Renewable and Sustainable Energy Reviews 74 (2017) 387–401

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser

A review on recent developments and progress in the kinetics and MARK

deactivation of catalytic acetylation of glycerol—A byproduct of biodiesel
⁎
P.U. Okoye, A.Z. Abdullah, B.H. Hameed
School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia

A R T I C L E I N F O A BS T RAC T

Keywords: The increased awareness and demand for green energy sources, such as biodiesel (BD), have impelled an
Acetylation increase in the production of its byproduct, glycerol, which is now considered an oversupplied commodity.
Biodiesel However, the excessive supply and physicochemical properties of glycerol render this compound as an attractive
Catalyst material for fine chemical synthesis, which can boost the BD market. Pathways for synthesis of fine chemicals
Deactivation
from glycerol have been proposed by a number of researchers by using different heterogeneous or homogeneous
Glycerol
Kinetics
catalysts, with the former being more environmentally benign. Glycerol acetylation pathway with acetic acid has
received increased research attention because of the vast potential applications of its products. Therefore,
studies were conducted to propose kinetic models for acetylation reaction and catalyst deactivation and
determine parameters influencing acetylation rate. This study also provides insights into assumptions of pseudo
first-order rate, PSSH, mass transfer, and diffusion limitation and discusses the future trends of catalytic
acetylation of glycerol.

1. Introduction
Fossil fuels consumed by transport and energy industries are major
sources of CO2 and constitute over 60% of global pollution [1,2].
Environmental degradation caused by CO2 released from human
industrial activities into the atmosphere has raised awareness on the
use of renewable and eco-friendly sources of energy. Alternative energy
sources, such as ethanol and biodiesel (BD), have been proposed to
avert or reduce the adverse impact of fossil fuels on the environment
[3–6]. BD has received increased research attention and commercia-
lization either as pure BD (100%) or blended with conventional diesel
to reduce CO2 emissions by 52% compared with that from fossil diesel
[7]. Triglycerides from biomass feedstocks, such as vegetable oil,
Jatropha seeds, algae, and animal fats, undergo transesterification
reaction in the presence of acid or basic catalysts to produce BD and
glycerol [8–14]. For every 100 kg of BD produced, 10 kg of glycerol is
synthesized as a by-product. Increased awareness of BD contribution in
reducing CO2 emission has led to increased production and demand for
this type of diesel. According to the OECD report [15], the projected
production of BD in 2020 is estimated to be 42 billion liters, which
translates to 4.2 billion liters of glycerol produced in the market. In this
case, glycerol becomes a readily available commodity and combines
with contaminants, namely, methanol, soap, and water, which pose
difficulties in purification, to reduce the crude glycerol market value
compared with refined glycerol [16]. These challenges create a wide
cost margin between crude and refined glycerol, as reported by Quispe
et al. [17] in their study on global glycerol market and cost analysis. For
instance, in North Asia, refined glycerol is sold at USD 0.825–0.880/
kg, whereas crude glycerol is sold at USD 0.044/kg; this cost difference
renders BD production via transesterification as unattractive.
Surplus glycerol commodity must be functionalized or upgrade to
boost the BD market [18]. To avoid difficulties in glycerol refining,
studies have focused on production of glycerol-free BD or its higher
molecular blend. Glycerol derivatives, such as monoglycerides or
glycerol carbonates, are produced when utilizing lipids and different
acyl acceptors, instead of methanol [19]. Acyl acceptors, such as ethyl
acetate [20], methyl acetate [21], and dimethyl carbonate [14], produce
three molecules of fatty acid methyl or ethyl esters and one molecule of
glycerol carbonate or glycerol triacetate (triacetin). Glycerol triacetate
or glycerol carbonate blended with FAME exhibits physicochemical
properties similar to those of biodiesel fuel and can be utilized in diesel
engines without modification. Calero et al. [22] studied recent tech-
nologies of producing glycerol-free or glycerol-blended (Ecodiesel® and
Gliperol®) BD; they reported that 100% atom efficiency can be achieved
because no glycerol is generated in situ, thereby avoiding purification
steps and saving energy. However, glycerol-free BD production is
mostly performed on a laboratory scale because it is a new field that
has yet to be fully commercialized.

⁎
Corresponding author.
E-mail address: chbassim@usm.my (B.H. Hameed).

http://dx.doi.org/10.1016/j.rser.2017.02.017
Received 5 November 2015; Received in revised form 8 December 2016; Accepted 3 February 2017
Available online 24 February 2017
1364-0321/ © 2017 Elsevier Ltd. All rights reserved.
P.U. Okoye et al.
Nomenclature
CG, ΓG Concentration of glycerol
CA, ΓA Concentration of acetic acid
CM , CW , CD, CT Concentrations of monoacetin (MAG), water, dia-
cetin (DAG), and triacetin (TAG), respectively
rs Rate of surface reaction
−dCG
dt
, −rG Rate of glycerol consumption
−dCM
, YM , −rm,r1 Rate of MAG formation
dt
−dCD
−rD, YD, , r2 Rate of DAG formation
dt
−dCT
r3, −rT , YT , dt
Rate of TAG formation
−rAA Rate of acetic acid consumption
KG, KA Equilibrium rate constants of glycerol and acetic acid,
respectively
Kd Rate constant for desorption of MAG, DAG, and TAG
KS Equilibrium rate constant for the surface reaction
K1, K2, K3 Equilibrium rate constants for the forward reactions of
three consecutive steps
K ′2 , K ′4 , K ′6 Equilibrium rate constants for the reverse reaction of
three consecutive steps
Γ Γ Γ
KEQ ,1, KEQ,2, KEQ,3 Thermodynamic equilibrium constants for three-
step reactions, K =1–3
ΓEQ, i Composition of adsorbed phase for the ith component in
the reaction
Glycerol is a highly functional material that requires defunctiona-
lization to synthesize more than a thousand fine chemicals. Pathways
such as etherification [23], oligomerization [24], dehydration [25],
dehydrogenation [26,27], glycerol oxidation [28,29], transesterification
[30], glycerol reforming [31–33], ketalization [34,35] and esterification
[36–40] have been used to synthesize fine chemicals from glycerol.
Some of fine chemicals synthesized from glycerol are summarized in
our previous study [41]. These chemicals can be directly applied as a
food-grade material for poultry livestock, as a building block material
substituted to petroleum-based propylene, and as a component for
manufacturing explosives, industrial foams and textiles and pharma-
ceutical products, such as cough syrup, toothpaste, and skin care
products.
Fine chemical synthesis using a catalyst can reduce energy require-
ments and speed up the reaction compared with high-temperature
cracking of petroleum-based products without a catalyst. Based on their
role in catalysis, catalysts have been categorized as heterogeneous,
homogeneous, and enzymes [42]. Homogeneous catalysts are used to
catalyze glycerol upgrading processes but their applications are limited
because of their low recovery rate after the reaction, corrosive effects on
reactors and pipes (acid catalysts e.g., H2SO4), non-reusability, and
environmental challenges in terms of disposal [43,44]. As such, greener
and environmentally benign catalysts from microbial organisms, popu-
larly called enzymes, are used to synthesize fine chemicals from glycerol;
enzymes exhibit a catalytic stability of up to 15 cycles of reuse, has no
corrosion effects on reactors, and can be easily separated from the
reaction media [45–47]. Enzymes can catalyze pathways involving crude
glycerol, but their use also presents serious limitations, including time-
consuming, energy-intensive reactions (takes up to 24 h for the reaction to
reach equilibrium) and high cost, especially for large-scale production
[48]. Furthermore, enzymes are easily deactivated by impurities in crude
glycerol or by-products of carboxylation during glycerol upgrading. To
address the limitations of enzymes and homogeneous catalyst, current
research focus shifts to the use of heterogeneous catalysts, which feature
reusability, easy separation from the reaction mixture, and tunability;
these catalyst can be modified through functionalization with active
groups to obtain the product with high efficiency and less corrosive
effects on reactors and pipes [13,43].
388
Renewable and Sustainable Energy Reviews 74 (2017) 387–401
Vi,1, Vi,2, Vi,3 Stoichiometric coefficient in the ith component at three-
step reactions (1−3)
N Number of experiments (3)
CA0 Initial concentration of glycerol
2
CV Concentrations of vacant sites over the catalyst surface
Cm Molar concentration of the total sites
Cc Concentration of carbon on the catalyst surface (g/m2)
A Fouling parameters that are likely to be a function of feed
rate
t Time
C′ A , C′B Concentrations of reactant A and product B
K ′ A , KB, kr Rates constants of consumption and formation of A and
B
kr Reaction rate constant
φA Fraction of the remaining active sites (activity function)
K′d Sintering decay constant
a (t ) Catalytic activity, time dependent
Sa Catalyst active surface area
Sa0 Initial catalyst active surface area
K Activated kinetic rate constant for sintering
D Dispersion of metal
Cp Concentration of poison in gas-phase feed mixture
Cp0 Constant poison concentration
n Rate decay order
Acetylation of glycerol has received increased attention because it
produces ester compounds, namely, monoacetin (MAG), diacetin
(DAG), and triacetin (TAG), which can be applied in many processes,
as summarized in Fig. 1 [49]. Studies on glycerol acetylation with acetic
acid (AcOH) showed that TAG is preferred to other esters, but its
selectivity in the reaction is lower partly because the process is
thermodynamically resistant; moreover, polar media are often formed
in situ, and reaction parameters are poorly optimized [50]. Therefore,
knowledge of acetylation kinetics will facilitate understanding of the
adsorption–desorption dynamics of glycerol acetylation for effective
optimization of reaction parameters. Elucidating catalyst deactivation
kinetics is also vital for improving reactor operation and designing of
deactivation-resistant catalysts to obtain the optimum TAG yield.
Therefore, studies were conducted to propose kinetic models for
acetylation reaction and catalyst deactivation by poisoning from the
reaction by-product (water) on TAG yield and determine parameters
influencing acetylation rate. This study also provides insights into
assumptions of pseudo first-order rate, PSSH, mass transfer, and
diffusion limitation and discusses the future trends of catalytic
acetylation of glycerol.
2. Heterogeneous catalysis for glycerol acetylation with
acetic acid
Glycerol upgrading to obtain glycerol esters occurs through reaction
with acylation agents, namely, AcOH or acetic anhydride (Ac2O) [57].
K-Montmorillonite and zeolite beta can catalyze glycerol acetylation
with Ac2O to yield 100% TAG under mild conditions (20 min at 60 °C).
AcOH and Ac2O are also combined in a two-step acetylation process to
achieve 100% TAG yield [57]. Therefore, Ac2O, a simple carboxylic acid
with two acyl groups bound to oxygen, is a thermodynamically
preferable alternative to AcOH in TAG production; the reaction
between Ac2O and glycerol proceeds exothermically and generates
negative Gibbs free energy, whereas glycerol acetylation with AcOH has
positive Gibbs free energy [50]. However, using Ac2O leads to release of
high heat of reaction, occurrence of violent reactions, and absence of
significant changes on thermodynamic parameters even at ambient
P.U. Okoye et al. Renewable and Sustainable Energy Reviews 74 (2017) 387–401

Fig. 1. Specific applications of glycerol acetylation with acetic acid and products [13,51–56].

temperature when the reaction temperature is varied [50]. Moreover,
Ac2O is a raw material for narcotic production and enlisted as contra-
band in most countries, thereby prohibiting its use even for research
purposes. In this regard, the cost of Ac2O considerably increases, and
its supply becomes relatively scarce; as such, Ac2O is impractical to use,
in contrast to AcOH, which is readily available. Furthermore, synthesis
of only TAG reduces glycerol acetyl esters analogues (MAG and DAG),
that have vital industrial applications and can be obtained from low
cost glycerol [54,55]. The acetylation reaction of glycerol with AcOH or
Ac2O is a three-step reaction, which includes MAG conversion to TAG
and releases three molecules of water as a by-product [58,59]. These
reactions are reversible and equilibrium controlled; hence, the reaction
is shifted to produce high amounts of TAG and DAG through several
approaches, such as continuous removal of in situ water molecules,
increase in reaction temperature, increase in AcOH/glycerol molar
ratio, or a combination of these methods [49,57,60]. Acetylation with
AcOH requires an oxygen electron lone pair of one hydroxyl group of
glycerol to attack a carbonyl carbon of AcOH and consequently form
MAG; thereafter, the formed MAG reacts with AcOH to form DAG and
TAG, releasing three molecules of water [58]. The schematic of the
proposed glycerol acetylation pathway with AcOH is presented in
Fig. 2. This acetylation reaction with AcOH differs from that of Ac2O,
which proceeds in two possible pathways: Aac2 mechanism, which
involves carbonyl oxygen lone pair protonation and nucleophilic attack
in carbonyl to form intermediate quaternary carbon atom; and Aac1
mechanism, in which protonation occurs at the oxygen atom of the
carbonyl group to form acylium ion [61].
The rate at which the acetylation reaction proceeds depends on
various kinetic or thermodynamic parameters, which must be opti-
mized to achieve significant yield of higher esters, namely, DAG and

Fig. 2. Mechanism of glycerol acetylation with acetic acid [62].

389
P.U. Okoye et al. Renewable and Sustainable Energy Reviews 74 (2017) 387–401

TAG. These parameters include temperature, molar ratio, catalyst
loading (i.e., number of available active sites), and speed of agitation,
which influence the reaction rate. The effects of these parameters are
studied, and their limits for specific reactions are determined.
3. Effects of influencing parameters on reaction rates
Reaction rates can be tailored to achieve the desired yield by
altering reaction parameters, such as reducing the activation energy
barrier or promoting fast molecular collision to surmount the binding
energies of the reactants. For instance, temperatures ranging from
100 °C to 120 °C are ideal for glycerol acetylation with AcOH to attain
efficient glycerol conversion and achieve the selectivity of MAG, DAG,
and TAG. In addition, glycerol/AcOH molar ratio is a key parameter to
obtain high ester yield [49,63,64]. Conversion of glycerol and selectiv-
ity of the reaction products can be calculated using Eqs. (1) and (2),
respectively.
⎛ initial mol − final mol ⎞
Conversion(%) = ⎜ ⎟ × 100
⎝ initial mol ⎠ (1)
⎛ moles of product formed ⎞
Selectivity(%) =⎜ ⎟X100
⎝ moles of substrate consumed ⎠ (2)
Several studies speculated that acetylation does not involve external
mass transfer limitation. This assumption can be validated using
appropriate kinetic and thermodynamic studies of the acetylation
process. As such, acetylation kinetics must be studied using process
data incorporated with influencing parameters to determine the effects
of these parameters on reaction rate and optimize them to obtain high
yields of DAG and TAG. Table 1 presents catalysts used in various
studies with their corresponding reaction conditions, selectivity of
acetyl esters (MAG, DAG, and TAG), and glycerol conversion. The
combination of highly acidic condition, an AcOH/glycerol molar ratio
of 6:1–9:1, and reaction temperatures between 80 and 115 °C results
in high DAG and TAG selectivity and glycerol conversion. Typically,
trial and error experiments are conducted to determine the effect of
each reaction parameter on the reaction rate; in these experiments, all
parameters are kept constant while varying the parameter under
investigation. The results are then validated using kinetic rate laws or
other statistical modeling techniques.

Table 1
Heterogeneous catalyst applied in glycerol acetylation, reaction conditions, and selectivity.

Catalyst Acidity Reaction Parameters Selectivity (%) Ref.

(mmol/g)
Catalyst Loading Molar ratio Temp. Reaction time MAG DAG TAG Glycerol
(g) (AcOH: GL) (°C) (h)

Amberlyst-15 4.7d 5w% 6:1 105 10 0 12.3 83.9 100 [40]

Amberlyst-70 2.55d 5w% 6:1 105 10 0 7.5 87.6 100
STA/S11 0.274 5w% 6:1 105 10 1 55.5 35.8 100
STP/S11 0.1549 5w% 6:1 105 10 4.9 71.3 21.8 100
TPA3/MCM-41 0.627 0.15 6:1 100 6 25 60 15 87 [51]
TPA3/ZrO2 0.840 0.15 6:1 100 6 60 36 4 80
PMo3_NaUSY – 0.2 10.5:1 – 3 37 59 2 68 [54]
PW2_AC – 0.2 16:1 120 3 25 63 11 86 [56]
Amberlyst-15(dried) 4.7 2.65 9:1 110 5 7.8 47.7 44.5 97.1 [59]
Amberlyst-15(wet, moisture – 2.65 9:1 110 5 18.5 43.2 38.3 93.5
3.2%)
Blank (without catalyst) – – 9:1 110 4.20 84.7 13.8 1.5 73.5
SBAH-15(15)j 0.86 0.4 6:1 110 3 14 67 19 100 [63]
S-Mo(15) 0.69 0.4 6:1 110 3 38 53 9 74
AC-SA5 0.890 0.8 8:1 120 3 38 28 34 91 [64]
Amberlyst-15 4.9 0.64 6:1 80 8 21.1 63.8 15.1 100 [65]
Silica-alumina 3.2 0.64 6:1 80 8 88.5 11.2 0.3 71
HUSY 0.9 0.64 6:1 80 8 72.7 25.7 1.6 94
PrSO3H-SBA15 1.2 0.64 6:1 80 8 15.8 64.6 19.6 100
HPMo/SBA15 0.6 0.64 6:1 80 8 77.1 22.0 0.9 96
HPMo/Nb2O5 0.7 0.64 6:1 80 8 81.8 17.5 0.7 87
SCZ 4.1 0.64 6:1 80 8 84.7 14.8 0.5 81
SO3H-SBA15 0.8 0.64 6:1 80 8 11.1 61.9 27.0 100
SO3H-Cell 1.3 0.64 6:1 80 8 37.6 55.0 13.4 100
Amberlyst-36 5.4 0.25 1:8 105 10 70.3 4.5 – 95.6a [66]
Aamberlyst-15 4.7 0.25 1:8 105 10 70.3 2.5 – 95.3a
Dowex-2 4.8 0.25 1:8 105 10 80.8 5.1 – 95.2a
Dowex-4 – 0.25 1:8 105 10 71.6 4.2 – 94.8a
Dowex-8 – 0.25 1:8 105 10 72.9 4.7 – 94.7a
Amberlyst-15 0.0042 0.47b 3:1 110 0.5 31 54 13 97 [67]
K-10 0.0005 4.0b 3:1 110 0.5 44 49 5 96
Niobic Acid 0. 0003 6.3b 3:1 110 0.5 83 – – 30
HZSM-5 0.0012 1.6b 3:1 110 0.5 83 10 – 30
HUSY 0.0019 1.1b 3:1 110 0.5 79 14 – 14
Ar-SBA-15 1.15c 0.2 9:1 125 4 15 e 47 e 38 e 96e [68]
F-SBA-15 1.04c 0.2 9:1 125 4 14 e 50 e 36 e 90e
Pr-SBA-15 0.30c 0.2 9:1 125 4 17 e 44 e 39 e 80e

a=conversion of acetic acid.

b=catalytic loading to achieve 2 mmol of acid sites in each experiment.
c=meq/g (miliequilvalent/gram).
d=eq/kg (equivalent/kilogram).
e=the estimated values obtained from the bar plot.
j=modified with P123 and Brij S100 surfactant.

390
P.U. Okoye et al.
3.1. Effect of reaction temperature
Glycerol esterification with AcOH to convert MAG into TAG is a
highly endothermic reaction and requires large amount of heat to drive
the reaction. This phenomenon explains why MAG formation is
dominant at low temperatures, whereas high concentrations of DAG
and TAG are produced at high temperatures. Zhu et al. [49] determined
the effects of temperature on acetylation product distribution by using
HPA-supported zirconia catalyst. The results showed that an increase
in temperature from 60 °C to 120 °C increases glycerol conversion from
54% to 100% and enhances selectivity of DAG and TAG compared with
reduced selectivity of MAG. Testa et al. [69] and Patel and Singh [51]
also reported a similar pattern in their studies using different solid
heterogeneous catalysts and reaction conditions. However, no signifi-
cant changes were observed in the selectivity of DAG and TAG, and
glycerol conversion at temperature above 120 °C. This finding implied
that equilibrium is rapidly attained because of fast reaction rates.
Mufrodi and Sutijan [58] indicated that TAG selectivity decreases at
reaction temperatures higher than 115 °C because of uncontrolled
evaporation of AcOH, which boils at 118 °C. In addition, the choice of
catalyst is critical in temperature studies because heat can deactivate
thermally unstable catalysts. For instance, Amberlyst-15, a sulfonic
acid resin, is thermally unstable when operated around 120 °C and
results in a sharp decrease in catalytic activity [57]. As such, the effect
of temperature on reaction rates can be determined by validating
experimental runs of various temperature ranges (e.g., 60–120 °C)
with Arrhenius equation, as presented in Eq. (3). The equation shows
the relationship between intrinsic temperature and equilibrium con-
stants and thus can be used to obtain rate law parameters in constant
volume batch reactors, creep rates, and other thermally induced
reactions.
K = Ae−Ea / RT
−1 −1
where Ea (kJ/mol) is the activation energy, R (J mol K ) is the gas
constant or the Boltzmann constant obtained by multiplying with T
(°C), K is the reaction rate constant, and A(s−1 for the first-order
reaction) is the frequency factor, which varies with the rate order and
has the same unit as the rate constant. Based on Eq. (3), an increase in
temperature or a decrease in activation energy (when catalyst is
applied) will result in increased rate constant, which is directly
proportional to the rate of the reaction. RT is the average kinetic
energy, and the exponential term, which is the ratio of Ea and RT ,
implies that large ratios correspond to low rate constants and explains
the negative sign. Hence, the rate constant K is the number of
molecular collisions per second, the pre-exponential factor A is the
sum of all collisions, and e−Ea / RT is the probability that a collision will
result to a reaction.
3.2. Effect of AcOH/glycerol molar ratio
The stoichiometric equation of glycerol/AcOH in the acetylation
reaction with bimolecular consecutive steps suggests that three molar
AcOH is required to react with one molar glycerol to convert MAG into
TAG. Previous studies showed that AcOH molar ratio above the
stoichiometric value is required to achieve high DAG and TAG
formation in the product distribution. Zhou et al. [59] investigated
the effects of glycerol/AcOH molar ratio (varying from 3:1–9:1, AcOH/
glycerol). The results showed that molar ratio as high as 9:1 could not
result in 100% TAG selectivity because of thermodynamic limitations
caused by in situ aqua media, which hinder AcOH consumption (only
74% of AcOH was consumed at the end of reaction). As such, a reactive
distillation process should be used for continuously removing the water
by-product to positively shift the equilibrium toward fast and enhanced
TAG formation. Moreover, Dean–Stark apparatus can be used to
remove in situ water. Similarly, other studies demonstrated the
influence of glycerol/AcOH molar ratio on acetylation toward increas-
Renewable and Sustainable Energy Reviews 74 (2017) 387–401
ing the rates of DAG and TAG formation [53,59,65].
Equilibrium molar concentrations are measured when a single
reaction attains equilibrium. The concentrations of all molecules
involved in the reaction are measured, and the ratio of product
concentration to reactant concentration is then calculated. AcOH/
glycerol molar ratio with excess AcOH affects the equilibrium time
and can delay the equilibrium product distribution of the ester
products; glycerol concentration exhibits major effects on ester dis-
tribution and reaction time. Equilibrium constants are the same for a
given reaction (liquids and solids) and independent of initial concen-
tration, which ideally determines the reaction rate; however, Zhou et al.
[59] reported that rate constants are independent of the initial
concentrations, and that varying AcOH/glycerol molar ratios results
in different K-values. This behavior is attributed to the nonlinear
relationship or physical interactions that possibly occur at the mole-
cular level. Melero et al. [68] observed through a 3D response surface
methodology that glycerol/AcOH molar ratio is a predominant factor
that influences high TAG selectivity. The optimal molar ratio for DAG
formation is 1:6; beyond which, selectivity declines because DAG is
converted into TAG.
3.3. Effect of catalyst loading
Although Arrhenius equation does not show the explicit relation-
ship between catalyst and reaction rate, elementary chemistry shows
that chemical reactions proceed by forming charged ions at a high
energy level to overcome the activation barrier. High temperature input
enhances molecular collision and bond dissociation and eventually
surmounts the activation barrier, leading to the formation of a highly
energy-intensive reaction; as such, catalysts with active centers are
established to enhance the formation of the charged ions, thereby
reducing the activation energy barrier and speeding up reaction rates.
(3)
In glycerol acetylation with AcOH, the catalyst enhances the formation
of acylium ion moiety, which undergoes electrophilic attack on the
hydroxyl group of glycerol. The active centers of the catalysts are
usually anionic radicals of the so-called super acid groups (e.g., sulfuric
or sulfonic acids, nobic acids, and phosphoric acids); the activity of
these radicals is directly related to their pore channel structure, nature
of the acid group, and acid strength [68].
Functionalization using super acids reduces the specific surface
area of the catalyst support material and may likely block the catalyst
pore channel, thereby reducing catalytic activity; these acids also
agglomerate and tend to be loosely bound on the catalyst surface
(depending on the synthesis technique), resulting in leaching of the
active groups and undesired homogeneous catalysis [70]. The effects of
acidity on selectivity and conversion are discussed in Section 3.4.
Although glycerol acetylation with AcOH can proceed without a catalyst
and generates more than 70% MAG yield, glycerol conversion is very
low and the desired products, namely, DAG and TAG, are not produced
[68]. Therefore, heterogeneous acid catalysts, which favor glycerol
acetylation with AcOH, must be applied, considering that high glycerol
conversion ( > 90%) and higher acetyl esters are desirable.
Catalysts such as AC-SA5 [64], sulfonic Amberlyst resins [59,66],
HPA-functionalized zirconia [49], WO3 polypyrrole [71], and dodeca-
molybdophosphoric acid-functionalized USY zeolite [54] have been
applied in acetylation reactions. Khayoon and Hameed [64] reported
that an increase in catalyst loading from 0.2 to 0.8 g linearly increases
the selectivity of DAG and TAG as a result of increased number of
available active sites; however, saturation was attained at 0.8 g loading
without significant changes in selectivity recorded. Similar results were
reported by other studies [63,67,72].
3.4. Effect of surface acidity
Few studies have assessed the effect of catalyst surface acidity,
surface strength, and type of acid site on the rate of glycerol acetylation
391
P.U. Okoye et al.
with AcOH. Existing studies indicate that acid density and acid
strength of heterogeneous solid catalysts are vital in tailoring acetyla-
tion reaction to obtain high yields of DAG and TAG [73]. Surface
acidity can be described by determining acid strength and number of
acid centers. Typically, acid strength can be determined through
neutralization titration for Bronsted acidity [74], temperature-pro-
grammed desorption of ammonia (NH3-TPD) for total acidity, and
temperature-programmed desorption of acetonitrile (CH3CN-TPD) for
Lewis acidity [75,76]. Inabe et al. [65] reported that acid strength
affects the rate of acetylation because it increases intrinsic glycerol
conversion turnover rate. However, comparison of different solid acids
showed that the proportional correlation between acid strength and
glycerol turnover rate is not valid; PrSO3H-SBA15 and Amberylst
catalysts with moderate acidity (4.9 and 1.2 mmol/g, respectively)
exhibit superior selectivity of TAG. These findings are attributed to the
spatial arrangement and configurations of surface acid moieties. The
turnover rate (h−1) for glycerol conversion is the ratio of moles of
converted glycerol for each product species (MAG, DAG, and TAG) per
−1
unit catalyst amount and time (mol .gcat *h−1) to the acidity of the catalyst
−1
(mol .gcat ) [65].
The preferred acid strength range is Bronsted acidity to obtain high
selectivity of combined DAG and TAG. Previous studies indicated that
Bronsted acidity results in superior glycerol conversion and selectivity
of acetylation products compared with Lewis acids [62]. For instance,
the Bronsted acidity (0.405 mmol/g) of 20% (w/w) Cs-DTP/K-10
catalyst can be ascribed to its higher DAG and TAG selectivity and
glycerol conversion compared with UDCaT-4 and −5 catalysts with
higher Lewis acidity (0.582 and 0.560, respectively) [62]. Konwar et al.
[61] evaluated the effects of catalyst acidity for glycerol acetylation with
acetic anhydride by using the same amount of active sites; they
reported that TAG selectivity increases with increasing surface acid
density, regardless of fixed catalyst amount. Furthermore, Khayoon
et al. [77] reported a higher selectivity for combined DAG and TAG
(34% and 55%, respectively) by using Y/SBA-3 catalyst compared with
SBAH-15 and the sulfated activated carbon AC-SA5 under the same
conditions. The superior catalytic activity of Y/SBA-3 is ascribed to its
surface acidity, which decreases in the order of Y/SBA-3 > SBA-15 >
AC-SA5 (1,342, 960, and 890 μmol/g, respectively). The derived rate
kinetic model (Table 2) incorporates the concentration of vacant sites
2 surface.
over the catalyst surface CV , which depends on surface acidity;
hence, reaction rate is influenced by catalyst acid strength. Moreover,
Khayoon and Hameed [63] used hybrid silica templated with molyb-
denum acid, SBAH15(15), and pure silica support in their study and
reported that catalytic activity depends on acid density as well as on
surface acidity and type of support material. The hybrid SBAH15(15)
with a surface acidity of 0.86 mmol/g exhibits superior catalytic activity
compared with S–Mo (acidity=0.69 mmol/g).
3.5. Effect of agitation speed
Acetylation of glycerol with AcOH and catalysts is a liquid–solid
slurry reaction that involves external mass transfer from the bulk liquid
phase to the catalyst, followed by intra- and inter-particle diffusion,
adsorption, reaction, and desorption of the products. These inter- and
intraphase diffusion of the reactants encounters mass-transfer resis-
tance, which results in slow or decreased yield. Various techniques can
be used to eliminate or determine if the acetylation reaction is mass
transfer-controlled or -limited. A plausible method is by conducting
experiments to determine interphase mass-transfer resistance by
varying the agitation speed, e.g., from 300 to 1200 rpm. The data
obtained for each agitation speed are plotted for comparison, and
overlapping of the plotted data indicates negligible mass-transfer
limitations. Meanwhile, intraphase mass-transfer limitations can be
determined through blank experiment (nonreactive) using water,
catalyst, and glycerol [78]. Koros and Nowak [79] proposed a technique
392
Renewable and Sustainable Energy Reviews 74 (2017) 387–401
for measuring if a heterogeneous catalytic reaction is limited by heat or
mass transfer by using the same catalyst dispersion; however, various
loadings and comparison were performed under the same glycerol
conversion, where the observed similar turnover frequency indicates
that the reaction rates are not subjected to mass- or heat-transfer
limitations [51,80]. Moreover, crushing the synthesized catalyst to fine
powder (125–180 μm ) can enhance mass transport and eliminate
intraparticle mass-transfer limitation [65]. Gelosa et al. [78] studied
the difference between transport time and reaction time by monitoring
the concentration of the liquid phase during the reaction through gas
chromatography. When the characteristic reaction time is 1 h, the mass
transport process is about 10 min; this finding indicates that intra-
phase mass-transfer limitations can adversely affect the reaction rates.
To study the effect of mass-transfer limitations on bimolecular
reactions, models using the Wilke–Chang equation [78,81,82] or
Scheibel relation [83] are used to determine the diffusivity of the
reactants and products from the catalyst pores. In glycerol acetylation,
the stoichiometric value of AcOH is in excess of glycerol; therefore, the
reaction is very likely to encounter external mass-transfer resistance,
which may occur from the bulk liquid phase to the catalyst surface, or
an intraphase diffusion limitation, which can be determined using the
Glueckauf pore diffusion model [84]. Therefore, a similar case pre-
sented by Yadav et al. [85–87] can be adopted in the acetylation
process for a solid–liquid reaction to evaluate external mass-transfer
resistance, as presented in Eqs. (4)–(7).
G + xAcOH ←⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ Products
solid catalyst (4)
Overall, glycerol acetylation with AcOH is represented as a single-
step reaction, which generates products such as MAG, DAG, and TAG.
where x is the stoichiometric ratio of AcOH (AcOH), which is ideally
3 mol, and G is glycerol.
RG = ∅SL − G aP*{[G0] − [GS ]} (5)
Rate of mass transfer of glycerol G from bulk liquid to the catalyst
surface.
x
RAA = ∅SL − ACOH ap{[AcOH0 ] − [AcOHs]x } (6)
Rate of mass transfer of AcOH, RAA from bulk liquid to the catalyst
=Rexp (7)
Rate of reaction calculated from the experimental observations ,Rexp .
where [G0]and[GS ] are the glycerol concentrations in the bulk and
solid phases, respectively; [AcOH0 ]x and [AcOHs ]x are the AcOH concen-
tration in the bulk and solid phases, respectively; ∅SL is the diffusion
coefficient for glycerol and AcOH; and ap is the surface area per unit
volume.
Yadav and Krishnan [86] derived mathematical models on mechan-
isms controlling the rate of diffusion for different reaction scenarios,
where case 1,CG 0 / CAA0≠1 (molar ratio of glycerol/AcOH not equal to
unity), is applicable to the acetylation reaction. Therefore, the inverse
of the observed rate must be higher than that of the glycerol and AcOH
rates to ascertain that external mass-transfer limitations are negligible:
1 1 1
≫ and
Rexp ∅SL − Gap[G0] ∅SL − AcOHap [AcOH0 ]x (8)
Surface area per unit volume, aP , can be calculated from Eq. (9); the
mass transfer coefficients for glycerol and AcOH can be obtained from
the Sherwood relation (Eq. (10)), assuming a low limiting value, which
is typically 2 [87].
6w
ap =
ρp × dp (9)
where w is the catalyst loading per unit liquid volume, ρp is the density
of particle, and dp is the surface area of the particle.
 Table 2
Kinetic models and rate mechanisms in glycerol acetylation with AcOH.

Catalyst Derived kinetic model Activation energy Rate order Rate Reaction Reaction Remarks Ref
(KJ/mole) mechanism regime conditions
P.U. Okoye et al.

H2SO4 −rm = k1CGCA − K ′2 CM CW − K3CM CA + K ′4 CDCW E1=3.94 1st order Power model – AcOH/Gly=3:1, The activation energy is similar [58]
−rD = k 3CM CA − K ′4 CDCW − K5CDCA + K ′6 CT CW E2=33.8012E3=51.7679 1.5 h, 100– to Cs-DTP/K−10 catalyst and
−rT = k5CDCA − K ′6 CT CW 120 °C, catalyst suggest that power model have
−rG = −k1CGCA − K ′2 CM CW loading= 2.5 w/w a trend in activation energy of
% three consecutive step reaction.
−rAA = −k1CGCA + K ′2 CM CW − K3CM CA + K ′4 CDCW − k5CDCA + K ′6 CT CW
However, the activation energy
values are not similar as
different reaction conditions
and catalysis was applied.

Amberlyst−15 CM K1K2 E1=57.26 Homogeneous LHHW Surface AcOH/Gly=3:1– Contrarily, the above [59]
YM = = [e−k 2t − e−k1t ]
CA0 K1 − K2 E2=31.87 1st order controlled 9:1, 6 h, 80– assertions, activation energy
CD K1K2 ⎡ e−k 2t − e−k 3t e−k1t − e−k 3t1 ⎤ E3=13.90 110 °C, catalyst increased in opposite direction
YD = = ⎢ K −K − ⎥ loading= 2.645 g in this study. Although no
CA0 K1 − K2 ⎣ 3 2 K3 − K1 ⎦
explanation of the possible
CT K1 K1K2 ⎡ e−k 2t − e−k 3t e−k1t − e−k 3t1 ⎤
YT = =1−e−k1t − [e−k 2t − e−k1t ] − ⎢ K −K − ⎥ causes was offered, however,
CA0 K1 − K2 K1 − K2 ⎣ 3 2 K3 − K1 ⎦
phase interactions between the
reactants and products, and
conditions of the reactions may
have likely favored TAG
formation and resulted in a
lower activation energy
compared to DAG and MAG.

393
Cs-DTP/K−10 −dCG
= K1CGCAW −K1CM CW W E1=45.35 1st order Power model Surface AcOH/Gly=9:1, Activation energy increases [62]
dt E2=57.28 controlled 4 h, 120–180 °C, from E3 > E2 > E1, implying
−dCM
= K1CGCAW −K1CM CW W −K2CM CAW +K2CDCW E3=80.5 catalyst loading= that increase in temperature
dt
−dCD 0.01 g/cm3 from 120 to 180 °C affects the
= K2CM CAW −K2CDCW W −K3CDCAW +K3CT CW W glycerol
dt rate. Also, the high activation
−dCT energy in E3 , indicates that
= K3CDCAW −K3CT CW W
dt
conversion from DAG to TAG is
most sensitive to temperature
changes and confirms the low
selectivity of TAG.
Y/SBA−3 2 21.54 PSSH LH Surface AcOH/Gly=4:1, Treated as one-step reaction, [77]
CV ⎛ Kd (CM + CD + CT ) ⎞
rs = ⎜K K C C − ⎟ controlled 2.5 h, 100– with an overall activation
Cm ⎝ G A G A KS ⎠
120 °C, catalyst energy which do not have any
loading= 0.4 g physical meaning as relates to
temperature or molar ratio.
2
However, CV term incorporates
mass transfer and intra-
particle limitations term used
to evaluate the reaction regime.

Amberlyst−15a Vi,1 ᴦ E1=62.8 1st order LH Mass AcOH/Gly=3.9, Also, the Amberlyst−15 [78]
r1 = K1ᴦ Gᴦ A[1−∏iN=1 (ᴦ EQ, i) /KEQ,1]
E2=17.57 transfer 0.5 h, 80 °C, activation energies are close in
Vi,2 ᴦ E3=18.41 controlled catalyst loading= values and trend to this study.
r2 = K2ᴦ Gᴦ A[1−∏iN=1 (ᴦ EQ, i) /KEQ,2]
N Vi,3 ᴦ
15 wt% TAG selectivity was favored in
r3 = K3ᴦ Gᴦ A[1−∏i =1 (ᴦ EQ, i) /KEQ,3] this case as reactive
chromatography was used to
remove in situ water formed in
the reaction media.
Renewable and Sustainable Energy Reviews 74 (2017) 387–401
P.U. Okoye et al.
shi = ∅SLi × id / Di
p (10)
where i is either AcOH or glycerol, D is the diffusivity value, sh is the
Shearwood value, and ∅SLi is the diffusion coefficient for the ith compound.
4. Kinetics of glycerol acetylation with acetic acid
The kinetics of acetylation reaction with AcOH has received
minimal research attention. Thus far, only a few kinetic studies on
acetylation with heterogeneous catalysts were conducted
[59,72,77,84,85,87–89]. Reactants are usually adsorbed in the catalyst
active centers, where protonation occurs. The rate of adsorption of
these reactants is proportional to the fraction of the unoccupied active
sites on the catalyst, and the partial pressure of the component in the
gas phase and species adsorption only occur at monolayer coverage.
Acetylation reaction of glycerol and AcOH is a parallel consecutive
three-step reaction from MAG to TAG; therefore, developing an
intrinsic kinetic model of the process relies on observed experimental
data. Kinetic analysis for acetylation process involves rate-determining
steps (RDSs), which are expressed in terms of reactant and inter-
mediate concentration; in RDS, the gas-phase concentrations of the
reactants and products are directly related to the concentrations of the
intermediates, a phenomenon called adsorption isotherm. Changes in
concentration with respect to time, which are used to determine
reaction rate constant and reaction order, are analyzed by applying
differential, regression, integral, or least square methods. These
analytical or statistical techniques provide insights into the dynamics
of the underlying process.
Effect of reactant concentration on the reaction, diffusion limitations,
and various mass transfer scenarios are evaluated using different
mechanisms or approaches, such as simple power law [58,62,90,91],
Eley–Rideal mechanism [92], neuclophilic substitution mechanism [89],
Langmuir–Hinshelwood (LH) mechanism or formalized Langmuir–
Hinshelwood–Hougen–Watson (LHHW) model [48–52]; these mechan-
isms are usually adopted to describe the process kinetics for a given
reactor system. Pengyong and Zuhairi [89] derived and compared these
mechanisms (e.g., simple power law, neuclophilic substitution mechan-
ism, Eley–Rideal mechanism, and LH mechanism) to investigate the
esterification reaction of glycerol with lauric acid. The derived models are
based on different assumptions deemed theoretical for model simplifica-
tion; as such, insights can be gained over the surface coverage of
intermediates, surface reactions, and reaction influencing parameter
correlations [93]. The LH or LHHW is the most popular of these derived
kinetic models for acetylation reaction [59,72,77,84,85,87–89]; this
model optimally describes the process with high reliability and accuracy
and involves equations that can be well-fitted to kinetic data [89]. In the
acetylation reaction of glycerol with AcOH, assumptions are made to
simplify the rate equation derivations, as summarized below
[59,72,77,84,85,87–89]:
1. Glycerol is assumed as a limiting reactant because AcOH is in excess
and cannot be completely consumed during the reaction.
2. Pseudo first-order reaction is proposed under isothermal condition.
3. The rate of forward reaction is faster than that of backward reaction,
thereby reducing the reaction rate constants to three for easy kinetic
calculation.
4. The catalyst amount throughout the study is constant.
5. The catalytic surface reaction is faster than that of the bulk liquid;
therefore, the reaction regime is surface controlled and not kineti-
cally controlled.
6. The adsorption and desorption of the reactants as well as the
products are very fast and at equilibrium.
7. The acetylation reaction is irreversible.
8. The adsorption of the main reactant is weak; thus, the resistance
term in the LHHW model can be ignored.
9. No external mass-transfer limitation exists.
394
Renewable and Sustainable Energy Reviews 74 (2017) 387–401
LHHW is oversimplified from these assumptions, and its kinetic
parameters derived from the fitted experimental data has no physical
meaning and cannot be used to theoretically distinguish MAG and DAG
types (i.e., 1-monoacetin, 2-monoacetin, 1,3-diacetin, and 1,2-diacetin)
[94,95]. Therefore, density functional theory (DFT), molecular dy-
namics, and Monte Carlo (MC) simulations are adopted for modeling of
heterogeneous catalytic reactions to incorporate molecular data into
modeling of reactors [50,98]. DFT provides molecular information that
can be fed into MC simulations, where surface reaction rates can be
computed as a function of fluid-phase partial pressure, adsorbate
structure, and temperature [98]. Furthermore, these methods can be
applied to determine the most stable types of MAG and DAG. However,
the evolved reaction rates are yet to be applied in models tractable to
simulations of technical systems.
Most AcOH esterification reactions assume the surface reaction as
the RDS [59,77,88,99], and that LH mechanism assumptions are often
based on pseudo-steady state hypothesis (PSSH) and imply the
presence of relatively low-surface species activity; therefore, the
reaction mechanism must be proposed based on small concentrations
of the active sites [100]. However, the active site concentrations of
heterogeneous catalysts are difficult to determine because they are
mostly replaced by the total exposed surface area, which causes
misleading results. Moreover, most heterogeneous catalysts, especially
acetylation catalysts (zeolites, activated carbon, and functionalized
zirconium), which require high Bronsted acidity and surface area, do
not fulfill the PSSH conditions (concentrations of the active sites must
be less than one tenth of the highest reactant concentration) [94].
Therefore, if the PSSH criterion for LH kinetics is not satisfied, then the
experimental parameters can only be used in the region of the reported
experiment and its evolved kinetic parameters are reduced to only
curve-fitting parameters; this phenomenon is clearly reported in Ref.
[88], and additional details can be found in Ref. [100].
Heterogeneous catalytic reactions are either kinetically, surface, or
intraparticle controlled. In particular, glycerol acetylation with AcOH
reaction regime is assumed to be surface controlled, and assumptions
on negligible intraparticle diffusion or mass transfer resistance, which
influences the reaction rates without validation, is likely to result in
wrong kinetic representation of the system. For instance, in the kinetic
studies of acetylation process by Zhou et al. [59], the resistance term of
LHHW was ignored and AcOH was assumed to be completely
consumed because it is in excess during the reaction; hence, AcOH
concentration is constant in the catalyst sites. Different K-values were
obtained at different initial AcOH/glycerol molar ratios, which can be
attributed to the physical-phase interaction of the reactants and
products and to the ignored mass transfer or intraparticle resistance
effects. Therefore, the external mass transfer resistance in acetylation
must be validated using the methods explained in a previous study
[86]. Furthermore, kinetics study of acetylation reaction of glycerol
with AcOH has not considered intraparticle diffusion and but assumes
constant catalyst loading. Internal diffusion or Weber and Morris
model [101], which is vital in determining the adsorption rate for
liquid–solid systems, can be utilized to evaluate the influence of
intraparticle diffusion resistance by varying catalyst loading at a fixed
particle size and constant temperature with the Weisz–Prater criterion
described in Ref. [102].
Acetylation from MAG to TAG is a reversible reaction and involves
six rate constants, three each for forward and backward reactions. The
rate equation derived from the three consecutive acetylation reaction
shown in Eqs. (11)–(13) is presented in Eqs. (14)–(19) [58].
K1
G + AcOH ↔ MAG+H2O
K2 (11)
K3
MAG + AcOH ↔ DAG+H2O
K4 (12)
P.U. Okoye et al.
K5
DAG + AcOH ↔ TAG+H2O
K6 (13)
rG = −K1[G ][AcOH ] + K2[M ][W ] (14)
rAA = −K1[G ][AcOH ] + K2[M ][W ] − K3[M ][AcOH ] + K4[D][W ]
− K5[D][AcOH ] + K6[T ][W ] (15)
rM = K1[M ][AcOH ] − K2[M ][W ] − K3[M ][AcOH ] + K4[D][W ] (16)
rD = K3[M ][AcOH ] − K4[D][W ] − K5[D][AcOH ] − K6[T ][W ] (17)
rW = K1[G ][AcOH ] − K2[M ][W ] + K3[M ][AcOH ] − K4[D][W ]
+ K5[D][AcOH ] − K6[T ][W ] (18)
rT = K5[D][AcOH ] − K6[T ][W ] (19)
where G is glycerol, AcOH is acetic acid, K1–K6 are rate constants of
forward and backward reactions, M is MAG, D is DAG, T is TAG, and W
is water.
Although these equations can be solved to obtain the six rate
constants for forward and reverse reactions, the formed assumptions
stated that the rates of reverse reactions are less than the forward
reaction, thereby reducing the rate equation to three. Table 2 shows the
summary of derived kinetic models from different rate mechanisms
with remarks. In Ref. [58], a small reverse rate constant was obtained
than the forward rate constant, which validates the assumption of
neglecting the backward rates. In addition, conducted thermodynamics
studies on glycerol acetylation with AcOH at 105 °C indicated that
when the Gibbs free energies of the three-step reaction are all positive,
those of acetylation with acetic anhydride are negative; hence, glycerol
acetylation with acetic anhydride is thermodynamically favored than
AcOH [50]. Moreover, the Gibbs energies of MAG and DAG reaction
steps are relatively lower than those of TAG, explaining the usual slow
selectivity or yield of TAG. Varying the reaction temperature to alter
equilibrium rate constant and shift Gibbs free energy does not
significantly change TAG selectivity. Gibbs free energy is energy change
associated with substance formation at their most stable form (ele-
ments of the substance) under standard conditions of 1 atm and 25 °C
[103]. Therefore, assuming that only glycerol is adsorbed on the
catalyst surface (as AcOH is used in excess, its concentration is
assumed as constant during the reaction course) and considering the
external and internal mass-transfer limitations for the solid–liquid
reaction system, the rate at which glycerol is consumed is shown in Eq.
(20).
dXG
− = kmam(XG, b − XG, s )
dt (20)
where km, am , XG, b , XG, s are the mass transfer coefficient, the catalyst
external surface area, the bulk concentrations, and the solid catalyst
phase, respectively. Assuming that the reaction rate is faster in the
catalyst surface than that in the bulk liquid phase and solving Eq. (20),
the linear equation form can be derived; this equation explains the
fractional conversion of glycerol and solves the mass transfer coeffi-
cient km from the slope of the plot (details of complete mathematical
derivation are presented in Ref. [77]). Eq. (21) represents glycerol
concentration as a function of the fractional conversion of glycerol θG
and the initial glycerol concentration XG0 :
XG = XG 0(1−θG ) (21)
5. Kinetics of catalytic deactivation in glycerol acetylation
Loss of catalytic activity with time during the acetylation reaction of
glycerol with AcOH is a major drawback that slows the industrial
application of heterogeneous catalysts. This loss of activity, called
395
Renewable and Sustainable Energy Reviews 74 (2017) 387–401
deactivation, can be physical, chemical, or both and occurs in many
categories, such as poisoning, coking or fouling, possible mechanical
failure because of attrition or erosion, thermal degradation, and phase
transformation [104]. Catalyst deactivation is inevitable [105] but can
be slowed or avoided in some cases by removal or inhibiting the
formation of identified deactivating agents. Catalyst deactivation in
glycerol acetylation with AcOH commonly occurs as a result of reduced
surface area caused by mechanical handling, attrition or functionaliza-
tion of the support, thermal degradation of Amberlyst resins, poison by
in situ formed water, leaching of active functional groups from the
catalyst surface, and carbon deposition in the active centers of the
catalyst [49,57,69,71,73,106,107]. For instance, utilizing Amberlyst
resins above the stated temperature limits can lead to decomposition of
the sulfonic functional groups, followed by loss of surface area and
reduced activity or complete loss of activity [108]. Furthermore, in situ
water molecules, which are a reversible poison, are selectively adsorbed
in the Amberlyst active sites, thereby reducing the number of active
sites for adsorption and can lead to possible hydrolysis of the formed
esters.
Understanding the deactivation mechanism is vital for design of
deactivation-resistant catalysts, development of methods for regener-
ating deactivated catalysts, and improvement of the operation of
industrial chemical reactors. The duration of catalyst life cycle for a
given chemical process can be evaluated using reusability test on the
synthesized catalyst. Four cycles and above are usually used, and loss of
activity is recorded. Moreover, leaching or homogeneity test using hot
filtration method is conducted to determine if the functional groups in
the catalyst surface leach into the reaction media and constitute
“undesired” homogeneous reactions. However, catalytic activity can
be regenerated after each cycle by washing with solvents such as
methanol, water, and acetone. The catalyst is dried in the oven for
above 4 h and/or calcined thereafter. In-depth analysis on heteroge-
neous catalyst deactivation and regeneration can be found in previous
studies [104,105,109–112].
Thus far, no kinetics research has been conducted on acetylation
and catalyst deactivation, and only few studies describe heterogeneous
deactivation mechanisms [104,112–116]. As such, developing suitable
deactivation kinetics can provide insights into the process dynamics
and knowledge to optimize the design of deactivation-resistant cata-
lysts and the operation of the catalytic process. Different mechanisms
have been proposed by Butt and Petersen [114] to explain and model
catalyst deactivation. Fogler [116] reported various empirical rate
decay orders and examples of such deactivation encountered in
processes and provided with in-depth details of mathematical deriva-
tion of other deactivation mechanisms, namely, coking and sintering.
The commonly encountered derived kinetic models for sintering,
coking, and poisoning from the literature are presented in Table 3
with corresponding remarks. Kinetics of catalyst deactivation varies
according to active-site blockage. The reported acetylation deactivation
mechanisms exhibit different deactivation trends, ranging from sharp
decline in catalyst activity after the first cycle to gradual or stepwise
decrease in catalyst activity up to four cycles [56,107]. Modeling
acetylation rate of the reaction for different reactors by using hetero-
geneous catalyst should implicitly include deactivation terms for
efficient design of the reactors; the design should also incorporate
adjustment of catalyst decay activity with time a(t ). Fogler [116]
divided reaction kinetics into separable and non-separable kinetics in
his study of chemical reactions and catalyst decay over time. Separable
kinetics is simpler to model because the rate law and activity can be
independently studied, whereas non-separable kinetics assumes non-
ideal surface or modeling of several elementary reaction steps to
explain the deactivation mechanism. The activity of a deactivating
catalyst for considered separable case according to Fogler [116] can be
represented as a ratio of the kinetic rate of the reaction on the used
catalyst at time t to that of the fresh catalyst at t=0 (Eq. (22)).
 P.U. Okoye et al.

Table 3
Kinetic models for different deactivation mechanisms with remarks.

Deactivation Derived Kinetic model form Rate Mechanism Assumptions Remarks Ref.
Mechanism

Coking Cc=At n Empirical rate Equation Coke formation is independent of the hydrocarbon The validity of this assumption depends on the [125]
feed rate concentration of coke present on the catalyst surface.
Catalyst deactivated by coke can be regenerated by
calcination to burn off carbon.

Coking ⎛ C′ ⎞ ⎛ C′ ⎞ LHHW Single step reaction for A (reactant) to B (product). The second equation can be applied to consecutive [126,127]
krCtK ′A φA⎜C ′A − B ⎟ krCtK ′A φA⎜C ′A − B ⎟
⎝ K ⎠ ⎝ K ⎠ coke formation reaction is assumed to be parallel to step reactions and the both Equations can be solved
r= r=
1 + K ′A C ′A + KBC ′B 1 + K ′A C ′A + KBC ′B the main reaction path and the reaction rate is simultaneously accounting for both coke formation
Surface controlled. with respect to catalyst activity, temperature and
composition of feed mixture.

Sintering rd = K ′d a 2 2nd order rate expression – Current activity with respect to time is a function of [116]
Integral form of a(t ) is: with respect to current the decay rate constant and active surface species.
1 catalyst activity Because of the second order rate, expected nonlinear
a (t ) =

396
1 + k ′d t relationship is likely to predominate sintering
Amount of sintering with respect to active catalyst mechanism.
surface area is:
Sa 0
Sa =
1 + k ′d t
Sintering d (D / D 0 )
= − K (D /D0 − Deq /D0 )n Generalized power law – Ordinary power law expression are usually a functions [111,128]
dt expression, GPLE of time and cannot quantitatively calculate kinetic
parameters of deactivation, hence the use of GPLE.
Deq /D0term in GPLE, accounts for arbitrary limits
observed in time vs dispersion curve.
Poisoning-in feed df – Removal of poison from gas phase feed stream onto (1 − f ) is the fraction of unpoisoned site in the catalyst [116]
= Kd (1 − f )Cp
stream dt the catalyst sites is proportional to the fraction of and essentially is the activity of the catalyst with
unpoisoned active site and gas phase poison respect to time. This equation relates catalyst activity
concentration. with time and the concentration of poison in the gas
phase for petroleum feed contaminated by sulfur.
Poisoning- either by da n n Empirical decay rate law, For separable kinetics resulting in contacting a This can be applied to acetylation, by assuming [116]
− = rd = Kd′ Cpoa (t ) = Kda n
reactant or products dt with respect to n order of poison in the feed or product at constant constant poison (in situ water) concentration on the
decay. concentration Cp , with no spatial variation catalyst surface.
Renewable and Sustainable Energy Reviews 74 (2017) 387–401
 P.U. Okoye et al.

Table 4
Heterogeneous catalyst and deactivation mechanism in acetylation.

Catalyst Reaction conditions No. of Mechanism of deactivation Report/Reasons for catalyst deactivation Ref.
reuse

HSiW/ZrO2, HPW/ZrO2 AcOH:Gly=10:1, 120 °C, t=4 h, C.L= 0.3 g 4 – Constant catalytic activity was observed with HSiW/ZrO2 catalyst for all the cycles [49]
while HPW/ZrO2 catalyst activity decreased slightly for cycle 1 and 2 then the glycerol
conversion remained constant. The stable performance of HSiW/ZrO2 catalyst was
ascribed to its hydrolytic stability in the in situ polar environment and strong bond
interaction between HSiW and ZrO2.

PW2_AC AcOH:Gly=1:16, 120 °C, t=3 h, C.L= 0.2 g 4 Slight leaching Leaching of the heteropoly acid used to functionalize activated carbon, AC and as [56]
such the activity of the catalyst decreased slightly but stabilized in the third cycle.

Amberlyst AcOH:Gly=0.3:0.1, 105 °C, t=4 h, 5 Possible thermal degradation and functional groups No significant deactivation recorded even when reaction time is extended to 12 h. [57]
C.L= 0.5 g; after 15 min add acetic volatilization and poisoning by in situ water. However, likely deactivation may occur via thermal degradation when reaction is
anhydride. performed at temperature limits of the catalyst (120 °C).

SBAH−15(15) AcOH:Gly= 6:1, 110 °C, t=3 h, C.L=0.38 4 Possible attrition resulting in reduced surface area Slight decrease of glycerol conversion and combined DAG and TAG was observed. [63]
and consequent acid sites decrease. Slight leaching. However, catalytic activity of the catalyst stabilized for the 3 and 4 cycle indicating
that active sites cannot be leached out. The stabilization in 3 and 4 cycle is attributed
to the restoration of the kegging structure on exposure of beta-MoO3 species to the in

397
situ byproduct water environment.

Amberlyst−36Dowex−2 AcOH:Gly=1:8, 105 °C, C.L= 0.25 g/40 ml 4 poisoning Recovered catalyst via centrifuge can be directly reused without any treatment and [66]
glycerol drying for four cycles without significant loss in activity, however, as the number of
water molecule occupy the resin active sites (selective adsorption because of their
high affinity to water than glycerol), pretreatment is desirable in order to prevent
slowed catalyst activity or hydrolysis of MAG, DAG, TAG.

SAS, SSBA, Amberlyst−15 AcOH:Gly= 3:1, 105 °C, t=1 h, C.L=50 mg 5 Leaching of active sites and poisoning SAS catalytic activity declined significantly due to leaching of the sulfonic [69]
functionalities from the catalyst. Amberlyst−15, was stable up to 3rd cycle then
declined at the end of the fifth cycle. SSBA catalytic activity was stable with no
significant decrease in activity and no leaching detected.

3%Y/SBA−3 AcOH:Gly= 4:1, 110 °C, t=2.5 h, C.L= 0.2 g 4 Poisoning (adsorbed reaction products) Catalytic activity decreased after 3 run from 100% to 80% for glycerol conversion and [77]
55–50% for TAG selectivity. The decrease was ascribed to mass transfer limitations
and reaction conditions.

SZ−1 AcOH:Gly=100g/l: 40 ml, 54.85 °C, 4 Leaching of active group Although the catalyst presents better mechanical resistance compared with other [65]
t=24 h, C.L=250 mg/40 ml of glycerol tested catalyst in their study, however, it deactivates linearly down during successive
cycle and was completely deactivated at the 4th cycle, due to leaching of sulfur groups
used in functionalizing the zirconia.

Note. C.L=catalyst loading, t=reaction time in hours (h) or minutes (min), Gly=glycerol.
Renewable and Sustainable Energy Reviews 74 (2017) 387–401
P.U. Okoye et al. Renewable and Sustainable Energy Reviews 74 (2017) 387–401

−rt
a (t ) =
−r(t =0) (22)

Szepe and Levenspiel [117] categorized the separability of reaction

rates as time-dependent kinetic rates and activity-dependent kinetics,
which is time-independent. Hence, Eq. (23), which is the ratio of the
number of available active sites on the fresh catalyst (non-deactivated
catalyst),N0 , to the number of active sties at time t of deactivation ,Nt ,
can be used to represent the fraction of the active sites on the catalyst
surface at time t.
Nt
γ=
N0 (23)

By combining Eqs. (22) and (23) for enhanced modeling, Butt and
Petersen [114] extended the LHHW mechanism to explain the
dynamics of systems with changing activity by using the dehydrogena-
tion reaction of methyl-cyclohexane to toluene with coke formation;
they considered surface reaction as the rate-limiting step and were able
to combine γand a(t ). Further details on the deactivation and its kinetics
for heterogeneous catalysts using various reactors are presented in
previous studies [98,111,113,118,119]. As shown in Table 4, some
catalysts during glycerol acetylation with AcOH deactivates either by
poisoning, leaching of active sites, or thermal degradation. Hence,
catalyst decay can be quantified as a decrease in the number of
available active functional sites with respect to the initially available
active sites (fresh catalyst) because the activity of acid catalysts used in
acetylation is related to the active functional groups on the catalyst
surface.
Poisoning mechanism can be determined from various models for
heterogeneous porous catalyst, considering the surface-controlled
reaction assumed for determination of kinetic rates of glycerol acetyla-
tion with AcOH [104,113–116]. In situ water as poison deactivates
catalysts (e.g., zeolites) for aldol condensation reaction and has been
kinetically modeled for enhanced reactor and catalyst design
[120,121]; glycerol acetylation with AcOH suffers similar challenges.
Forzatti and Lietti [104] reported three limiting pore-poisoning
models, which are categorized as uniform, pore-mouth, and core
poisonings. The poison distribution on the catalyst surface for the
three poisoning models was drawn from Wheeler's work [122]. For all
types of catalytic poisoning, decrease in catalytic activity with respect to
fraction of poisoned sites is presented in Fig. 3. In the presence of
nonselective poison, pore-mouth and uniform poisonings are linearly
related to the amount of adsorbed poison under kinetic regime (Fig. 3
curve a). However, a different case exists for internal diffusional
regime, where pore-mouth poisoning results in a sharp decline in
catalytic activity compared with that in the kinetic regime case (Fig. 3,
curves f and g). Under diffusion-controlled regime (only at ideal cases),
decrease in catalytic activity is slower than the chemical regime because
the reactants tend to utilize more surface areas than what should have
been used; this phenomenon results in less decline of rapid catalytic
activity with the adsorbed amount (Fig. 3, curves b and c) [104]. These
poisons can be selective or nonselective and result in eroding (through
hydrolysis) or masking of active sites, respectively (Fig. 4).
An appropriate heterogeneous catalyst design can enhance resis-
tance to poisoning and is therefore needed because some poisons occur
on the outer surface of the catalyst. Using shape-selective catalyst with
non-uniform active surface distribution may theoretically favor the
desired reaction with respect to poisoning [123,124]. Furthermore, in
situ water that acts as poisons can be removed in real-time during
reaction through reactor modification by using the Dean stark appa-
ratus. Therefore, considering poisoning from in situ water in glycerol
acetylation, consecutive steps derived in [77] (Eqs. (24)–(27)) include
a fourth equation, which is represented as Eq. (28):
(24)
M . S + D. S + T . S + W . S → M + D + T + W +4S
Eq. (24) is the general equation for product desorption of glycerol
Fig. 3. Decline in catalytic activity for various types of poisoning with respect to fraction
of poisoned sites. (a) All types of poisoning, ∅ (Thiele modulus)≪2; (b) Uniform
Poisoning, ∅ ≫ 2; (c) core poisoning, ∅ = 3; (d) core poisoning, ∅ = 5; (e) core
poisoning, ∅ ≫ 5; (f) pore mouth poisoning, ∅ = 10; (g) pore mouth poisoning,
∅ = 100 [114].
acetylation from the catalyst surface.
where M, D, T, W, and S are MAG, DAG, TAG, water, and solid
catalyst, respectively.
rM = kdXM − kdXM XV (25)
rD = kdXD − kdXDXV (26)
rT = kdXT − kdXT XV (27)
rW = kdXW − kdXW XV (28)
where rM , rD, rT , rW are the desorption rates of MAG, DAG, and TAG, and
water, respectively, from the catalyst. Kd is the desorption rate
constant; and XM , XD , XT , XW ,XV are the concentrations of desorbed
MAG, DAG, TAG, water, and vacant site over the catalyst surface,
respectively. Therefore, the assumed surface-controlled rate law from
Ref. [77] can be modified to consider time-dependent catalyst activity,
as presented in Eq. (29), for modeling the deactivation of glycerol
acetylation.
XV2 n ⎛ k (X + XD + XT + XW ) ⎞
rS = a (t )⎜kGkAAXGXAA − d M ⎟
Xm ⎝ ks ⎠ (29)
where n is the order of catalyst decay, XW is the concentration of water
formed as acetylation reaction byproduct, and a n(t ) is the fraction of
active sites available for adsorption. For separable kinetics rate law that
results from poisoning at constant poison concentration, assuming the
first-order rate decay to be at n=1, the activity of any given catalyst can
be represented as Eq. (30):
a = e−kdt (30)
6. Conclusion and future trends
Based on studies on glycerol acetylation with AcOH, proper
representation of reaction rates by using kinetic models facilitates
understanding of the dynamic process and enhances robust reactor and
catalyst design. Heterogeneous catalyst can also be used to tailor the
rate of acetylation reaction to the desired yield and in successive cycles.
Reaction parameters such as temperature, catalyst loading, and molar
ratio evidently influence the reaction rate of acetylation. In particular,
temperature and molar ratio of glycerol/AcOH influence the selectivity

398
P.U. Okoye et al.
Fig. 4. (a) Non-selective poisoning of active sites and (b) selective poisoning of active sites with time.
of higher acetyl esters (DAG and TAG). The LHHW kinetic model is
popularly and widely applied in acetylation process. However, this
model is oversimplified, resulting in lapses often ignored by research-
ers. Moreover, phase interactions or mass-transfer resistance (from
bulk liquid to catalyst surface) may likely exist because of excess AcOH,
as evidenced by different rate constants obtained at different initial
glycerol/AcOH molar ratios. Therefore, the assumption of no resistance
to mass transfer or intraparticle diffusion limitation must be validated.
Most heterogeneous catalysts with high Bronsted acidity and surface
area are used in acetylation to validate the PSSH assumption. The
validation process forms a basis for the LHHW model derivation and
implies that the derived kinetic models are peculiar to the experiments
and conditions and cannot be applied outside the reaction zone.
Finally, catalyst deactivation poses serious limitation to industrial
applications. Therefore, proper knowledge on mechanisms and/or
kinetics of deactivation is required to improve the designs of reactors
and deactivation-resistant catalysts. Shape-selective catalyst is recom-
mended because of its resistance to certain molecular-shaped poisons
generated in situ.
Acknowledgement
The first author acknowledges the Universiti Sains Malaysia, USM
for their financial support under the USM fellowship scheme. The
authors acknowledge the financial support provided by the Ministry of
Education, Malaysia under the Transdisciplinary Research Grant
Scheme (TRGS) Phase2/2014 (203/PJKIMIA/6762002).
References
[1] International Energy Agency. Key trends in CO2 emissions excerpt from: CO2
399
Renewable and Sustainable Energy Reviews 74 (2017) 387–401
emissions from fuel combustion; 2015.
[2] Charles C, Gerasimchuk I, Bridle R, Moerenhout T, Asmelash E, Laan T. Biofuels—
At what cost? A review of costs and benefits of EU biofuel policies. Manitoba,
Canada; 2013.
[3] Serrano-Ruiz JC, Luque R, Sepúlveda-Escribano A. Transformations of biomass-
derived platform molecules: from high added-value chemicals to fuels via aqueous-
phase processing. Chem Soc Rev 2011;40:5266.
[4] Leung DYC, Wu X, Leung MKH. A review on biodiesel production using catalyzed
transesterification. Appl Energy 2010;87:1083–95.
[5] Xiu S, Shahbazi A. Bio-oil production and upgrading research: a review. Renew
Sustain Energy Rev 2012;16:4406–14.
[6] Pierpaolo C, Geoff M, Hiroyuki K, François C, Abbas G, Fulton L. Production costs
of alternative transport fuels. France: Paris Cedex; 2013.
[7] Verbeek R, Smokers RTM, Kadijk G, Hensema A, Passier GLM, Rabe ELM et al.
Impact of biofuels on air pollutant emissions from road vehicles. Netherlands;
2008.
[8] Bart JCJ, Palmeri N, Cavallaro S. 3 - Oleochemical sources: basic science,
processing and applications of oils. In: Bart JCJ, Palmeri N, Cavallaro S, editors.
Biodiesel sci technol. Woodhead Publishing; 2010. p. 62–113.
[9] Bart JCJ, Palmeri N, Cavallaro S. 4 – Vegetable oil formulations for utilisation as
biofuels. In: Bart JCJ, Palmeri N, Cavallaro S, editors. Biodiesel sci technol.
Woodhead Publishing; 2010. p. 114–29.
[10] Bart JCJ, Palmeri N, Cavallaro S. 7 – Transesterification processes for biodiesel
production from oils and fats. In: Bart JCJ, Palmeri N, Cavallaro S, editors.
Biodiesel Sci Technol. Woodhead Publishing; 2010. p. 285–321.
[11] Bart JCJ, Palmeri N, Cavallaro S. 8 – Biodiesel catalysis. In: Bart JCJ, Palmeri N,
Cavallaro S, editors. Biodiesel Sci Technol. Woodhead Publishing; 2010. p.
322–85.
[12] Bart JCJ, Palmeri N, Cavallaro S. 10 – Biocatalytic production of biodiesel. In:
Bart JCJ, Palmeri N, Cavallaro S, editors. Biodiesel Sci Technol. Woodhead
Publishing; 2010. p. 434–61.
[13] Bagheri S, Julkapli NM, Yehye WA. Catalytic conversion of biodiesel derived raw
glycerol to value added products. Renew Sustain Energy Rev 2015;41:113–27.
[14] Ilham Z, Saka S. Two-step supercritical dimethyl carbonate method for biodiesel
production from Jatropha curcas oil. Bioresour Technol 2010;101:2735–40.
[15] Oecd, Fao. Biofuels. Agric Outlook 2011–2020; 2011. p. 77–93.
[16] Ardi MS, Aroua MK, Hashim NA. Progress, prospect and challenges in glycerol
purification process: a review. Renew Sustain Energy Rev J 2015;42:1164–73.
[17] Quispe CAG, Coronado CJR, Carvalho JA. Jr., Glycerol: production, consumption,
prices, characterization and new trends in combustion. Renew Sustain Energy Rev
2013;27:475–93.
P.U. Okoye et al.
[18] Kong PS, Kheireddine M, Mohd W, Wan A. Conversion of crude and pure glycerol
into derivatives: a feasibility evaluation. Renew Sustain Energy Rev
2016;63:533–55.
[19] Luna C, Verdugo C, Sancho ED, Luna D, Calero J, Posadillo A, et al. Production of
a biodiesel-like biofuel without glycerol generation, by using Novozym 435, an
immobilized Candida antarctica lipase. Bioresour Bioprocess 2014;1:11.
[20] Kim Sok-Joong, Jung Sang-Min, Park Yong-Cheol, Park K. Lipase catalyzed
transesterification of soybean oil using ethyl acetate, an alternative acyl acceptor.
Biotechnol Bioprocess Eng 2007;12:441–5.
[21] Tan KT, Lee KT, Mohamed AR. A glycerol-free process to produce biodiesel by
supercritical methyl acetate technology: an optimization study via response
surface methodology. Bioresour Technol 2010;101:965–9.
[22] Calero J, Luna D, Sancho ED, Luna C, Bautista FM, Romero AA, et al. An overview
on glycerol-free processes for the production of renewable liquid biofuels,
applicable in diesel engines. Renew Sustain Energy Rev 2015;42:1437–52.
[23] Clacens JM, Pouilloux Y, Barrault J. Selective etherification of glycerol to
polyglycerols over impregnated basic MCM-41 type mesoporous catalysts. Appl
Catal A Gen 2002;227:181–90.
[24] Martin A, Richter M. Oligomerization of glycerol – a critical review. Eur J Lipid Sci
Technol 2011;113:100–17.
[25] Katryniok B, Paul S, Dumeignil F. Recent developments in the field of catalytic
dehydration of glycerol to acrolein. ACS Catal 2013;3:1819–34.
[26] Simakova O a, Davis RJ, Murzin DY. Biomass processing over gold catalysts. In:
Springer , editor. . SpringerBriefs Mol Sci, VIII. Springer; 2013. p. 11–33.
[27] Crotti C, Kaspar J, Farnetti E. Dehydrogenation of glycerol to dihydroxyacetone
catalyzed by iridium complexes with P-N ligands. Green Chem
2010;12:1295–300.
[28] Hejna A, Kosmela P, Formela K, Piszczyk Ł, Haponiuk JT. Potential applications
of crude glycerol in polymer technology – current state and perspectives. Renew
Sustain Energy Rev J 2016;66:449–75.
[29] Zhang C, Wang T, Liu X, Ding Y. Cu-promoted Pt/activated carbon catalyst for
glycerol oxidation to lactic acid. J Mol Catal A Chem 2016;424:91–7.
[30] Malyaadri M, Jagadeeswaraiah K, Sai Prasad PS, Lingaiah N. Synthesis of glycerol
carbonate by transesterification of glycerol with dimethyl carbonate over Mg/Al/
Zr catalysts. Appl Catal A Gen 2011;401:153–7.
[31] Silva JM, Soria MA, Madeira LM. Challenges and strategies for optimization of
glycerol steam reforming process. Renew Sustain Energy Rev 2015;42:1187–213.
[32] Aline C, José H, Andrade R, Alves F, Sequinel R, Rossato V, et al. Overview of
glycerol reforming for hydrogen production. Renew Sustain Energy Rev
2016;58:259–66.
[33] Remón J, Ruiz J, Oliva M, García L, Arauzo J. Effect of biodiesel-derived
impurities (acetic acid, methanol and potassium hydroxide) on the aqueous phase
reforming of glycerol. Chem Eng J 2016;299:431–48.
[34] Paul Ş, Pap T. Glycerol acetals and ketals as possible diesel additives. A review of
their synthesis protocols. Renew Sustain Energy Rev J 2016;62:804–14.
[35] Nanda MR, Zhang Y, Yuan Z, Qin W, Ghaziaskar HS, Charles C. Catalytic
conversion of glycerol for sustainable production of solketal as a fuel additive: a
review. Renew Sustain Energy Rev 2016;56:1022–31.
[36] Ghaziaskar HS, Afsari S, Rezayat M, Rastegari H. Quaternary solubility of acetic
acid, diacetin and triacetin in supercritical carbon dioxide. J Supercrit Fluids
2017;119:52–7.
[37] Murakami N, Oba M, Iwamoto M, Tashiro Y, Noguchi T, Bonkohara K, et al. L-
Lactic acid production from glycerol coupled with acetic acid metabolism by
Enterococcus faecalis without carbon loss. J Biosci Bioeng 2016;121:89–95.
[38] San P, Kheireddine M, Mohd W, Wan A, Cognet P, Pérès Y. Enhanced microwave
catalytic-esterification of industrial grade glycerol over Brønsted-based methane
sulfonic acid in production of biolubricant. Process Saf Environ Prot
2016;104:323–33.
[39] Rosiene M, Arcanjo A, Silva IJ, Rodríguez-castellón E, Infantes-molina A, Vieira
RS. Conversion of glycerol into lactic acid using Pd or Pt supported on carbon as
catalyst. Catal Today 2017;279:317–26.
[40] Kale S, Armbruster U, Umbarkar S, Dongare M, Martin A. Esterification of
glycerol with acetic acid for improved production of triacetin using toluene as an
entrainer. In: Proceedings of the 10th green chem conference; 2013. p. 70–71.
[41] Okoye PU, Hameed BH. Review on recent progress in catalytic carboxylation and
acetylation of glycerol as a byproduct of biodiesel production. Renew Sustain
Energy Rev 2016;53:558–74.
[42] Lam MK, Lee KT, Mohamed AR. Homogeneous, heterogeneous and enzymatic
catalysis for transesterification of high free fatty acid oil (waste cooking oil) to
biodiesel: a review. Biotechnol Adv 2010;28:500–18.
[43] Zhou C-HC, Beltramini JN, Fan Y-X, Lu GQM. Chemoselective catalytic conver-
sion of glycerol as a biorenewable source to valuable commodity chemicals. Chem
Soc Rev 2008;37:527–49.
[44] Cole-Hamilton DJ, Tooze RP. Homogeneous catalysis — advantages and pro-
blems. Catal. Sep. Recover. Recycl. Chem. Process Des., Springer; 2006, p. 1–8.
[45] Tudorache M, Negoi A, Protesescu L, Parvulescu VI. Biocatalytic alternative for
bio-glycerol conversion with alkyl carbonates via a lipase-linked magnetic nano-
particles assisted process. Appl Catal B Environ 2014;145:120–5.
[46] Waghmare GV, Vetal MD, Rathod VK. Ultrasound assisted enzyme catalyzed
synthesis of glycerol carbonate from glycerol and dimethyl carbonate. Ultrason
Sonochem 2014;22:311–6.
[47] Kim SC, Kim YH, Lee H, Yoon DY, Song BK. Lipase-catalyzed synthesis of glycerol
carbonate from renewable glycerol and dimethyl carbonate through transester-
ification. J Mol Catal B Enzym 2007;49:75–8.
[48] Hruby SL, Shanks BH. Acid-base cooperativity in condensation reactions with
functionalized mesoporous silica catalysts. J Catal 2009;263:181–8.
400
Renewable and Sustainable Energy Reviews 74 (2017) 387–401
[49] Zhu S, Zhu Y, Gao X, Mo T, Zhu Y, Li Y. Production of bioadditives from glycerol
esterification over zirconia supported heteropolyacids. Bioresour Technol
2013;130:45–51.
[50] Liao Xiaoyuan, Zhu Yulei, Wang Sheng-Guang, Hongmei Chen YL. Theoretical
elucidation of acetylating glycerol with acetic acid and acetic anhydride. Appl Catal
B Environ 2010;94:64–70.
[51] Patel A, Singh S. A green and sustainable approach for esterification of glycerol
using 12-tungstophosphoric acid anchored to different supports: kinetics and
effect of support. Fuel 2014;118:358–64.
[52] Rao PV, Rao BVA. Effect of adding Triacetin additive with Coconut oil methyl ester
(COME) in performance and emission characteristics of DI diesel engine; 2011. p.
1.
[53] Mufrodi Z, Rochmadi R, Sutijan S, Budiman A. Synthesis acetylation of glycerol
using batch reactor and continuous reactive distillation column. Eng J
2014;18:29–40.
[54] Ferreira P, Fonseca IM, Ramos aM, Vital J, Castanheiro JE. Esterification of
glycerol with acetic acid over dodecamolybdophosphoric acid encaged in USY
zeolite. Catal Commun 2009;10:481–4.
[55] Farinha J, Caiado M, Castanheiro JE. Valorisation of glycerol into biofuel additives
over heterogeneous catalysts. A. Méndez-. Lisbon, Portugal: FORMATEX; 2013.
[56] Ferreira P, Fonseca IM, Ramos AM, Vital J, Castanheiro JE. Acetylation of glycerol
over heteropolyacids supported on activated carbon. Catal Commun
2011;12:573–6.
[57] Liao X, Zhu Y, Wang SG, Li Y. Producing triacetylglycerol with glycerol by two
steps: esterification and acetylation. Fuel Process Technol 2009;90:988–93.
[58] Mufrodi Z, Rochmadi S, Budiman A. Chemical kinetics for synthesis of triacetin
from biodiesel byproduct. Int J Chem 2012;4:101–7.
[59] Zhou L, Nguyen TH, Adesina A a. The acetylation of glycerol over amberlyst-15:
kinetic and product distribution. Fuel Process Technol 2012;104:310–8.
[60] Zhou L, Al-Zaini E, Adesina A a. Catalytic characteristics and parameters
optimization of the glycerol acetylation over solid acid catalysts. Fuel
2013;103:617–25.
[61] Konwar LJ, Mäki-Arvela P, Begum P, Kumar N, Thakur AJ, Mikkola J-P, et al.
Shape selectivity and acidity effects in glycerol acetylation with acetic anhydride:
selective synthesis of triacetin over Y-zeolite and sulfonated mesoporous carbons.
J Catal 2015;329:237–47.
[62] Suraj Onkar Katole. Synthesis of green bioadditives through esterification of
glycerol. Mumbai, India: Institute of Chemical Technology (ICT); 2014.
[63] Khayoon MS, Hameed BH. Synthesis of hybrid SBA-15 functionalized with
molybdophosphoric acid as efficient catalyst for glycerol esterification to fuel
additives. Appl Catal A Gen 2012;433–434:152–61.
[64] Khayoon MS, Hameed BH. Acetylation of glycerol to biofuel additives over
sulfated activated carbon catalyst. Bioresour Technol 2011;102:9229–35.
[65] Kim I, Kim J, Lee D. A comparative study on catalytic properties of solid acid
catalysts for glycerol acetylation at low temperatures. Appl Catal B Environ
2014;148–149:295–303.
[66] Dosuna-Rodríguez I, Gaigneaux EM. Glycerol acetylation catalysed by ion
exchange resins. Catal Today 2012;195:14–21.
[67] Gonçalves VLC, Pinto BP, Silva JC, Mota CJ a. Acetylation of glycerol catalyzed by
different solid acids. Catal Today 2008;133–135:673–7.
[68] Melero J a, van Grieken R, Morales G, Paniagua M. Acidic mesoporous silica for
the acetylation of glycerol: synthesis of bioadditives to petrol fuel. Energy Fuels
2007;21:1782–91.
[69] Testa ML, La Parola V, Liotta LF, Venezia AM. Screening of different solid acid
catalysts for glycerol acetylation. J Mol Catal A Chem 2013;367:69–76.
[70] Ghoreishi KB, Yarmo MA. Sol-gel sulfated silica as a catalyst for glycerol
acetylation with acetic acid. J Sci Technol 2013;5:65–78.
[71] Ghoreishi KB, Yarmo MA, Nordin NM, Samsudin MW. Enhanced catalyst activity
of WO3 using polypyrrole as support for acidic esterification of glycerol with acetic
acid. J Chem 2013:2013.
[72] Bhorodwaj SK, Dutta DK. Activated clay supported heteropoly acid catalysts for
esterification of acetic acid with butanol. Appl Clay Sci 2011;53:347–52.
[73] Popova M, Szegedi Á, Ristić A, Tušar NN. Glycerol acetylation on mesoporous
KIL-2 supported sulphated zirconia catalysts. Catal Sci Technol
2014;4:3993–4000.
[74] Zhang C, Fu Z, Liu YC, Dai B, Zou Y, Gong X, et al. Ionic liquid-functionalized
biochar sulfonic acid as a biomimetic catalyst for hydrolysis of cellulose and
bamboo under microwave irradiation. Green Chem 2012;14:1928–34.
[75] Penzien J, Müller TE, Lercher JA. Hydroamination of 6-aminohex-1-yne over zinc
based homogeneous and zeolite catalysts. Microporous Mesoporous Mater
2001;48:285–91.
[76] Haw JF, Hall MB, Alvarado-swaisgoad AE, Mudsod EJ, Lin Z, Beck LW, et al.
Integrated NMR and Ab initio study of acetonitrile in zeolites: a reactive complex
model of zeolite acidity. J Am Chem Soc 1994;116:7308–18.
[77] Khayoon MS, Triwahyono S, Hameed BH, Jalil AA. Improved production of fuel
oxygenates via glycerol acetylation with acetic acid. Chem Eng J
2014;243:473–84.
[78] Gelosa D, Ramaioli M, Valente G, Morbidelli M. Chromatographic reactors:
esterification of glycerol with acetic acid using acidic polymeric resins. Ind Eng
Chem Res 2003;42:6536–44.
[79] Koros RM, Nowak EJ. A diagnostic test of the kinetic regime in a packed bed
reactor. Chem Eng Sci 1967;22:470–5.
[80] Iglesia E, Michel B. Unimolecular and bimolecular formic acid decomposition on
copper. J Phys Chem 1986;20:5272–4.
[81] Wilke CR, Chang P. Correlation of diffusion coefficients in dilute solutions. AIChE
J 1955;1:264–70.
P.U. Okoye et al.
[82] Sitaraman R, Ibrahim SH, Kuloor NR. A generalized equation for diffusion in
liquids. J Chem Eng Data 1963;8:198–201.
[83] Poling BE, Prausnitz JM, O’Connell JP. The properties of gases & liquids. vol. 1;
1988. http://dx.doi.org/10.1016/0894-1777(88)90021-0.
[84] Lode F, Houmard M, Migliorini C, Mazzotti M, Morbidelli M. Continuous reactive
chromatography. Chem Eng Sci 2001;56:269–91.
[85] Yadav GD, Ramesh P. Selectivity engineering in the 0- versus C-alkylation of p-
cresol with cyclohexene over sulfated zirconia. Can J Chem Eng 2000;78:917–27.
[86] Yadav GD, Krishnan MS. Solid acid catalysed acylation of 2-methoxy-naphthalene:
role of intraparticle diffusional resistance. Chem Eng Sci 1999;54:4189–97.
[87] Yadav GD, Joshi aV. A green route for the acylation of resorcinol withacetic acid.
Clean Technol Environ Policy 2002;4:157–64.
[88] Akbay E, Altıokka MR. Kinetics of esterification of acetic acid with n- amyl alcohol
in the presence of Amberlyst-36. Appl Catal A: Gen 2011:13–9.
[89] Hoo P, Abdullah AZ. Kinetics modeling and mechanism study for selective
esterification of glycerol with lauric acid using 12-tungstophosphoric acid post-
impregnated SBA-15. Ind Eng Chem Res 2015;54:7852–8.
[90] Baxter S, Zivanovic S, Weiss J. Molecular weight and degree of acetylation of high-
intensity ultrasonicated chitosan. Food Hydrocoll 2005;19:821–30.
[91] Beard AD, James BB. Power-law kinetics of tracer washout from physiological
system. Ann Biomed Eng 1998;26:775–9.
[92] Venuto P. Organic reactions catalyzed by crystalline aluminosilicates III.
Condensation reactions of carbonyl compounds. J Catal 1966;6:237–44.
[93] Patrick G, Annie F. Aromatic benzoylation. In: Eric GD, editor. Catal FINE Chem
Synth Microporous Mesoporous Solid Catal. vol 4, Lisbon, Portugal; 2006. p. 95–
104.
[94] Dezheng W. Experimental conditions for valid Langmuir-Hinshelwood kinetics.
Chin J Catal 2010;31:972–8.
[95] Kumar KV, Porkodi K, Rocha F. Langmuir–Hinshelwood kinetics – a theoretical
study. Catal Commun 2008;9:82–4.
[98] Kunz L, Maier L, Tischer S, Olaf D. Modeling the rate of heterogeneous reactions.
Model Heterog Catal React From Mol Process to Tech Syst, Germany: Wiley-VCH,
Weinheim 2011; 2011. p. 1–59.
[99] Izci A, Bodur F. Liquid-phase esterification of acetic acid with isobutanol catalyzed
by ion- exchange resins. React Funct Polym isobutanol catalyzed by ion-exchange
resins; 2015.
[100] Heineken FG, Tsuchiya HM, Aris R. On the mathematical status of the pseudo-
steady state hypothesis of biochemical kinetics. Math Biosci 1967;1:95–113.
[101] Tsibranska I, Hristova E. Comparison of different kinetic models for adsorption
of heavy metals onto activated carbon from apricot stones. 43; 2011. p. 370–7.
[102] Fogler HS. Elements of chemical reaction engineering elements of chemical
reaction engineering, 3rd ed. New Delhi: Prentice-Hall International, Inc; 1995.
[103] Anderson DL. Thermodynamics and equations of state. Theory of the earth, 1998.
Boston: Blackwell Scientific Publications; 1989. p. 84–101.
[104] Forzatti P. Catalyst deactivation. Catal Today 1999;52:165–81.
[105] Argyle M, Bartholomew C. Heterogeneous catalyst deactivation and regeneration:
a review. Catalysts 2015;5:145–269.
[106] Farinha J, Caiado M, Castanheiro JE. Valorisation of glycerol into biofuel
additives over heterogeneous catalysts; 2013. p. 422–9.
401
Renewable and Sustainable Energy Reviews 74 (2017) 387–401
[107] Dosuna-Rodríguez I, Adriany C, Gaigneaux EM. Glycerol acetylation on sulphated
zirconia in mild conditions. Catal Today 2011;167:56–63.
[108] Singare PU. Thermal degradation studies of some strongly acidic Ca-tion
exchange resins. Open J Phys Chem 2011;1:45–54.
[109] Okoye PU, Abdullah AZ, Hameed BH. Glycerol carbonate synthesis from glycerol
and dimethyl carbonate using trisodium phosphate. J Taiwan Inst Chem Eng
2016;0:1–8.
[110] Okoye PU, Abdullah AZ, Hameed BH. Stabilized ladle furnace steel slag for
glycerol carbonate synthesis via glycerol transesterification reaction with dimethyl
carbonate. Energy Convers Manag 2016.
[111] Walke* Santosh, Kambale S. Catalyst deactivation and regeneration. Int J Sci Eng
Technol 2015;5:281–5.
[112] Moulijn JA, van Diepen AE, Kapteijn F. Catalyst deactivation: is it predictable?:
what to do?. Appl Catal A Gen 2001;212:3–16.
[113] Levenspiel O. Experimental search for a simple rate equation to describe
deactivating porous catalyst particles. J Catal 1972;25:265–72.
[114] Butt JB, Petersen EE. {CHAPTER} 10 – Deactivation in Fixed Beds. In: Petersen
JBBE, editor. Act Deactiv Poisoning Catal, Elsevier; 1988, p. 347–425.
[115] Jossens LW, Petersen EE. A novel reactor system that permits the direct
determination of deactivation kinetics for a heterogeneous catalyst. J Catal
1982;73:366–76.
[116] Fogler HS. 10.7 Catalyst deactivation. Catal Deactiv 2014:56–78.
[117] Stephen Szépe, Levenspiel O, Laan T. Proc 4th Eur Symp Chem React Eng,
Brussel, London: Pergamon Press; 1970.
[118] Bartholomew CH. Sintering kinetics of supported metals: new perspectives from a
unifying GPLE treatment. Appl Catal A Gen 1993;107:1–57.
[119] Bartholomew CH. Mechanisms of catalyst deactivation. Appl Catal A Gen
2001;212:17–60.
[120] Wakabayashi F, Kondo JN, Domen K, Hirose C. FT-IR study of H218O adsorption
on H-ZSM-5: direct evidence for the hydrogen-bonded adsorption of water. J Phys
Chem 1996;100:1442–4.
[121] Panov A, Fripiat J. Poisoning of aldol condensation reaction with H2O on acid
catalysts. Catal Lett 1999;57:25–32.
[122] Wheeler A. Reaction rates and selectivity in catalyst pores. Adv Catal
1951;3:249–327.
[123] Karanth NG, Luss D. Selectivity enhancement in catalytic purification reactions by
poisons. Chem Eng Sci 1975;30:695–8.
[124] Yang H, Chen H, Chen J, Omotoso O, Ring Z. Shape selective and hydrogen
spillover approach in the design of sulfur-tolerant hydrogenation catalysts. J Catal
2006;243:36–42.
[125] Voorhies A. Carbon formation in catalytic cracking. Ind Eng Chem Res
1945;37:318–22.
[126] Froment GF, Bischoff KB. Kinetic data and product distributions from fixed bed
catalytic reactors subject to catalyst fouling. Chem Eng Sci 1962;17:105–14.
[127] Froment GF, Bischoff KB. Non-steady state behaviour of fixed bed catalytic
reactors due to catalyst fouling. Chem Eng Sci 1961;16:189–201.
[128] Fuentes GA, Gamas ED. Towards a better understanding of sintering phenomena
in catalysis. In: Bartholomew CH, Butt JB, editors. Catal Deactiv 1991
Proceedings 5th Int Symp, vol. 68, Elsevier; 1991, p. 637–44.