible for industry to use acetic 1 glycerol - - - - 40.4 40.6
anhydride alone to prepare TAG. In order to reduce the cost of MAG 22.0 15.8 12.3 8.4 44.6 34.2
the overall process for higher production of TAG, we employed DAG 67.0 72.2 73.2 71.8 15.0 24.8
a two-step protocol to achieve TAG quantitatively in short time TAG 11.0 12.0 14.5 19.8 - 0.4
by employing highly stable and recyclable carbon-based solid 2 glycerol - - - - 34.6 33.2
acid catalyst derived from glycerol. In the first step, glycerol was MAG 20.1 20.4 9.8 7.5 21.8 30.9
esterified with cheap acetic acid to the mixture of MAG, DAG, DAG 63.4 62.2 70.3 70.2 41.2 33.8
and TAG in the presence of carbon acid catalyst. In the second TAG 16.5 17.4 19.9 22.3 2.4 2.1
step, both MAG and DAG were acetylated with acetic 3 MAG 17.1 11.0 - - 41.5 48.9
anhydride to TAG (Scheme 1). DAG 61.5 65.3 65.2 63.0 54.5 46.6
3.1. First Step: Esterification of Glycerol with Acetic TAG 21.4 23.7 34.8 37.0 4.0 4.5
Acid. Glycerol esterification reactions were conducted with 4 MAG 12.7 8.0 - - 31.1 22.8
acetic acid in the presence of carbon acid catalyst at 115 °C. To DAG 61.9 64.0 61.1 60.2 62.0 65.7
obtain maximum conversion and selectivity in the first step of TAG 25.4 28.0 38.9 39.8 6.9 11.5
the process, different reaction parameters such as glycerol to a
Reaction conditions: glycerol = 9.2 g, 0.1 mol; catalyst = 0.46 g, 5 wt
acetic acid molar ratio, reaction time, and catalyst loading were % of glycerol; T = 115 °C.
studied. Reactions were also performed without catalyst as a
control, to evaluate the diversity of the reactions performed in esterification of glycerol (1 mol) with less moles of acetic acid
the presence of catalyst. (4 mol) to its acetylated glycerols (MAG, DAG, and TAG)
3.1.1. Effect of Reaction Time and Acetic Acid Mole Ratio. within 1 h.
Initially, effect of reaction period on the esterification of Effect of acetic acid mole ratio on the esterification of
glycerol with 1:4 mol ratio of acetic acid in the presence of 5 wt glycerol to TAG was investigated by varying the acetic acid
% of the catalyst at 115 °C for 1 to 4 h was studied. The mole ratio from 1:4 to 1:10 in the presence of catalyst (5 wt %)
composition of the acetylated product mixture (glycerol at 115 °C for 1 to 4 h, and this was compared with the control
conversion to MAG, DAG, and TAG) obtained was analyzed (1:10 and without catalyst) reaction (Table 1). The results
by GC, and the results in wt % are given in Table 1. From this clearly indicated that a marginal increase in the formation of
study, complete esterification of glycerol with acetic acid DAG (67 to 73%) and TAG (11 to 20%) was observed in 1 h
resulting in acetylated glycerols with high content of DAG even by increasing the amount of acetic acid from 1:4 to 1:10.
(67%) along with MAG (22%) and TAG (11%) was observed Whereas, in the control reaction even with high amount of
within 1 h. With further increase of reaction period to 4 h, TAG acetic acid (1:10 mol), only 60% glycerol conversion with
content increased from 11 to 25%, whereas MAG and DAG selectivity of MAG (34%), DAG (25%), and traces of TAG was
decreased slightly. In the case of the control reaction (without observed under similar conditions.
catalyst), only 60% glycerol conversion was observed, and the In order to see the effect of reaction period on the complete
esterified product mixture after 1 h of reaction was found to conversion of glycerol to DAG and TAG, the study was
contain only MAG (45%) and DAG (15%) along with 40% extended for 4 h with varying acetic acid ratio from 1:4 to 1:10,
glycerol without any TAG (Table 1). This study revealed that and the results are given in Table 1. By increasing the acetic
the carbon acid catalyst has the capability to complete the acid ratio from 1:4 to 1:8, selective esterification of glycerol to
C dx.doi.org/10.1021/ie503079m | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research Article

DAG and TAG was observed with considerable TAG content Efforts were also made to push the reaction for selective
after 3 h of reaction (Table 1). However, maximum selectivity formation of TAG by using Dean−Stark apparatus for the
of TAG obtained is 39% with 1:8 and 40% with 1:10 glycerol to azeotropic removal of water formed in the reaction. However,
acetic acid ratio even after 4 h of reaction. Whereas, for control this study also does not have any encouraging results to obtain
reaction with 1:10 ratio of acetic acid complete glycerol 100% TAG conversion even after 4 h and also with increase of
conversion was observed only after 3 h and the product acetic acid ratio from 1:4 to 1:10. From the above discussion,
composition obtained after 4 h was found to be almost similar the optimal reaction conditions in the first step for obtaining
to that of solid acid catalyzed reaction with 1:4 mol ratio of 100% conversion of glycerol to glycerol acetate derivatives is
acetic acid after 1 h. On the basis of this study, it was found that
the reaction of 1:4 mol of glycerol to acetic acid with 5 wt % of
1:4 mol ratio of glycerol:acetic acid and reaction time of 1 h is
catalyst for a period of 1 h at 115 °C temperature. After
optimum for the complete conversion of glycerol to biofuel
additives. completion of reaction, the catalyst was filtered, washed with
3.1.2. Effect of Catalyst Loading. The effect of catalyst methanol, and dried at 110 °C for 1 h to make it moisture free
loading on the complete conversion of glycerol (1 mol) to for reuse.
acetylated glycerol derivatives with acetic acid (4 mol) was 3.2. Second Step: Acetylation of Glycerol Ester
investigated by varying from 5 to 20 wt % for a period of 1 to 4 Mixture with Acetic Anhydride. In the second step,
h, and the results are correlated with control reaction (without according to Scheme 1, acetic anhydride (0.1 mol, 1:1 with
catalyst). Results in Table 2 clearly indicate that 100% respect to glycerol used in the first step) was added to the
reaction mixture of the first step after 1 h, and the reaction
Table 2. Effect of Catalyst Loading on the Esterification of continued for 4 h at 115 °C. The product obtained was found
Glycerol with Acetic Acida to contain only 50% TAG along with 50% DAG. In order to
accelerate the reaction toward 100% TAG, the esterified
catalyst (wt % of glycerol)
reaction product obtained after 1 h in the first step was
5 10 15 20 control subjected to a pretreatment step involving separation of the
time (h) product [composition (wt %) of the product by GC] catalyst by filtration and removal of excess acetic acid and water
1 glycerol - - - - 40.4 formed during esterification reaction by distillation under
MAG 22.0 22.4 14.4 12.3 44.6 reduced pressure. The pretreated product was acetylated with
DAG 67.0 66.4 71.5 73.1 15.0 acetic anhydride (9.56 mL, 0.1 mol, 1:1 with respect to glycerol
TAG 11.0 11.2 14.1 14.5 - in the first step) in the presence of 5 wt % of catalyst at 115 °C
2 glycerol - - - - 34.6 for 30 min and resulted in 100% selectivity for TAG in
MAG 20.1 15.7 11.1 9.0 21.8 quantitative yield. In the case of the control reaction, only 23%
DAG 63.4 64.8 67.2 67.4 41.2
TAG formation along with 77% DAG was observed even after
TAG 16.5 19.5 21.7 23.6 2.4
4 h indicating the efficient catalytic activity of the catalyst in
3 MAG 17.1 9.1 8.7 8.0 41.5
acetylation of MAG and DAG to 100% TAG.
DAG 61.5 67.0 66.3 66.7 54.5
Attempts were also made for the acetylation by heating a
TAG 21.4 23.9 25.0 25.2 4.0
4 MAG 12.7 7.3 4.3 3.8 31.1
mixture of glycerol with acetic acid and acetic anhydride (1:4:2
DAG 62.9 66.0 68.4 68.4 62.0 mol ratio) at 115 °C for 4 h in the presence of 5 wt % of the
TAG 24.4 26.7 27.3 27.8 6.9 catalyst and resulted in 45 and 55% of DAG and TAG,
a
Reaction conditions: glycerol (9.2 g, 0.1 mol); AcOH (23 mL, 0.4 respectively. Increase in the reaction time (4 h) and acetic
mol); T = 115 °C. anhydride content (1:2 mol with respect to glycerol in the first
step) also did not result in 100% TAG. On the basis of the
above results, the optimized reaction conditions for 100%
selectivity to TAG are esterification of glycerol with acetic acid
conversion of glycerol to biofuel additives with selectivity of (1:4 mol) using 5 wt % of catalyst at 115 °C for 1 h followed by
MAG (22%), DAG (67%), and TAG (11%) was observed with acetylation of pretreated esterified product with acetic
minimum amount of catalyst loading (5 wt %) in 1 h. Whereas, anhydride (1 mol with respect to glycerol) using 5 wt % of
for control reaction, 100% of glycerol conversion with catalyst at 115 °C for 30 min. The advantage of this protocol is
selectivity of 42% MAG, 54% DAG, and 4% TAG was obtained use of less moles of acetic acid (1:4), shorter reaction time (1
only after 3 h of reaction, thus indicating that without catalyst h), low catalyst loading (5 wt %), and easy recovery and
the esterification reaction is slow. However, selectivity of TAG reusability of the catalyst compared to the reported two-step
after 4 h in the presence of catalyst increases from 25 to 28%
synthesis of TAG.21
indicates that increase in selectivity of TAG is very little with
3.3. Reusability of Catalyst. To check the reusability of
respect to catalyst percentage and hence there is no need to go
for high catalyst loading. The highest catalytic activity signified the carbon acid catalyst, esterification reactions of glycerol with
by glycerol conversion (100%) and the highest selectivity acetic acid (1:4) were conducted at 115 °C for 1 h for five
toward MAG, DAG, and TAG attributes the acidity of the cycles (Figure 1). After each cycle the catalyst was recovered by
catalyst with enhanced surface interactions between acetic acid filtration, washed with methanol, and reused after drying in an
and glycerol. The carbon acid catalyzed esterification protocol oven at 110 °C for 1 h. The solid acid catalyst has excellent
succeeded in resulting 100% conversion of glycerol to reusability without any significant reduction in the conversion
acetylated glycerols within 1 h and was demonstrated to be of glycerol to acetylated glycerols due to its high stability
superior compared to the reported solid acid catalysts with without any deactivation and leaching under the reaction
respect to acetic acid molar ratio and reaction time. conditions.
D dx.doi.org/10.1021/ie503079m | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
Figure 1. Reusability of the catalyst on the esterification reaction with
acetic acid. (Reaction conditions: glycerol = 9.2 g, 0.1 mol; acetic acid
= 23 mL, 0.4 mol; catalyst = 0.46 g, 5 wt % with respect to glycerol; T
= 115 °C, time = 1 h).
4. CONCLUSIONS
In conclusion, the present study demonstrated excellent
catalytic activity of the glycerol-based solid acid catalyst for
the preparation of TAG in a two-step method with lower molar
ratios of acetic acid and acetic anhydride in shorter reaction
times. The optimized conditions for the complete esterification
of glycerol with acetic acid was found to be 1:4 glycerol to
acetic acid at 115 °C for 1 h followed by acetylation with one
mole of acetic anhydride for 30 min employing 5 wt % catalyst.
This protocol would be commercially feasible for industrial
applications with high selectivity and conversion rate of glycerol
to biofuel additives with outstanding recyclability of the
catalyst.
■
ASSOCIATED CONTENT
*
S Supporting Information
Glycerol-based carbon acid catalyst characterization [XRD
(Figure 1), XPS (Figure 2), FTIR (Figure 3), 13C MAS NMR
spectra (Figure 4)], effect of reaction time (Figure 5) and effect
of acetic acid mole ratio (Figure 6) on the esterification of
glycerol, and GC chromatograms of glycerol esters obtained by
esterification of glycerol with AcOH for 1 h (Figure 7a)
followed by acetylation with Ac2O for 30 min (Figure 7b). This
material is available free of charge via the Internet at http://
pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: prabhavathi@iict.res.in. Tel.: +91 40 27191845. Fax:
+91 40 27193370.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The author U.C. gratefully acknowledges the Council for
Scientific and Industrial Research (CSIR), New Delhi, India, for
the financial support as Project Research Fellow under 11th
FYP FAC project.
■
REFERENCES
(1) Zhou, C. H.; Beltramini, J. N.; Fan, Y. X.; Lu, G. Q.
Chemoselective catalytic conversion of glycerol as a biorenewable
source to valuable commodity chemicals. Chem. Soc. Rev. 2008, 37,
527−549.
E dx.doi.org/10.1021/ie503079m | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Article
(2) Behr, A.; Eilting, J.; Irawadi, K.; Leschinski, J.; Lindner, F.
Improved utilization of renewable resources: new important
derivatives of glycerol. Green Chem. 2008, 10, 13−30.
(3) Rodrigues, R.; Isoda, N.; Gonçalves, M.; Figueiredo, F. C. A.;
Mandelli, D.; Carvalho, W. A. Effect of niobia and alumina as support
for Pt catalysts in the hydrogenolysis of glycerol. Chem. Eng. J. 2012,
198−199, 457−467.
(4) Gonçalves, V. L. C.; Pinto, B. P.; Silva, J. C.; Mota, C. J. A.
Acetylation of glycerol catalyzed by different solid acids. Catal. Today
2008, 133−135, 673−677.
(5) Khayoon, M. S.; Hameed, B. H. Acetylation of glycerol to biofuel
additives over sulphated activated carbon catalyst. Bioresour. Technol.
2011, 102 (19), 9229−9235.
(6) Khayoon, M. S.; Hameed, B. H. Synthesis of hybrid SBA-15
functionalized with molybdophosphoric acid as efficient catalyst for
glycerol esterification to fuel additives. Appl. Catal., A 2012, 433−434,
152−161.
(7) Balaraju, M.; Nikhitha, P.; Jagadeeswaraiah, K.; Srilatha, K.; Sai
Prasad, P. S.; Lingaiah, N. Acetylation of glycerol to synthesize
bioadditives over niobic acid supported tungstophosphoric acid
catalysts. Fuel Process. Technol. 2010, 91, 249−253.
(8) Reddy, P. S.; Sudarsanam, P.; Raju, G.; Reddy, B. M. Synthesis of
bio-additives: Acetylation of glycerol over zirconia-based solid acid
catalysts. Catal. Commun. 2010, 11, 1224−1228.
(9) Reddy, P. S.; Sudarsanam, P.; Raju, G.; Reddy, B. M. Selective
acetylation of glycerol over CeO2-M and SO42‑/ CeO2-M (M= ZrO2
and Al2O3) catalysts for synthesis of bioadditives. J. Ind. Eng. Chem.
2012, 18 (2), 648−654.
(10) Sudarsanam, P.; Mallesham, B.; Reddy, P. S.; Reddy, B. M.
Highly promising sulfate ion promoted M-ZrO2 (M= Al2O3 and
CeO2) heterogeneous solid acids for biodiesel derived glycerol
esterification. J. Chem. Sci. Technol. 2013, 2 (3), 161−168.
(11) Wang, C.; Dou, B.; Chen, H.; Song, Y.; Xu, Y.; Du, X.; Zhang,
L.; Luo, T.; Tan, C. Renewable hydrogen production from steam
reforming of glycerol by Ni−Cu−Al, Ni−Cu−Mg, Ni−Mg catalysts.
Int. J. Hydrogen Energy 2013, 38, 3562−3571.
(12) Janaun, J.; Ellis, N. Glycerol etherification by t-butanol catalysed
by sulfonated carbon catalyst. J. Appl. Sci. 2010, 10 (21), 2633−2637.
(13) Ayoub, M.; Khayoon, M. S.; Abdullah, A. Z. Synthesis of
oxygenated fuel additives via the solvent less etherification of glycerol.
Bioresour. Technol. 2012, 112, 308−312.
(14) Rahmat, N.; Abdullah, A. Z.; Mohamed, A. R. Recent progress
on innovative and potential technologies for glycerol transformation
into fuel additives: A critical review. Renewable Sustainable Energy Rev.
2010, 14, 987−1000.
(15) Melero, J. A.; Grieken, R. V.; Morales, G.; Paniagua, M. Acedic
mesoporous silica for the acetylation of glycerol: Synthesis of
bioadditives to petrofuel. Energy Fuels 2007, 21, 1782−1791.
(16) Jagadeeswaraiah, K.; Balaraju, M.; Prasad, P. S. S.; Lingaiah, N.
Selective esterification of glycerol to bioadditives over heteropoly
tungstate supported on Cs-containing zirconia catalysts. Appl. Catal., A
2010, 386, 166−170.
(17) Silva, L. N.; Goncalves, V. L. C.; Mota, C. J. A. Catalytic
acetylation of glycerol with acetic anhydride. Catal. Commun. 2010, 11,
1036−1039.
(18) Ferreira, P.; Fonseca, I. M.; Ramos, A. M.; Vital, J.; Castanheiro,
J. E. Acetylation of glycerol over heteropolyacids supported on
activated carbon. Catal. Commun. 2011, 12, 573−576.
(19) Ferreira, P.; Fonseca, I. M.; Ramos, A. M.; Vital, J.; Castanheiro,
J. E. Glycerol acetylation over dodecatungstophosphoric acid
immobilized into a silica matrix as catalyst. Appl. Catal., B 2009, 91,
416−422.
(20) Dosuna-Rodríguez, I.; Adriany, C.; Gaigneaux, E. M. Glycerol
acetylation on sulphated zirconia in mild conditions. Catal. Today
2011, 167 (1), 56−63.
(21) Liao, X.; Zhu, Y.; Wang, S. G.; Li, Y. Producing triacetylglycerol
with glycerol by two steps: Esterification and acetylation. Fuel Process.
Technol. 2009, 90, 988−993.
Industrial & Engineering Chemistry Research Article

(22) Kang, S.; Jun, Y.; Chang, J. Recent advances in carbon-based

sulfonated catalyst: preparation and application. Inter. Rev. Chem. Eng.
(I.RE.CH.E.) 2013, 5 (2), 132−144.
(23) Prabhavathi Devi, B. L. A.; Gangadhar, K. N.; Sai Prasad, P. S.;
Jagannadh, B.; Prasad, R. B. N. A Glycerol-based carbon catalyst for
the preparation of biodiesel. ChemSusChem 2009, 2, 617−620.
(24) Prabhavathi Devi, B. L. A.; Gangadhar, K. N.; Siva Kumar, K. L.
N.; Shiva Shanker, K.; Prasad, R. B. N.; Sai Prasad, P. S. Synthesis of
sulfonic acid functionalized carbon catalyst from glycerol pitch and its
application for tetrahydropyranyl protection/deprotection of alcohols
and phenols. J. Mol. Catal. A: Chem. 2011, 345, 96−100.
(25) Prabhavathi Devi, B. L. A.; Gangadhar, K. N.; Vijayalakshmi, K.;
Prasad, R. B. N.; Sai Prasad, P. S. Glycerol-based carbon-SO3H: an
efficient and recyclable solid acid catalyst for the pre-treatment of free
fatty acid containing vegetable oils for biodiesel production. J. Lipid Sci.
Technol. 2012, 44, 126−133.
(26) Prabhavathi Devi, B. L. A.; Vijai Kumar Reddy, T.; Vijaya
Lakshmi, K.; Prasad, R. B. N. A green recyclable SO3H-carbon catalyst
derived from glycerol for the production of biodiesel from FFA-
containing Karanja (Pongamia glabra) oil in a single step. Bioresour.
Technol. 2013, 153, 370−373.
(27) Gangadhar, K. N.; Vijay, M.; Prasad, R. B. N.; Prabhavathi Devi,
B. L. A. Glycerol-based carbon-SO3H catalyzed benign synthetic
protocol for the acetylation of alcohols, phenols and amines under
solvent-free conditions. Green Sust. Chem. 2013, 3, 122−128.
(28) Vijay, M.; Prasad, R. B. N.; Prabhavathi Devi, B. L. A.
Bioglycerol-based sulphonic acid functionalized carbon: An efficient
and recyclable, solid acid catalyst for the regioselective azidolysis of
epoxides in aqueous acetonitrile. J. Oleo Sci. 2013, 62, 849−855.

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