Review

Received: 25 January 2021 Revised: 1 July 2021 Accepted: 15 July 2021
DOI: 10.1002/cjce.24295
REVIEW ARTICLE
A review on bi/multifunctional catalytic oxydehydration of

bioglycerol to acrylic acid: Catalyst type, kinetics, and
reaction mechanism
Anas Abdullah1 | Ahmad Zuhairi Abdullah1 | Mukhtar Ahmed1 |

Patrick U. Okoye2 | Mohammad Shahadat1,3
1
School of Chemical Engineering,
Universiti Sains Malaysia, Nibong Tebal,
Abstract
Malaysia Acrylic acid, conventionally produced via propylene (non-renewable fossil fuel
2
Laboratorio de Bioenergía, Instituto de route), is an industrially important chemical. The bio-based feedstock process
Energías Renovables (IER-UNAM),
employing glycerol (a by-product of biodiesel production) has attracted the
Temixco, Mexico
3
Department of Biochemical Engineering
attention of researchers due to its non-polluting and renewable characteristics.
and Biotechnology, Indian Institute of Bi/multifunctional catalysts using a combination of zeolites, metal oxides,
Technology IIT, Delhi, India heteropoly acids, and phosphates have been mainly studied for the glycerol
Correspondence
oxydehydration process. Brønsted acid sites favour acrolein generation over
Ahmad Zuhairi Abdullah, School of Lewis acid sites, whereas the redox sites convert the generated acrolein to
Chemical Engineering, Universiti Sains
acrylic acid. So far, the maximum acrylic acid yields of 60% and 59% have been
Malaysia, Engineering Campus, 14300
Nibong Tebal, Penang, Malaysia. reported on heteropoly acid and mixed metal oxide catalysts, respectively.
Email: [email protected] Some DFT studies also revealed the deprotonation energy of acid sites and fur-
ther helped in designing efficient catalysts. Despite these accomplishments,
Funding information
Universiti Sains Malaysia, Grant/Award catalyst deactivation because of coking and stability remains a major problem.
Number: 8014059 In this paper, various bi/multifunctional catalysts employed in glycerol
oxydehydration to acrylic acid are critically reviewed. Different catalyst forms,
preparation techniques, reaction kinetics, reaction mechanisms, deactivation,
reactivation, process operating parameters, and sustainability are considered.
In addition, the challenges associated with each catalyst type and strategies to
overcome low yield, deactivation, and future directions are discussed.
KEYWORDS
acrolein, acrylic acid, catalyst behaviour, glycerol, green process, oxydehydration
1 | INTRODUCTION esters of long-chain fatty acids) is now recognized glob-

ally as an alternative fuel.[3] The by-products and residual
Fossil fuels are the primary source of energy and account wastes obtained during the biodiesel production process
for about 85% of worldwide energy consumption.[1] The can be successfully utilized to produce industrially impor-
excessive use of non-renewable fossil fuels by industries, tant chemicals, thereby making the whole process
automobiles, and various other sectors has led to several sustainable.[4]
problems such as severe pollution, adverse health effects, Biodiesel by-products and the remainder include glyc-
and damage to the ecosystem.[2] Biodiesel (mono-alkyl erol, oil cake, methanol, and biodiesel washing
2956 © 2021 Canadian Society for Chemical Engineering. wileyonlinelibrary.com/journal/cjce Can J Chem Eng. 2022;100:2956–2985.
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ABDULLAH ET AL. 2957
wastewaters. Glycerol is the major by-product added products that can be obtained from glycerol as a
obtained during the production of biodiesel through starting material.
the transesterification process. [5] It is estimated that, Acrylic acid or 2-propenoic acid (C3H4O2) is an unsat-
during transesterification, 1 kg of glycerol is obtained urated carboxylic acid with a vinyl group connected to
for every 10 kg of biodiesel produced.[6,7] The steep the terminal carboxylic acid. It is miscible with most sol-
increase in biodiesel production has resulted in the co- vents such as alcohol, benzene, water, chloroform, and
production of a large amount of glycerol. It is esti- acetone and can easily polymerize to polyacrylic acid in
mated that by 2022, about 4.1 Mm3 of crude glycerol an exothermic reaction.[13] It is used to manufacture plas-
will be produced according to the estimated demand tics, super-absorbent polymers (SAPs), adhesives, surface
for biodiesel production of 41 Mm3. It is also estimated coatings, textiles, elastomers, resins, paints, polishes,
that by 2024, the global glycerol market will be worth leather, and adhesives.[14,15] In 2018, acrylic acid had a
USD 5 billion.[8] market share of 8.84 MTPA (million tons per annum),
Glycerol (C3H8O3) is a viscous, non-toxic, colourless and it is expected that, by 2023, its production will peak
triol. Glycerol’s poly-hydric unique three hydroxyl struc- to 9.92 MTPA. In terms of monetary value, the global
ture supports the production of value-added chemicals acrylic acid market will be worth $22.55 billion by
via chemical and biological conversion routes.[6] Glycerol 2022.[16,17]
can be utilized to produce various value-added chemicals The acrylic acid conventional production process
and commodities such as acrolein, formic acid, lactic includes partial oxidation of propylene (obtained from
acid, hydrogen, syngas, ethanol, methanol, fuel additives fossil fuels), employing heterogeneous catalysts through a
(acetin, glycerol ethers, glycerol formal), glycerol carbon- two-step process.[18] It is estimated that for a ton of pro-
ate, 1,3-propanediol,[9] polyglycerol, and olefins through pylene burned, 175 kg of CO2 is generated.[19] In general,
different routes such as dehydration, esterification, the pollution and the complexities associated with the
etherification, acetalization, reforming, carbonylation, conventional production routes make it an unsustainable
hydrogenolysis, and oxidation.[10,11] It is estimated that process. Renewable routes for acrylic acid production
over 1500 products ranging from food ingredients, cos- include employing 3-hydroxypropionic acid,[20] lactic
metics, medicines, and pharmaceuticals contain glyc- acid,[21,22] acrylonitrile, allyl alcohol, and propylene as
erol.[12] Figure 1 shows various sources of glycerol intermediates.[23,24] Table 1 shows the production routes
production and some of the chemicals and the value- of acrylic acid via various routes. Propylene can be
FIGURE 1 Glycerol production routes, intermediate chemicals, and applications

2958 ABDULLAH ET AL.
TABLE 1 Acrylic acid conventional and renewable production routes
Acrylic acid
production routes Reaction mechanism Reaction conditions By-products

(a) Conventional process Vapour phase (300–370 C AC, AD, CO2
and 260–300 C)
(b) Lactic acid Liquid phase (160–250 C) GLA, GLYCA,

intermediate followed by gas phase AA, OA, FA,
(330–410 C) AD, PA,
2,3-pen
(c) Propylene Vapour phase (250–300 C PP, 1-PO, AC,
intermediate and 260–300 C) AD
(d) Allyl alcohol Liquid phase (140–240 C) AT, 1,2-prop,

intermediate followed by gas phase PL, AC, AA,
(340–360 C) AC, PL, PA
(e) Acrylonitrile Vapour phase (280–400 C) NA
intermediate
(f) Direct conversion Vapour phase AC, AA, AD,

(Oxydehydration) (280–350 C) PA
Abbreviations: 1,2-prop, 1,2 –propanediol; 1-PO, 1-propanol; 2,3-pen, 2,3-pentanedione; AA, acetic acid; AC, acrolein; AD, acetaldehyde; AT, acetol; FA, formic
acid; GLA, glyceric acid; GLYCA, glycolic acid; NA, data not available; OA, oxalic acid; PA, propanoic acid; PA, propionic acid; PL, propanal; PP, propane.
and energy advantages over the other routes. The forma-

tion of an intermediate (b-d) and combination of the liq-
uid phase and vapour phase (b and d) results in product
losses, side reactions, and by-products formation, which
reduces the atomic efficiency and economy of the pro-
cesses. In terms of reaction mechanism, the (c), (d), and
(f) processes release water (H2O), whereas (b) releases
hydrogen (H2) gas. Further, other than the (f) glycerol
oxydehydration process, all reactions require two differ-
ent temperatures depending on the intermediate.[25–27]
Also, oxydehydration can occur in a mild oxidative envi-
ronment compared to other processes. Hence, consider-
ing all the factors, the glycerol oxydehydration exhibits
F I G U R E 2 Data of articles published on ‘oxydehydration of
higher atom efficiency and atom economy.
glycerol to acrylic acid’[28]
The process of glycerol oxydehydration to acrylic acid
is new and has gained momentum during the last decade.
efficiently converted to acrylic acid (conventional route) Though many publications are available on the glycerol
without evident catalyst deactivation. However, the pro- oxydehydration process (Figure 2), in-depth understand-
cess suffers from high propylene prices and low atom effi- ing and commercialization have not been achieved.[28]
ciency. For the renewable glycerol route, similar atom This review exclusively covers all the research conducted
efficiency and energy input can be expected for all the on the glycerol oxydehydration process (2010–2021). Both
processes (Table 1b–f) since both the starting material the liquid phase and gas phase glycerol oxydehydration
(glycerol) and the final product (acrylic acid) are the reaction routes are discussed. However, the dehydration
same. However, a detailed analysis reveals that the glyc- of glycerol to acrolein is not considered. Various
erol oxydehydration route shows several possible atomic bi/multifunctional catalysts are critically reviewed,
focusing on catalyst type, reaction conditions, yield, reac- acid, and 3-hydroxypropionic acid as an intermediate,
tion mechanism, surface properties, deactivation, and and (ii) a single-step process through the simultaneous
reactivation strategies. Finally, the challenges associated dehydration-oxidation process.[29] For the two-step pro-
with the glycerol oxydehydration route and the prospects cess, two reactors are required for loading acid and redox
are discussed. catalyst separately. The product of the first reactor acts as
a reactant of the second catalyst. This route is complex
and involves excess engineering investment.[30] However,
2 | A C R Y LI C AC ID P R O D U C T I O N for the case of a single-step process, only one reactor is
F R O M G LY C E R O L employed. Simplified design, easy operation, improved
productivity, and lower investment cost makes the single
Glycerol dehydration to acrolein and acrolein oxidation reactor a viable option.
to acrylic acid has been studied for the last five decades. Table 2 shows the relative comparison of the two-step
However, the bio-based route for acrylic acid production and the single-step processes. The combined advantages
from glycerol has attracted the attention of researchers of the single-step process outweigh the two-step process.
owing to the excess production of glycerol obtained as a Further, in terms of large-scale production and process
biodiesel by-product. There are two routes to produce technology implementation, the two-step method may
acrylic acid from glycerol: (i) a two-step process via fail. The single-step process can be further subdivided
allyl alcohol, acrolein, acrylonitrile, propylene, lactic according to the type of catalyst: (i) a dual-layer catalyst
TABLE 2 Relative comparison of two-step and single-step processes to produce acrylic acid from glycerol
Parameters Two-step Single-step Reference

Reactor system Two reaction systems required Needs only a single reaction system Sun et al.[24]
Reactor design Simple Complex (fluidized/moving bed) Witsuthammakul
et al.[31]
Selectivity Good selectivity to acrylic acid Moderate Thanasilp et al.[32]
Formation of Intermediates such as acrolein, Oxydehydration (intermediates directly Suganuma et al.[33]
intermediates propylene, allyl alcohol are generated. converted to acrylic acid)
Complex handling, transportation,
and storage of intermediates because
of high reactivity, combustibility, and
toxicity
By-products Treated as waste Dehydration by-products can be further Witsuthammakul
oxidized et al.[31]
Deactivation/coking Chances of high catalyst deactivation Low catalytic deactivation low (using Yun et al.[34,35]
O2-containing flow)
Regeneration of Difficult Continuous regeneration of the catalyst Pestana et al.[7]
catalyst possible through coke burning
Catalyst design and Relatively easier Complicated design and synthesis Chieregato et al.[36]
synthesis
Thermal/heat balance Difficult to achieve Optimum thermal balance, combines Witsuthammakul
exothermic reaction (oxidation step) et al.[31,37]
with endothermic (dehydration step)
Cost Low cost of the catalyst, but the overall Bifunctional catalyst synthesis increases Thanasilp et al.[32]
investment is high the cost of catalysts. But, overall, it
can be economically practical because
of a significant reduction in
engineering investment
Catalyst amount/Mass High catalyst mass Less amount of catalyst required Rasteiro et al.[38]
Overall Complicated, time-intensive, total Low production cost, moderate to good Shen et al.[39]
process cost is high acrylic acid yield. Fast and techno-
economic process
F I G U R E 3 (A) Dual layer catalyst scheme (sequential acrylic acid production) and (B) single layer bifunctional catalytic reactor scheme
(glycerol oxydehydration) for acrylic acid production
TABLE 3 Dual-layer catalysts for the sequential acrylic acid production process
Catalyst
Bottom WHSV Glycerol Acrylic acid

Top layer layer Temp. ( C) (h1) conversion (%) selectivity (%) TOS (h) Reference
H4SiW12O4/ MoVO 300 0.3 100 46.2 2 Liu et al.[41]
Al2O3
Cs2.5H0.5PW12O40 MoVO– 300 0.2 100 75 70 Liu et al.[42]
SiC
WOx/ZrO2 WVMo 305 125 (gh/mol) >99 44 3 Massa et al.[43]
HZSM-5 MoVO 250 0.7 100 47.2 2 Witsuthammakul
et al.[31]
HZSM-5 MoVW 250 125 (gh/mol) 99 47 2 Yun et al.[34]
Abbreviations: TOS, time on stream; WHSV, weight hourly space velocity.
(consecutive layer of two catalysts, i.e., stacked catalyst) components may not be fully active under the same
or (ii) a single layer–bi/multifunctional catalyst.[40] In temperature and reaction conditions. The complex
dual-layer catalysts, glycerol first dehydrates into acrolein sequential loading, operation, and maintenance of a
and with subsequent oxidation becomes acrylic acid, two-bed continuous system make it an unattractive and
whereas in single layer catalysts, direct glycerol conver- expensive process. Compared to dual-layer catalysts,
sion to acrylic acid occurs. Figure 3 shows the two-bed single-layer catalysts have the advantage of easy load-
reactor scheme (dehydration and oxidation catalyst) and ing, high catalytic activity under the same reaction con-
a single layer bifunctional catalytic reactor scheme. ditions, targeted product formation, and higher catalytic
There are some reports available in the literature on stability as the oxidizing medium partially inhibits coke
double-layer catalysts. Table 3 discusses the various formation.
dual-layer catalysts studied for sequential acrylic acid In summary, in a single-layer bi/multifunctional cata-
production. Acrylic acid selectivity up to 75% has been lyst, a single catalyst is loaded at the start of the reaction.
achieved over Cs2.5H0.5PW12O40 / MoVO–SiC. The other The final product is obtained without any change of cata-
studies involved focused on optimizing the reaction con- lyst. The catalyst must possess both acid and redox sites
ditions.[10,31,34,41–43] The sequential acrylic acid produc- suitably spaced for efficient dehydration and the oxida-
tion reaction over dual layer catalysts results in tion step, respectively. The incorporation of both acid
undesired side reactions if incomplete glycerol conver- and redox properties in a single catalyst is a challenging
sion occurs in the first bed. Lack of heat balance for the procedure, but it significantly eases the overall produc-
reaction and formation of toxic acrolein as intermediate tion process. The economic advantages and the simplicity
are also major issues. Further, two different catalyst of the engineering process make it an interesting and
FIGURE 4 Catalysts support and active sites studied for the glycerol oxydehydration process
TABLE 4 Zeolite-based catalysts studied for the glycerol oxydehydration process
Selectivity
(%)
Metal loading Temp. WHSV Glycerol AA TOS
Catalyst (wt.%) ( C) (h1) conversion (%) Ac AA yield (%) (h) Reference
V-BEA 5 275 1.5 75 45 25 - - Pestana
(a = 30) 10 250 47 44 10 et al.[7]
Fe-BEA 1.2 275 7.6 50 - - 10 8 Diallo

(a = 10) 2.0 90 - - 10 et al.[49]
4 100 - - 23
(V2O5/MFI) 10 300 0.9 100 30 25 - 6 Possato
(a = 40) et al.[50]
V2O5/MFI 10 350 0.9 100 15 17 - 8 Possato
(a = 40) et al.[37]
V-MFI 10 320 5.0 100 8 19 - 8 Possato
(a = 40) et al.[51]
V/H-β 5 320 8.6 87.6 46.3 20.2 17.7 10 Silva et al.[52]
(a = 30)
Fe-MFI 0.6 320 2770c 58 32 47 27 8 Diallo
(a = 45) et al.[53]
Fe-MCM-22 1.2 320 8.6 92.6 9.0 56.8 52.6 10 dos Santos
(a = 30) et al.[54]
VSiO - 320 2 93.6 5.3 89.6 - 1 Paula et al.[55]
VSiO - 350 3.8 74.0 - 78 - 6 Vieira
et al.[56]
Abbreviations: a, zeolite Si/Al ratio; AA, acrylic acid; Ac, acrolein; Temp., temperature; TOS, time on stream; VSiO, vanadosilicates; WHSV, weight hourly
space velocity.
attractive route. Therefore, nowadays, most researchers (ii) mixed-metal oxide catalyst, (iii) heteropoly acid cata-
focus on the monophasic bi/multifunctional catalyst lyst, and (iv) phosphate-containing catalyst. Figure 4
single-step process to produce acrylic acid. The shows all the four major types of catalysts (support and
catalyst for the glycerol oxydehydration process can be active sites) employed in the glycerol oxydehydration
classified into four major types: (i) zeolite-based catalyst, process.
3 | C AT A L Y S T S FO R G LY C E R O L maximum acrylic acid yield of 23% was recorded at 4 wt.%

OXYDEHYDRATION PROCESS Fe loading. Fe (+III) tetrahedral species were assumed to be
the key site for redox reactions.[49] The addition of metals
3.1 | Zeolite-based catalysts results in a change of textural properties of the precursor,
as reported for the V-BEA catalyst.[7] However, no signifi-
Zeolites are porous and powdered materials.[44] They are cant differences were observed between the precursor and
crystalline and possess a stable microporous structure Fe-loaded BEA zeolite.[49]
comprising Si and Al cations, in the form of a tetrahedral
arrangement, enveloped by four anions of oxygen
(O2).[45] There are 200 types of zeolites reported in the 3.1.2 | ZSM-5
literature, of which 50 are naturally occurring.[46,47] Zeo-
lite lattice is relatively stable, and the removal of ions can ZSM-5 is a siliceous, acidic zeolite that consists of eight
be achieved, keeping the zeolite framework intact.[48] 5-member ring units intersected by two channels.[62] Its
The diffusion of reactants and products can be suitably channels and pores have standardized diameters suitable
controlled to avoid undesired products formation. Due to for targeted catalysis.[63] For the acrolein production from
their optimum acidity, stable framework, large surface glycerol, various types of ZSM-5 have been effectively
area, and uncomplicated active component loading, they studied with up to 75% selectivity to acrolein (SiO2/
have been widely studied for the glycerol oxydehydration Al2O3 = 30).[30,64] Recent advanced studies for acrolein
process. Table 4 discusses the different types of zeolite- production include transition metal hydrogen phos-
based catalysts studied for the oxydehydration pro- phates/meso-HZSM-5 hybrid catalysts (84.7% acrolein
cess.[7,37,49–56] selectivity)[65] and modifying the b-axis channel length of
ZSM-5 zeolite (87% acrolein selectivity).[66]
Possato’s group studied V2O5 and MoV2O8 loaded on
3.1.1 | Zeolite beta the ZSM-5 catalyst to analyze the effect of vanadium
loading and improve acrylic acid selectivity.[37,51] By load-
Zeolite beta is a high silica zeolite with distinctive three- ing ZSM-5 with vanadium oxide, up to 97% conversion
dimensional 12-ring intersecting channels, large surface and a moderate yield of 17% acrylic acid were achieved.
area, changeable acidity, and good thermal stability. Remarkably, it was observed that the presence of vana-
These properties render it suitable for use as a catalyst for dium led to an increase in the lifetime of the catalyst.[37]
biomass conversion, and for chemical and petrochemical The interaction of zeolites (microporous structure) with
processes. Its channel pore diameters are 0.76 0.64 nm2 the bulky glycerol molecules creates transportation prob-
and 0.55 0.55 nm2.[57,58] Zeolite beta has been investi- lems since the reaction rate is faster than the diffusion
gated for the dehydration of glycerol to acrolein.[59,60] rate, leading to coking and deactivation. The change in
The highest acrolein selectivity reported was 60.1% (SiO2/ zeolite structure from purely microporous to mesoporous
Al2O3 = 25).[61] is beneficial in enhancing diffusion, resulting in less
For the glycerol oxydehydration to acrylic acid in the deactivation. Methods used to obtain zeolites with micro-
gas phase, preliminary studies over vanadium and mesoporosity characteristics include synthesis with
(V) impregnated zeolite beta (BEA) were performed, with double templating, zeolitization of a mesoporous mate-
V loadings of 5 and 10 wt.%. The effect of temperature rial, assembly of zeolite nanocrystals, recrystallization of
with varying metal content (V) was also studied. It was zeolites, desilication, and dealumination. Alkaline treat-
observed that the impregnation with V significantly ment of zeolite (using NaOH or Na2CO3) to obtain micro-
decreased the specific surface area, but it did not consid- mesoporous structure is an effective method to overcome
erably impact the BEA acidity. The major product deactivation. Through the alkaline and acid treatment
obtained was acrolein, while the maximum acrylic acid (oxalic acid/HCl) of ZSM-5, improvement in acrylic acid
selectivity of more than 20% was obtained with 5% V selectivity was reported.[50] In another study using 10 wt.
loading at 275 C. Interestingly, less selectivity towards % of vanadium oxide (V2O5) loading on ZSM-5, only 18%
acrylic acid was observed at higher metal loading of selectivity of acrylic acid was observed. For the case of
10 wt.% vanadium. But, at a lower temperature of 250 C, MoV2O8 loaded ZSM-5, 17% selectivity for acrylic acid
the results differed; higher selectivity for 10 wt.% com- was obtained. However, the yield was not reported.[51]
pared to 5 wt.% loading was reported.[7] Owing to the The effect of the preparation procedure was studied
toxic nature of vanadium, readily available iron (Fe) was by Diallo et al.[53] over Fe-MFI catalyst with a Fe content
loaded onto the zeolite beta. The conversion and yield of 0.6 wt.%. The catalysts were prepared through hydro-
increased with the Fe content from 1.2 to 4 wt.%. A thermal synthesis, impregnation, ion exchange, and
post-synthesis treatment (fluoride medium). The findings three-dimensional topology and is structurally similar to
indicated that the catalyst prepared by hydrothermal syn- MFI zeolite,[74] whereas offretite (OFF) zeolite is less
thesis favoured acrylic acid production. The reduction of studied as a catalyst.
crystallite size and the enhancement of the external sur- Silva et al.[52] studied different zeolite topologies such
face with Nc-Fe0.6-MFI-45 led to one of the most stable as FAU (zeolite Y), FER (ferrierite), ZSM-11 (MEL),
catalyst systems, with only 7% catalyst deactivation, a MOR (Mordenite), OFF (offretite), MWW (MCM-22),
90% glycerol conversion, 87% selectivity towards acrolein, BEA (zeolite beta), and ZSM-5 (MFI). The zeolites
and 27% acrylic acid yield after 24 h on stream. were impregnated with constant vanadium (V) loading of
5 wt.%. Maximum stability and initial selectivity towards
acrolein were exhibited by MCM-22 and ZSM-11, respec-
3.1.3 | MCM-22 tively. In general, for a time on stream of 10 h, the
sequence of acrolein selectivity could be summarized as
MCM-22 is an anionic and unique ordered porous struc- MCM–22 > ZSM–11ZSM–5FER > MOR > Y > OFF.
ture zeolite having a height and diameter of 1.82 and Meanwhile, for acrylic acid yield, the observed order was
0.71 nm, respectively. It is made up of two non-intersecting BEA (17.7%) > MCM-22 (16.0%) > ZSM-5 (12.0%)
pore systems with large 12-membered-ring super- > ZSM-11 (11.6%) > FER (5.5) > MOR (3.2%) > OFF
cages.[67,68] MCM-22 has been studied as a catalyst for the (1.8%) > FAU (1.1). MCM-22 and BEA showed the best
pyrolysis and Fischer-Tropsch process to produce phenolic product yield among all the studied catalysts. However, large
compounds and liquid fuels, respectively. For acrolein pro- coke deposition was reported for the catalysts with extra
duction from glycerol, MCM-22 was active with up to 50% open topologies, such as 12.7% for BEA and 10.3% for MWW
of acrolein selectivity.[69] The molar ratio of SiO2/Al2O3 (MCM-22) topology. An acid side density of 0.8 mmol1 was
and the density of acid sites were essential parameters in found to be optimum to achieve good acrylic acid yield. Also,
determining the desired product selectivity.[70] a reduction in acrolein selectivity was observed with a
Silva et al.[52] studied different zeolites to evaluate the decrease in the total density of acid sites.
effect of zeolite topology. Further, the dispersion and Vanadosilicates were also investigated for the glycerol
reducibility of the vanadium species were also consid- oxydehydration reaction to obtain value-added chemicals
ered. Among the different zeolites investigated, bifunc- from glycerol. High acrolein selectivity of 85.4% was
tional V/H-MCM-22 (MWW topology) showed superior reported.[55] According to the spectroscopic analyses, a
performance. Despite a moderate glycerol conversion of dynamic change of vanadium oxidation states (V5+/V4+)
76.2%, the catalyst reached a maximum acrylic acid selec- occurred, which promoted the catalyst activity. Vieira
tivity of 21% and an acrylic acid yield of 16% after 10 h. et al.[56] investigated the behaviour of Al-free
dos Santos et al.[54] studied the effect of iron (Fe) loading vanadosilicates through density functional theory (DFT)
on H-MCM-22 zeolite. The authors achieved a 52.6% analysis and experiments. Upon water adsorption of the
acrylic acid yield. This is the highest yield in a single-step samples, new sites, believed to be hydroxylated sites
process over zeolite catalysts. Interestingly the low Fe (O3V OH Si), were produced. These sites acted as Brøn-
content loaded zeolite exhibited better results than higher sted acid sites, which reduced and blocked the Lewis
metal content loading at 320 C. The reduced yield at high acidity of the samples. A reduction in side-product forma-
Fe loading could be attributed to the reduction of acid tion was also reported.
site density. Hence, Fe-containing zeolite catalysts are a
potential substitute for vanadium and other toxic heavy
metal-based catalysts. 3.1.5 | Relative comparison of zeolite-based
catalysts
3.1.4 | Other zeolite-based catalysts For the oxydehydration process, the need for zeolite as
an acid catalyst seems to be indispensable. However,
Faujasite type zeolite, Zeolite Y (FAU), has a super-cage appropriate zeolite topology, Si/Al ratio, metal loading,
and microporous structure. It is suitable for metal and acidity are critical parameters. Zeolite pore size and
impregnation and is generally employed for adsorption metal dispersion also play a significant role. The studies
and emission control.[71,72] Ferrierite zeolite (FER) is an on zeolite-based catalysts, ZSM-5, BEA, and MCM-22,
average pore-sized zeolite. It offers good selectivity as showed zeolites are excellent supports for the glycerol
an acid catalyst.[73] Mordenite (MOR) type zeolite offers oxydehydration process. ZSM-5 and BEA have moderate
good catalytic activity with appreciable thermal stability. acidity, good surface area, and easy metal loading capa-
Meanwhile, MEL (ZSM-11) is a high silica zeolite with bility. For the case of H-ZSM-5-based catalysts, the co-
presence of different types of acid sites (Lewis/Brønsted) a similar yield was obtained even at a low space velocity.
improved the acrolein yield and decreased the coke for- Furthermore, large pore size zeolites were found to be
mation.[65] Also, large metal loading increased the extra better for the process. Vanadosilicates showed relatively
framework species such as Fe, Al, and Fe-Al, which were good selectivity. However, they have not been widely
generated during the preparation methods (hydrolysis or investigated for the glycerol oxydehydration process. The
calcination).[75] The MCM-22 zeolite showed the highest complicated preparation process and high catalyst syn-
acrylic acid yield and good performance even under rig- thesis cost are some of their drawbacks.
orous reaction conditions. Its unique topology helped in To sum up, zeolites are promising acid catalysts, and
providing stability in radical conditions. They can be used with further improvement in the catalytic properties,
under extreme conditions such as high space velocity, but enhanced performance can be achieved. Improvement in
TABLE 5 Various mixed metal oxide catalysts studied for the glycerol oxydehydration reaction
Selectivity
Glycerol
(%)
Temp WHSV conversion Yield TOS
Catalyst Metal loading (wt.%) ( C) (h1) (%) Ac AA (%) (h) Reference
Fe-V Fe1V 300 20 98 - - 5 10 Wang et al.[79]
Fe1.2V 100 - - 14
Fe 1.4V 100 - - 5
Fe 1.6V 100 - - 4
Fe 1.8V 100 - - 4
Fe 2.0V 100 - - 3
Fe ∞ V 100 - - 4
1.2 100 - - 0
WV 0.23 318 0.6 >99 11 26 25 2 Soriano et al.[80]
W-V-Nb- V/(W + V + Nb) = 0.13 290 2.6 100 21 26.5 34 100 Chieregato et al.[81]
O
W-V-Nb- W/V/Nb = 1/0.2/0.15 265 3.8 100 - - 50.5 37 Chieregato et al.[40]
O
MoVW W/Mo/V = 1:0.45:0.04 290 3.4 100 - 42 51 69 Chieregato et al.[40]
MoV Mo1V0.25 300 - 100 - - 20.8 - Shen et al.[39]
MoVW (Mo/V/W/O): 250 0.8 100 8.2 30.5 - 14 Yun et al.[34]
12.3/1.7/16.1/70.0
W-V- W2.2V0.5Nb2.3O14 323 1.2 100 - 33.7 1–2 Omata et al.[82]
NbO W2.2V0.4Nb2.4O14 285 100 46.2
2.5 wt.% PO4/ 285 100 59.2
W2.2V0.4Nb2.4O14
MoVW - 290 3.4 100 - 42 28 69 Chieregato et al.[83]
MoVO - 350 5 94 15 - 32 6 Possato et al.[50]
Mo-V-O MoVO5/Mo4.65V0.35O14/ 320 - 100 33.5 - 29.6 6 Rasteiro et al.[84]
MoO3: 37.8/35.1/27.1
VW/ Si/W/V: 0.85/0.12/0.03 327 81a 100 - 30 - La Salvia et al.[85]
KIT6
W-V-O - 180–380 6.8a 100 - 32.5 - Delgado et al.[86]
MO-V MoV2O8 320 - 100 6 57 - 6 Rasteiro et al.[38]
(SDS-
0.10)
Abbreviations: AA, acrylic acid; Ac, acrolein; Temp., temperature; TOS, time on stream; WHSV, weight hourly space velocity.
a
W/F (gcath [molglycerol]1).
catalytic activity can be achieved through treatment method. It is believed that Fe and V combination
(before loading) with appropriate alkaline or acid solu- develops an oxide framework and acid–base pair. The
tions. The amount of loading is also crucial in determin- combination gives rise to a strong oxidizing catalyst capa-
ing the higher yield of the desired product. An optimum ble of catalysing C-C bond breakage.[88]
amount of metal loading must be applied as excess may
favour the products via the cracking route. Low-cost, Tungsten-vanadium catalyst (W-V)
non-toxic, and optimum metal loading, such as Fe, can Tungsten has moderate acidity, redox behaviour,
be considered in place of toxic metals (V, W). Further, good stability, and versatile properties that are advan-
the less studied zeolites such as ZSM-11 (MEL) can also tageous to its use as a catalyst for selective oxidation,
be explored. dehydrogenation, superconductivity, photocatalysis,
hydrocracking, isomerization, and fuel cells. Tung-
sten trioxide (WO 3 ), tungstic acid, and tungsten car-
3.2 | Mixed metal oxide catalyst bide are common tungsten catalytic forms. Tungsten
trioxide possesses acidic and redox properties, while
Metal oxides prepared by different synthesis techniques tungsten carbide (WC) resembles noble metals in
effectively dehydrate glycerol to acrolein. Up to 75% acro- terms of properties. Homogeneous tungsten-based
lein selectivity using WO3/ZrO2 and Ta2O5 catalysts has catalysts have many limitations, such as complex sep-
been achieved.[76,77] For the conversion of glycerol to aration and reuse. Hence, hetero-tungsten-based cat-
acrolein, pure and mixed metal oxides such as WO3/ alysts are mainly employed. A lacking oxygen catalyst
ZrO2, WO3/TiO2, and Nb2O5 possess sufficient acidity known as tungsten bronze has a unique framework
and stability to obtain a good yield.[78] Generally, it is that allows for the incorporation of a large amount of
observed that most metal oxides studied for the glycerol elemental loading. [89] For glycerol conversion,
oxydehydration process contain vanadium as the key ele- tungsten-based catalysts are efficient as they exhibit
ment. However, there are also few other metal oxides cat- good performance in the dehydration step resulting
alyst combinations that do not contain vanadium. in good acrolein yield. Also, tungsten imparts
Table 5 discusses the various mixed metal oxide catalysts enhanced stability to the catalyst. [85]
studied for the oxydehydration process. For the glycerol oxydehydration process, various
tungsten-containing metal oxide bronzes, such as hexago-
nal tungsten bronze h-WO3, could promote good acrolein
3.2.1 | Vanadium-containing mixed oxide formation. In contrast, molybdenum or vanadium modi-
catalyst fied h-WO3 showed a good yield of acrylic acid. The good
interaction between W and V metals results in improved
Vanadium, the lightest element of the V group, is used as selectivity and conversion for the glycerol oxydehydration
the key element for synthesizing several chemicals process. Tungsten has also been shown to be effective as
through dehydrogenation, hydrogenation, C C bond an inhibitor for total oxidation via the reduction of an
cleavage, alcohol oxidation, and deoxy-dehydration. It is oxidizing agent such as vanadium.[34]
the most employed metal due to its substantial oxidizing The optical atomic ratio is critically important for
property. Vanadium acts as an oxidizing species by pro- achieving the desired acrylic acid yield for the addition of
viding redox sites. The combination of vanadium with V to W. Soriano et al.[80] found that with increasing V/
other catalyst components such as iron (Fe) and tungsten (W + V) atomic ratio, the surface area increased. A 25%
(W) results in a promising catalyst for processes such as yield of acrylic acid was reported for a catalyst with a V/
electrocatalysis and acrolein oxidation.[87] When com- (W + V) atomic ratio of 0.23. A similar yield of 25.7%
bined with other metals, vanadium acts either as a pro- was reported by Shen et al.[39] by employing W1V0.25. It
moter (through a change in the solid crystalline was observed that large vanadium loading was not
structure), thermal stabilizer, or oxidizing agent. favourable towards acrylic acid selectivity, probably due
to an increase in COX formations. Similarly, lower vana-
Iron-vanadium catalyst (Fe-V) dium content resulted in the formation of heavier com-
Wang et al.[79] studied the glycerol oxydehydration pro- pounds, leading to reduced acrolein yield. Hence, an
cess by loading iron oxide on the surface of Fe optimum amount must be determined. For tungsten
orthovanadate. A maximum acrylic acid yield of 14% was vanadium complex catalysts, the type of precursor plays
obtained at 1.2 wt.% Fe loading. Also, it was reported that an important role in determining thermal stability, mor-
catalysts prepared by the solid-state synthesis method phology, and the ratio of monoclinic to hexagonal tung-
were better than those prepared by the impregnation sten phases (m-WO3 to h-WO3). The presence of h-WO3
in catalysts is also critical in determining the acrylic acid compounds.[94] Lacerda et al.[95] performed
yield. computational studies using T-Nb2O5 and T- Nb2O5 with
La Salvia et al.[85] studied the WV catalyst using vanadium doping. It was found that the addition of vana-
KIT-6 as inert support prepared using the reflux method. dium helped in promoting acrylic acid production. Also,
A better acrylic acid yield of 30% was observed with the vanadium helped in reducing energy costs. H2O2 was
use of inert support than when employing only a WV cat- found to be beneficial for the process as the peroxo
alyst (20% acrylic acid yield). This could be because of the groups involved imparted greater oxidation capacity.
reduction in the strong acid sites arising from the interac-
tion with the KIT-6 support and decreased undesired side Molybdenum-vanadium catalyst (Mo-V)
reactions. The improvement in the reactivity of vanadium Molybdenum has strong coordination geometry and a
oxide by adding tungsten oxide could be attributed to the unique structure. By incorporating vanadium as a pro-
(i) acidic character of tungsten, (ii) electron sharing moter into the molybdenum oxide system, the desired
between vanadium and tungsten, or (iii) change in the active phase for process-specific catalysis can be achieved.
structure of vanadium as a result of tungsten The incorporation of vanadium has a strong influence on
incorporation.[90,91] morphology, lattice factors, and properties. It can activate
C-H bonds to help in partial oxidation reactions, such as
Tungsten-vanadium-nibonium catalyst (W-V-Nb) in the case of propane oxidation.[96] Its three properties,
Niobium oxide catalysts have gained attention as a pro- providing acid sites, mild oxidation ability, and good sta-
moter, support, active phase, or redox and acid part of bility, makes it a suitable catalyst.
the catalyst. The introduction of niobium results in a The combination of Mo and W with V on the catalyst
strong interaction between niobium and other species.[92] elemental valence and oxide strength was investigated by
Nb oxide as a catalyst was found to be efficient for the Shen et al.[39] using Mo1V4 oxide and W1V0.25. The acrylic
glycerol dehydration to acrolein. An acrolein selectivity acid yields of 20.1% and 25.7% were obtained over Mo1V4
of 51% was reported on the Nb2O5 catalyst.[93] and W1V0.25, respectively. It was observed that with
The study of structure-reactivity to understand the increasing V content, the yields of CO and CO2 also
behaviour of oxidizing species and the effect of tri increased. Another significant finding was the acidity
component loading was studied. Chieregato and co- order: W1V0.25 > W1V1 > W1V4 > WO3 > V2O5. Vanadium
workers[40,81] studied the effect of Nb addition and found was found to have increased acidity when compared with
that with the addition of Nb as a promoter in the W-V-O, pure MoO3, WO3, and V2O5 catalysts. Rasteiro et al.[38]
selectivity towards acrolein increased. A 34% acrylic acid studied the Mo-V catalyst and the effect of the catalyst syn-
yield was reported for the W-V-Nb catalyst. On adding thesis method. Up to 57% selectivity towards acrylic acid
Nb, there was an increase in the acid sites. However, was obtained. The synthesis method and the materials
there was no considerable effect on acid sites density for involved in the process could significantly impact the mor-
both catalysts with and without Nb. Also, a significant phology and type of metal phase created. Surfactants could
increase in the surface area was observed.[81] In another bring about changes in the catalyst’s surface composition,
study, Chieregato et al.[40] observed that the incorpora- crystal structure, porosity, and stability. By using ionic sur-
tion of Nb to W-V oxide gave a very high yield of 50.5% factants, the authors obtained rod-like morphology, which
acrylic acid. The reaction was performed at a high glyc- was believed to have increased the redox behaviour prop-
erol concentration and lower contact time. The order of erty and stabilized the crystalline phase.
surface area reduction observed was W–V–Nb > W– The addition of Mo to V creates a catalyst with
V > Mo–V–W. Hence, the addition of niobium resulted medium/moderate acidity and good oxidation ability that
in a catalyst with superior properties. Omata et al.[82] is suitable for the glycerol oxydehydration process. The
studied the W-Nb-O catalyst, both with and without crystalline and amorphous phases exhibited by the MoV
vanadium. The incorporation of vanadium resulted in combination can easily support the redox reaction.[97]
increased acrylic acid yield; 46% acrylic acid yield was Compared to separate MoO3 and V2O5, Mo-V mixed
obtained for the W2.2V0.4Nb2.4O14 catalyst composition. oxide catalyst, that is, MoV2O8, exhibited large vacant
The authors concluded that vanadium is an essential ele- sites creation, resulting in an improved Mars-van
ment for converting acrolein to acrylic acid. Krevelen mechanism and hence better yield.
Nibonium-vanadium catalyst (Nb-V) Molybednum- vanadium-tungsten catalyst (Mo-V-W)

The association of the niobium oxide with other metals, The combination of the three metals (W, Mo, and V) was
such as vanadium or molybdenum, can generate high efficient for the glycerol oxydehydration process due to
catalytic activity towards the oxidation of organic their mild acidity combined with strong oxidizing power.
Chieregato et al.[36] obtained a high yield of 51% for acrylic strength, (iii) metal oxide lattice oxygen, (iv) host struc-
acid over the tri component catalyst. The incorporation of ture, and (v) the ordering and environment of oxygen
molybdenum helped in regulating the behaviour of atoms were observed to play a significant role.[55]
vanadium as a strong oxidizing agent. There are only a Comparatively, it can be observed that the use of
few studies based on computational software techniques vanadium is indispensable as an oxidizing catalyst. For
such as atomic simulation environment (ASE), Quantum vanadium-based metal oxide catalysts, parameters such
ESPRESSO, and DFT calculations. DFT is a tool that pro- as (i) amount of metal loading, (ii) density of acid sites,
vides an insight into the structure and properties of the cata- and (iii) active sites spatial isolation were found to be cru-
lyst and helps in understanding the mechanism. Yun cial for the oxydehydration of glycerol to acrylic acid.
et al.[34] synthesized a Mo-VW catalyst based on computa- Vanadium characteristics can be modified through dis-
tional calculations to study the properties and the structure persion, addition on supports, and additives. The use of
of the catalyst. Firstly, the effect of incorporating W was iron with vanadium does not necessarily lead to suitable
assessed by DFT calculations. Later, the computational catalysts for glycerol oxydehydration. This is mainly
results were compared and fitted with the experimental because of the lack of strong acidic properties of the
runs. A 30.5% selectivity for acrylic acid was obtained. catalyst.
The highest acrylic acid yield of 59.2% was reported
for the W-V-Nb oxide catalyst combination. The combi-
3.2.2 | Other mixed metal oxide catalysts nation of three metals enhanced the oxidative capability
and coke suppression property of vanadium. Improve-
Interestingly for mixed metal oxides, very few catalysts have ments in the surface area and acid site density were
been used without vanadium for the glycerol oxydehydration observed because of Nb addition. In contrast, the increase
reaction. W-Nb mixed oxide catalysts have been efficient in in Brønsted acid sites was attributed to tungsten addition.
reactions such as esterification, Friedel-Crafts, and alkylation. Further, the variation of Brønsted acid sites with the
Niobium oxide-containing catalysts favour the formation of a vanadium content in the catalyst can be studied to
C-C bond.[98] For tungsten niobium complex catalysts, by achieve high acrolein selectivity in the reaction. W-V
varying the niobium content, the acid and textural properties oxide catalyst exhibited good stability but suffered from a
of the catalyst can be easily tailored. The ratio of Brønsted to low surface area. The studies on Mo-V suggested ortho-
Lewis acid sites can also be easily altered to suit the specific rhombic structure formation of the catalyst. The exis-
catalyst application.[99] tence of highly charged ions (MO6+) and amphoteric ions
Hexagonal tungsten bronze usually promotes acrolein (V4+ and Mo4+) was necessary for glycerol
selectivity; further, by combining with niobium, the acrolein oxydehydration. These highly charged ions readily inter-
selectivity increases. However, the higher concentration of act with acrolein. Finally, in the absence of V, the W-Nb
Lewis acid sites probably arises because of higher niobium catalyst was found to be inefficient for the
loading. This decreases the yield because of the generation of oxydehydration process. In summary, mixed metal oxides
heavy compounds. Hence an optimum level of quantity of the are promising catalysts, and for enhanced glycerol dehy-
metal loading is necessary. Chieregato et al.[81] observed 73% dration and oxidation of acrolein, further fine-tuning of
acrolein selectivity for their W-Nb catalyst. However, a poor the crystal phase composition could be beneficial.
selectivity towards acrylic acid of 2.5% (330 C) was reported. Finally, designing a superior catalyst exhibiting excel-
Though the combination of W-Nb improved Brønsted sites lent properties combination of both computational and
acidity, it showed good acrolein yield whereas acrylic acid experimental fields is required. As there are very few
yield was poor in the absence of vanadium. Hence, a potent studies concerning the reaction mechanism, computa-
oxidizing agent such as vanadium is necessary to achieve good tional techniques such as DFT could be beneficial in fur-
acrylic acid yield. In summary, the W-Nb catalyst alone may ther understanding catalyst properties, design, reaction
not be suitable for glycerol oxydehydration. Incorporating mechanism, atomic structure, and reaction pathways.
vanadium or other suitable oxidizing agents might be the
solution to achieve good acrylic acid yield.
3.3 | Heteropoly acid–based catalyst
3.2.3 | Relative comparison of mixed metal Heteropoly acids (HPAs) are a group of materials with
oxides definite structures and adjustable acidity suitable as
acidic and redox catalysts.[100] Their composition includes
For the case of mixed metal oxide catalysts, factors such an oxygen atom, a hydrogen atom (acidic H), hetero
as (i) dynamic redox cycles, (ii) metal-oxygen bond atoms (such as phosphorous, arsenic, or silicon), and
TABLE 6 Heteropoly acid and phosphate-containing catalyst studied for the glycerol oxydehydration process
Selectivity
Glycerol
(%)
Loading Temp WHSV conversion AA
Catalyst (wt.%) ( C) (h1) (%) Ac AA yield (%) TOS Reference
SiW/Al2O3 4 90 - 83.78 - - 25.11 4 Thanasilp
et al.[105]
V-SiW/HZSM5 4 90 - 98.64 - - 32.44 4 Thanasilp
et al.[32]
SiO2–MnO2 0.9% Cu 70 - 77.1 11.6 72 57.6 30 Sarkar
et al.[106]
Mo3VOX/ - 325 0.3 100 2.9 12.1 - 2 Liu et al.[41]
H4SiW12O40/
Al2O3
Cs(VO)0.2(PMo)0.25 - 340 0.5 100 6.9 56.6 60 10–60 Li and
(PW)0.75 Zhang[107]
PV2Mo10 /ZSM5 - 350 100 8 29 33 6 Suganuma
et al.[33]
H3PO4/WVNbO 2.5 PO4/ 285 1.2 100 - 14 59.2 2 Omata
W2.2V0.4 (AA) et al.[82]
Nb2.4O14
Abbreviations: AA, acrylic acid; Ac, acrolein; Temp., temperature; TOS, time on stream; WHSV, weight hourly space velocity.
addenda atoms (usually molybdenum or tungsten). A investigated the effect of polyoxometalate at a low tem-
cluster is formed between addenda atoms and hetero perature of 90 C in the liquid phase. Polyoxometalate is a
atoms through the oxygen atoms. HPAs can be further conjugate anion of HPA. The highest yield of 25% was
classified as Keggin type (XM12O40x-8; X is the central obtained at 4 wt.% active components loading for
atom, M is the metal ions) and Wells–Dawson-type HPAs SiW/Al2O3. No significant improvement in yield was
([(Xn+)2M18O62](16 2n) ; Xn+ is a central atom and M observed on increasing the loading up to 8 wt.%, probably
is addenda cage atoms).[101] Molibdophosphoric acid, due to less oxidation. The yield of acrylic acid decreased
tungstophosphoric acid, and tungstosilicic acid are some in the order of SiW/Al2O3 > PW/Al2O3 > PMo/Al2O3.
of the most common HPAs.[102] However, the order of acidity observed was
Keggin type HPAs can be easily synthesized and are PW/Al2O3 > SiW/Al2O3 > PMo/Al2O3. No new sites
readily available. They possess good thermal stability and were observed on adding polyoxometalate. The combina-
a stable structure, while Dawson-type HPAs usually pos- tion of Al2O3 and polyoxometalate retained the Brønsted
sess high acidity and are considered as superacids. Major acid nature. The higher yield demonstrated by SiW/Al2O3
synthesis routes of HPAs include precipitation, ion could be attributed to its good oxidation ability with mod-
exchange, and electrodialysis.[101,103] HPAs possess good erate acidity. There are only a few studies in the literature
proton mobility, and their properties can be tailored upon involving the reaction in liquid phase.
their combination with suitable amounts of alkaline In another study, Thanasilp et al.[32] investigated SiW
metals through proton exchange. Owing to their non- by varying loadings (0–8 wt.%) of metal dopants such as
toxic and non-corrosive nature, they are also considered Ce, Co, Ni, and V on the ZSM 5. The reactions were
green catalysts. Glycerol dehydration over HPAs catalysts attempted in the liquid phase in a three-neck reactor at a
has exhibited remarkable results. Very high selectivity very low temperature of 90 C. Among all, 6 wt.% V load-
towards acrolein was reported.[24] Alhanash et al.[104] ing, V-SiW/HZSM-5, gave the best yield of 32.44%. Also,
obtained 98% acrolein selectivity on Cs2.5H0.5PW12O40 the V-based catalyst was found to be the most acidic with
(CsPW). Table 6 discusses the various heteropoly acid the highest surface area. Total acidity followed the
catalysts studied for the glycerol oxydehydration process. sequence V > Ni > Ce > Co. The same sequence was
A bifunctional catalyst is formed upon a combination observed for the acrylic acid yield, V > Ni > Ce > Co.
of heteropoly acid (oxidation) and zeolite (acid site for However, at a high loading of 8 wt.%, decrease in the
dehydration). In general, it is observed that the HPAs can yield was observed, possibly due to mass transfer restric-
be easily and efficiently distributed on silica, alumina, tions or the presence of high acid sites density combined
and aluminosilicate support.[108] Thanasilp et al.[105] with a deficiency of the oxidizing factor.
Liu et al.[41] studied the effect of calcination tempera- far, 60%, was reported for Cs(VO)0.2(PMo)0.25(PW)0.75.
ture on the reactive phase and obtained a good acetic acid HPAs possess strong Brønsted sites. In general, the Daw-
and acrylic acid yield. It was observed that the calcina- son type possesses more Brønsted sites than Keggin
tion temperature greatly influenced the structure and type.[110] The heteropoly anions act as reaction stabilizers
activity of the Mo3VOX/H4SiW12O40/Al2O3 catalyst, with and reduce the activation energy in the reactions. They
a 46.2% yield at 450 C. For this bifunctional catalyst, oxi- are suitably active for acidic and oxidation catalysis. Fur-
dation ability was provided by Mo3VOx, while ther, the catalytic activity can be increased through load-
H4SiW12O40 governed the dehydration step. The interac- ing HPAs on zeolites (mesoporous supports). A stable
tion of Al2O3 with H4SiW12O40 resulted in WOH2+ for- surface is formed upon the attachment of support and
mation, which increased the acidity, though Al2O3 HPAs.[101]
mainly had Lewis acid sites. The contact between For the case of caesium heteropoly tungstate
H4SiW12O40 and Al2O3 enhanced the Brønsted acidity. (CsHPW), the superior catalytic activity could be attrib-
On Al2O3, Brønsted acid sites appeared in a hydrated uted to the stable porous structure and optimum acidity.
environment, while the Lewis acid sites appeared in an For HPAs dispersed on zeolites, an optimum amount of
anhydrous environment. Further, the interaction with loading must be applied to prevent blockage of pores and
moisture resulted in the formation of active Brønsted avoid mass transfer limitations. Further, HPAs also suffer
sites.[57] from some drawbacks, such as fast deactivation because
HPAs have also been studied for the glycerol of their acidic nature. They are readily decomposed at
oxydehydration process by introducing vanadium to high temperatures, and therefore must be operated in a
substitute Mo or W. Strong agents such as vanadium suitable temperature range. Similarly, regeneration
and caesium further improve the heteropoly acid cata- becomes difficult through high-temperature calcination.
lytic activity and thus increase the acrylic acid yield. Li
and Zhang[107] reported up to 60% yield of acrylic acid
by employing Cs(VO)0.2(PMo)0.25(PW)0.75. Good stability 3.4 | Phosphate-containing catalyst
and less coke deposition were its remarkable features.
Because of the porous structure and large surface acid- Phosphorus is a potential element for various compound
ity, caesium heteropoly tungstate (CsHPW) demon- formations, owing to its remarkable ability of bond for-
strated elevated acidity. Hence, incorporating a strong mation, and hence, can be equated for carbon.[111] The
oxidizing agent (vanadium) into the secondary structure group of phosphate catalysts mainly include phosphoric
of the caesium salts of HPAs was advantageous for acid substituted composites and metal phosphates. Due
acrylic acid formation. The variations in surface acidity to the mesoporous structure and adjustable surface acid-
and oxidation ability of the catalyst also improved. Fur- ity, they have been studied for biomass conversion, syn-
ther, for the case of Cs2.5H0.5PW12O40, it was observed gas conversion, biodiesel production, and butane
that the acid–base and redox properties could be varied oxidation over catalysts such as sodium phosphate and
over a wide range by changing the chemical vanadium phosphate.[111]
composition. For the glycerol dehydration to acrylic acid, 92% acro-
To overcome low acrylic acid yield, Sarkar lein selectivity was reported over an iron phosphate
et al.[106,109] studied SiO2-MnO2 with Cu nanoclusters, (FePO4) catalyst. FePO4 is a weak acid catalyst. FePO4
resulting in 74.7% acrylic acid selectivity for the liquid was also studied for the glycerol oxydehydration process,
phase. The catalyst showed remarkably low deactivation. but a very low yield of acrylic acid was obtained.[112]
Interestingly low reaction temperature of 70 C favoured Phosphates suffer from rapid deactivation and low hydro-
the reaction. This was attributed to H2O2 used as an oxi- thermal stability. The effect of loading cobalt oxide (Co),
dizing agent. However, a long reaction time (>30 h) was Fe, and V on aluminium phosphate for the
required for the good selectivity of acrylic acid. oxydehydration reaction was investigated by Lopez-
Suganuma et al.[33] studied the effect of loading molybdo- Pedrajas et al.,[113] where Co exhibited the best acrylic
vanado-phosphoric acid on zeolite ZSM-5. The structure acid selectivity among the tested metals. In another study
and morphology of the catalyst helped in reducing the by Omata et al.,[114] phosphoric acid (H3PO4) loading to
side reactions like polymerization and auto-condensa- the W-V-NbO catalyst significantly improved the acrylic
tion. By loading 17.3 wt.% of PV2Mo10, a 31% yield of acid yield. A high yield of 59.2% was obtained by the
acrylic acid was attained. With the increase in the addition of phosphoric acid. A 13% improvement in yield
amount of PV2Mo10, acrylic acid yield decreased. was observed on adding H3PO4 to W-V-Nb. This could be
In summary, HPAs are a promising catalyst for the due to the increase in the acidity of the catalyst
oxydehydration process. The highest acrylic acid yield so (Brønsted) arising from the interaction between
vanadium and phosphoric acid. Further, an important Brønsted acid sites and suppressed any side reactions or
observation was the change of Lewis acid sites to Brøn- excess oxidation of acrylic acid to form COX through
sted sites upon the absorption of water. This change was interaction with vanadium. Metal phosphates with high
established through the obtained Fourier transform infra- surface area and large pore size have attracted particular
red (FTIR) results. interest due to their relatively low cost, tunable surface
To sum up, phosphoric acid helps in promoting both properties, and controllable morphologies. Their activity
dehydration and oxidation steps. It increased the depends not only on their acidity (mainly acid sites of
FIGURE 5 General schematic reaction setup employed for the (A) liquid phase and (B) gas phase of the glycerol oxydehydration process
weak-medium strength) but also on the redox sites. For literature concerning the reaction mechanism in detail.
the glycerol oxydehydration reaction, the highly efficient For the dehydration of glycerol, two possible paths have
phosphorus-modified metal oxides and metal been proposed. The first path is that the primary
phosphates-based catalysts could be suitable catalysts. hydroxy groups of glycerol are dehydrated to produce
acetol, while the secondary hydroxy groups get proton-
ated on Brønsted acid sites. The removal of H3O+
4 | R EACTION M ECHANISM results in the formation of 1,3-dihydroxypropene, which
further produces 3-hydroxypropionaldehyde (a highly
4.1 | Comparison of gas phase and liquid reactive intermediate) upon keto-enol rearrangement.
phase reaction scheme 3-hydroxypropionaldehyde instantly converts to pro-
duce acrolein at acidic sites. Acrolein further acts as an
For the glycerol oxydehydration process, the majority of intermediate for acrylic acid production through oxida-
studies have been performed in the gas phase. Only a few tion at the redox sites. If the reaction follows the second
studies were conducted in the liquid phase. The reaction path, that is, cracking instead of dehydration, it pro-
in the liquid phase has the advantage of better tempera- duces acetaldehyde that gets further oxidized to acetic
ture control to avoid issues such as hotspots but suffers acid. The reaction proceeds via the attachment of the
from reactor corrosion due to toxic chemicals and com- terminal OH group of glycerol to the Lewis site. The H+
plex catalyst separation.[64] However, the reaction at low from the internal carbon atom gets attached to the O
temperatures involving the liquid phase needs to be fur- atom. The formation of 2,3-dihydroxypropene takes
ther investigated. The detailed reaction setup commonly place, and 2,3-dihydroxypropene undergoes tauto-
employed for the liquid and gas phase oxydehydration merization to form acetol. Figure 6 shows the proposed
reaction is shown in Figure 5. glycerol oxydehydration reaction mechanism of glycerol
via Brønsted acid and Lewis acid sites. The kinetic factors
determine the possibility of the reaction to proceed
4.2 | Glycerol oxydehydration reaction through either path. A large quantity of the extra frame-
mechanism work active species could promote path 2 (cracking) by
suppressing path 1 (dehydration), that is, the conversion
The reaction mechanism of the glycerol oxydehydration would derail from the acrolein and acrylic acid
reaction is an important aspect to be studied as it pro- production.[115,116]
vides an insight into the processes happening at the The conversion of acrolein to acrylic acid requires cat-
molecular level. There are very few studies in the alysts with sufficient oxidizing properties. For high
FIGURE 6 Detailed reaction mechanism for the glycerol dehydration over (A) Lewis and (B) Brønsted acid sites and the oxidation of
intermediates
acrolein contact, highly charged ions having amphoteric played by the Brønsted sites instead of the Lewis sites.
behaviour and varying oxygen states are required. The Brønsted acid sites serve as the point of glycerol dehydra-
optimum amount, multifunctionality, spatial isolation, tion through the interaction of the C2-hydroxyl group.[52]
and good dispersion of oxides on the supports lead to The importance of the Brønsted sites is evident from the
atomic instability on the surface and allows easy charge previous studies where the glycerol conversion did not
transfer of the oxidizing catalyst. Acrolein is absorbed by significantly increase with the increase in the concentra-
these oxidizing species and gets oxidized to acrylic tion of Lewis sites.[37] Acidity in the range of
acid. Such as for the case of vanadium, acrolein is adsorbed 8.2 ≤ H0 ≤ 3.0 (Hammett acidity function: H0) was
on vanadium species and is oxidized to acrylic acid, with found to be suitable.[123] In terms of Brønsted acid sites
consequent reduction of V5+ to V4+. Then, the V4+ ions to total acid sites ratio, the acrolein yield was reported to
ðBrønstedÞ
are re-oxidized to V5+ through molecular oxygen following decrease with a decrease in ðBrønstedþLewis Þ. Indeed, Brøn-
the Mars-van Krevelen mechanism, thus completing the sted sites were required in a large number,[40] as Lewis
catalytic cycle.[37,51,117,118] The process of acrolein oxidation acid sites represent weak acid sites having less acidity;
for a MoV catalyst is shown in Figure 7.[24,30,119] For the hence, chances of high oxidation to undesired products
case of Fe-MCM-22, a high quantity of Fe (>1.2 wt.%) are higher. Undesired side products such as acetol are
resulted in deep oxidation of products, leading to COX for- likely to be formed.[32,120]
mation and reduced acrylic acid yield.[54] The detailed It is to be noted that glycerol dehydration is an
mechanism of acrolein and acrylic acid formation over endothermic reaction (ΔH = 222.32 kJ mol1), whereas
vanadosilicates is shown in Figure 8.[55] acrolein oxidation is an exothermic reaction
The role of acid sites is also critical. There are three (330.23 kJ mol1).[112,124] Hence, an optimum thermal
theories to describe the behaviour of acid sites: balance is necessary. It is also important to investigate
(i) Brønsted acid sites promote acrolein formation, the effect of individual species involved in the reaction.
whereas Lewis acid sites promote the formation of Thanasilp et al.[32] made an important observation
acetol[120]; (ii) Brønsted acid sites surrounded by Lewis regarding the order of reaction for the case of a liquid-
sites are beneficial for glycerol dehydration to acro- phase reaction. The glycerol conversion followed pseudo-
lein[121]; or (iii) The primary group of glycerol produces first-order kinetics. First-order kinetics was observed for
acetol while the secondary OH group produces acrolein glycerol concentration, while the oxidizing agent (H2O2)
upon interaction with strong Brønsted acid sites and showed almost no effect or approximate zero-order.
moderate strength Brønsted acid sites, respectively.[122] Among the tested models, the Langmuir–Hinshelwood
Among the three theories, the first theory is widely model (LH model) and Eley–Rideal model (ER model),
accepted, that is, the role of the acidic site is mainly the latter model better fitted the results. The standard
FIGURE 7 Mars-van Krevelen mechanism for acrolein oxidation to acrylic acid[24,30,119]

F I G U R E 8 Mechanism of (A) glycerol conversion to acrolein and (B) acrolein conversion to acrylic acid. (reprinted from Paula et al.,[55]
copyright (2016), with permission from Elsevier)
enthalpy change for the dehydration step was In summary, the reaction at different hydroxyl radi-
18.0 kJ mol1, and for the oxidation step, it was cals of glycerol produces acetic acid and acrylic acid at
298.3 kJ mol1.[75,82] The heat of adsorption and the Lewis and Brønsted sites, respectively.[41,125] Among the
activation energy was 18.45 and 28.57 kJ mol1, two steps of the glycerol oxydehydration reaction (oxida-
respectively.[32] tion and dehydration), glycerol dehydration to acrolein
TABLE 7 Properties of catalysts studied for the oxydehydration reaction
Carrier gas, Total acid

glycerol sites
Preparation Reactor composition Products BET surface density Deactivation
Catalyst method type (wt.%) reported area (m2 g1) (mmol g1) (%) Reference
H, Fe-MCM22 IE FB O2, 36 AC, HAT, PAL, 419 1.57 16.3a dos Santos
AD, ACA, AA et al.[54]
Fe-BEA IS FB Air, 99 AC, AA, AD, 614 0.806 - Diallo
ACA, ACT et al.[49]
Fe-MFI PS FB Air, 40 - 469 0.31 7 Diallo
et al.[53]
Mo-V-ZSM5 WI FB N2 & O2, 10 AC, AD, ACA, 77 0.417 6 Possato
AA et al.[51]
WVNb HT FB O2 & He, 6 AC, AA, ACA, 57 0.192 - Chieregato
AD et al.[40]
V-SiW/HZSM-5 SI BR Liquid phase FA, AC, AA, PA 225 2.12 - Thanasilp
H2O2, 20 et al.[32]
Cs(VO)0.2 PI FB O2/He, 20 AC, AA, ACA, 95.1 - - Li and
(PMo)0.5(PW)0.5 Zhang[107]
PV2Mo10 /ZSM5 WI FB N2 and O2, 30 AC, AA, AD, - 0.32b - Suganuma
ACA et al.[33]
H3PO4/WVNb HT FB N2 and O2, 5 AC, AA, AD, 97 0.25 - Omata
PL, HAT, et al.[114]
ACA
Abbreviations: AA, acrylic acid; AC, acrolein; ACA, acetic acid; ACT, acetol; AD, acetaldehyde; AT, acetone; BR, batch reactor; FA, formic acid; FBR, fixed bed
reactor; GA, glycolic acid; HAT, hydroxy acetone; HT, hydrothermal; IE, ion exchange; IS, isomorphous substitution; PA, propionic acid; PAL,
propionaldehyde; PI, precipitation; PL, propanol; PSI, post-synthesis isomorphous substitution; SI, sequential-impregnation method; WI, wetness
impregnation.
a
% coke.
b
Amount of Brønsted acid site/mol kg.
was identified as the rate-determining step. The reaction 4.3 | Role of carrier gas
process requires catalysts with mild or weak acidity to
perform the dehydration step efficiently; nearly spaced Oxygen is usually introduced in the feed as a carrier in
acid sites are not preferred for this process, as they might acrylic acid production from glycerol. It is either supplied
hinder the intermediate desorption, resulting in unde- in pure form or a mixture of N2 and O2 or air. The molec-
sired reactions.[85] The proper isolation of the acid and ular oxygen introduced with the feed helps regain the
redox sites helps improve the internal selectivity of original oxidation states of the oxidizing species, pro-
3-HPA from glycerol. The reaction environment should motes the redox characteristics of the oxidizing species,
support the dehydration of 3-HPA and suppress its oxida- enhances acrolein selectivity, and reduces coking.
tion. Further, undesirable secondary reactions such as In the case of vanadium, a strong oxidizing agent, a
condensation and oligomerization must be checked. They dynamic change in its oxidation state from +4 to +5
reduce the interaction of the active sites, resulting in occurs. Oxygen helps in increasing the concentration of
reduced desired product formation. Also, the efficient V5+ sites, resulting in a better oxidation reaction.[105,126]
dehydration of 3-hydroxypropionaldehyde in the first The reduction of vanadium brings about the conversion
step for producing acrolein is necessary. The deep oxida- of acrolein (generated on acid sites) to acrylic acid. The
tion must be prevented to avoid the large formations of O2 supplied in the reaction process to the reactor rein-
COX from the easily combusted compounds such as states the vanadium oxidation state and the oxygen
3-hydroxypropionaldehyde.[41] The catalyst preparation vacancy of the reduced vanadium atom of the oxide lat-
methods, properties, process operating parameters, and tice. This dynamic reduction and oxidation of vanadium
products obtained for the glycerol oxydehydration pro- atoms (from V5+ to V4+, and then from V4+ to V5+) and
cess are discussed in Table 7. the oxidation of acrolein occur according to the Mars-van
Krevelen process.[84] Similarly, the redox behaviour of Fe In summary, for the gas phase glycerol
(+III) species in the framework position was sustained oxydehydration reaction, the optimum temperature
by the presence of oxygen from the air.[49] depends mainly on the catalyst type and structure. A bal-
Oxygen also provides stability to the catalyst, reduces carbo- ance between good yield and less COX emissions is neces-
naceous deposits, and decreases coke formation. These benefits sary. Further, owing to the exothermic reaction nature,
were confirmed by performing the reaction both in the absence precise temperature regulation is difficult.
and presence of O2 over the same catalyst.[52,70,105] Diallo
et al.[49] performed the reaction in an atmosphere comprising
N2 only. Rapid deactivation, diminished activity, and the pres- 4.5 | Effects of contact time and total
ence of acrolein as a major product were detected. Li and reaction time
Zhang[107] studied the effect of varying oxygen concentrations.
It was observed that COX production and acrylic acid selectivity 4.5.1 | Contact time
reduced by decreasing the oxygen O2/He content below 5%.
Meanwhile, increasing the composition above 5%, COX pro- In terms of contact time, long contact time favoured acro-
duction increased, and the acrylic acid selectivity decreased. lein production and decreased acrylic acid selectivity.
Similar results were obtained by varying the gas flow rate. The contact time of both the reactant (glycerol) and of
the intermediate compound (acrolein) should be opti-
mized for the sake of optimized acrylic acid production.
4.4 | Effect of reaction temperature Yun et al.[34] observed a 6.5% increase in the acrylic acid
selectivity and a 5.4% decrease in COX formation on
The optimum reaction temperature is critical for the glyc- 0.16 s contact time compared to 0.05 s for the Mo-V-W
erol oxydehydration process to obtain high product selec- catalyst. This might be due to the lack of interaction
tivity and render stability to the catalyst. Pestana et al.[7] between the reactant and intermediate species with acid-
observed low glycerol conversion and lower selectivity of redox sites at the shorter contact time, resulting in unde-
acrylic acid at 250 C for the V/BEA catalyst. A significant sired product formation. Similarly, acrylic acid selectivity
amount of acetol was also detected. About 15% improve- decreased for contact time above 0.2 s, while COX selec-
ment in acrylic acid yield was recorded on increasing the tivity increased, with a corresponding increase in acetic
temperature from 250 to 275 C. Li and Zhang[107] acid yield. This could be due to the increased interaction
observed improved acrylic acid selectivity for increasing between the reactants and the intermediates with the
temperature in the range of 260–380 C, reaching a maxi- redox sites. Chieregato et al.[81] observed good acrolein
mum of 60% at 340 C. Meanwhile, acrolein selectivity selectivity, moderate acrylic acid yield, and low selectivity
was reduced for the same temperature range (260– towards heavy compounds for the gas-phase reaction for
380 C). Further increase in the temperature caused contact times of less than 0.1 s. Between 0.08–0.20 s, a
excess oxidation to form side or undesired products such maximum of 33% acrylic acid selectivity was reported at
as acetic acid and COX, resulting in decreased selectivity 0.15 s. Above a contact time of 0.20 s, the acrylic acid
towards acrylic acid. These findings suggest the forma- selectivity decreased, whereas oxidative degradation rap-
tion of acrolein as the main intermediate, which gets idly increased, resulting in increased COX production.
converted to acrylic acid at elevated temperatures. The effect of contact time on acrylic acid and acrolein
Shen et al.[39] predicted 300 C as the optimal temper- selectivity for some catalysts is shown in Figure 9C.
ature for the Mo/V oxide catalyst. On increasing the tem- In terms of weight hourly space velocity (WHSV), low
perature, although the conversion increased, the WHSV (0.25 h1) enables moderate acrylic acid yield
emission of COX also increased. The 100% glycerol with increased acetic acid production, whereas, at a high
conversion was achieved at 350 C. However, the carbon WHSV (1.0 h1), the low yield was noted.[107] In general,
balance only increased on lowering the reaction tempera- low WHSV favours the re-adsorption of generated acro-
ture and increasing the V content, indicating that low lein on oxidation sites.[54]
reaction temperature and high V content inhibited cok-
ing in the glycerol oxydehydration reaction over the
Mo/V oxide catalysts. Figure 9A shows the variation of 4.5.2 | Total reaction time
acrolein selectivity and yield with temperature, and 9B
shows the acrylic acid selectivity and yield with tempera- The catalysts before industrial commercialization must
ture for some of the catalysts. As can be from the figure, exhibit stability for a long reaction time. In most glycerol
the temperature range of 320–350 C appears to be the oxydehydration reaction studies, a decrease in the catalyst
optimum. activity was reported with time. Fe-MCM-22 zeolite
F I G U R E 9 (A) Variation of acrolein selectivity and yield and (B) acrylic acid selectivity and yield for Cs(VO)0.2(PMo)0.25(PW)0.75,[107]
WV,[83] MoVW,[34] and WV/KIT-6[85] catalyst with temperature. (C) Effect of contact time on acrylic acid and acrolein selectivity for
MoVW,[34] and WVNb[81] catalysts (Ac: acrolein, AA: acrylic acid). (D) Variation of acrylic acid selectivity with time on stream (TOS) at
320 C for vanadosilicates,[55] H-Fe-MCM22,[54] MoV,[84] and MoV (SDS0.10)[38] catalysts
exhibited decreased acrolein selectivity for the gas phase To determine the amount and nature of acid sites,
and increased acrylic acid selectivity for 10 h TOS. For generally, ammonia temperature-programmed desorption
Cs(VO)0.2(PMo)0.25(PW)0.75, the acrylic acid yield remained (NH3-TPD) and Pyridine-FTIR (Py-FTIR) characteriza-
constant for the first 10 h (60%). A 16% decrease in yield tion techniques are employed. NH3-TPD provides infor-
was observed for the next 10 h on stream (10–20 h). mation about low and high-temperature desorption
Finally, a 38% yield was reported at 56 h.[107] In the liquid peaks, which corresponds to weak and strong acid sites.
phase, Thanasilp et al.[32] observed an increase in glycerol The strength of acidic sites can be generally classified
conversion with time (0–270 min). However, above according to the desorption temperature as weak (150–
120 min, glycerol conversion remained almost constant. 300 C), medium (300–500 C), and strong (500–650 C).[64]
Initially, high acrolein and low acrylic acid were reported However, the TPD analysis sometimes results in an
(0–120 min), while after 120 min, acrylic acid yield ambiguous interpretation of acidic properties due to the
improved. The variation of acrylic acid selectivity with re-adsorption of ammonia and overlapping desorption
time is depicted in Figure 9D for some catalysts. peaks. Further, during the NH3- TPD analysis, both Brøn-
sted and Lewis acid sites interact with NH3, resulting in
complex analysis of the individual acid sites. Therefore,
4.6 | Effect of catalyst acidity Py-FTIR becomes essential to determine the exact acidic
behaviour of the catalyst. The IR ranges are unique for
The catalyst’s acidity plays a significant role in determin- pyridine interacting with a particular acid site. The sig-
ing the acrolein selectivity in the glycerol oxydehydration nals associated with chemically adsorbed pyridine are
process. In the first step of glycerol oxydehydration usually obtained in the range of 1700–1400 cm1. For
(i.e., dehydration of glycerol to acrolein) Lewis acid pyridine adsorbed on H-ZSM-5, the IR peaks obtained at
sites, and more so Brønsted acid sites, are essential to reg- 1622 and 1450 cm1 were attributed to Lewis acid sites
ulate the dehydration of the glycerol secondary hydroxyl (PyL), whereas the peaks at 1636 and 1544 cm1 were
group selectively to generate acrolein. In the second step attributed to Brønsted acid sites (PyH+). The IR peak
(i.e., acrolein oxidation to acrylic acid), redox sites are obtained at 1490 cm1 was attributed to both Brønsted
required.[83,127] The analysis of the spent catalyst showed and Lewis acid sites.[65] Table 8 discusses the catalysts’
a significant decrease in acid density, illustrating their acidity determined through NH3-TPD and Py-FTIR anal-
considerable utilization in the reaction.[128] ysis along with activity results.
The NH3-TPD analysis of the MCM-22 catalyst in the of ZSM-5 zeolite. The incorporation of metal led to a
acid form (H-MCM-22) showed two types of acid sites reduction in acid sites, particularly the Brønsted acid
with different strengths. The sites at 246 C were attrib- sites, with respect to the parent H-zeolites. Other
uted to weak acid sites, while the desorption peak at researchers also reported similar observations, where the
397 C was attributed to strong acid sites. The Fe loading incorporation of metal reduced the Brønsted acid sites.[52]
on MCM-22 resulted in the shift of peaks to lower tem- The effect of polyoxometalates (POM) impregnation
peratures, that is, the conversion of strong acid sites to on the surface acidity of Al2O3 was studied by Thanasilp
moderate strength acid sites. The H+ ions were replaced et al.[105] The POM impregnation resulted in the shift of
by Fe3+ ions in the zeolite exchangeable sites, resulting TPD peaks to lower temperatures, indicating the decrease
in reduced acidity. Further, an additional shift in the in acid concentration and acidic strength of the catalysts.
peaks to lower temperatures was recorded on increasing The authors believed POM resulted in the replacement of
the Fe loading, signifying the decrease in total acidity. acidic sites. On the contrary, Liu et al.[41] observed a sig-
Possato et al.[37] observed a reduction in acid sites inten- nificant increase in the number of acidic sites from 69 to
sity and shift of high-temperature NH3-TPD peaks to 283 μmol/g upon loading HSiW to Al2O3. Further, the
lower temperature upon metal impregnation (vanadium) effect of calcination temperature on catalyst acidity was
T A B L E 8 Acid strength distribution and quantification based on ammonia temperature-programmed desorption (NH3-TPD) and
pyridine-Fourier transform infrared (Py-FTIR) analysis of the catalysts
NH3-TPD (μmol/g) Py-FTIR (μmol/g)
Catalyst Type Acidity Brønsted Lewis Catalyst activity Reference

Fe1.2-MCM-22 Weak 940 - 9.0% Ac (Y); 52.6% AA (Y) dos Santos et al.[54]
Moderate 630
Strong -
Fe0.6-MFI Total 402 198 50 32.0% Ac (S); 47.0% AA (S) Diallo et al.[53]
Mo-V-ZSM-5 Total 417 2.6 (B/L molar ratio) 12% Ac (S); 15% AA (S) Possato et al.[51]
V-H-ß Weak 600 - 40.5% Ac (Y); 17.7% AA (Y) Silva et al.[52]
Moderate 830
Strong 100
V-H-MCM-22 Weak 270 - 42.8% Ac (Y); 16.0% AA (Y) Silva et al.[52]
Moderate 380
Strong 230
V-MFI Total 1080 - 18% Ac (S); 15% AA (S) Possato et al.[37]
VW/KIT-6 Total 107 - 4% Ac (Y); 30% AA (Y) La Salvia et al.[85]
Mo-V Weak 45.5 - 4% Ac (S); 33.5% AA (S) Rasteiro et al.[84]
Medium 21.7
Strong 8.5
W2.2V0.5Nb2 Total 148 - - 53.8% Ac (Y) Omata et al.[82]
WV Total 131.5 - - 20.8% AA (Y) Shen et al.[39]
SiW/Al2O3 Weak 119 - 5.44% Ac (Y); 25.11% AA (Y) Thanasilp et al.[105]
Medium 230
MoV/SiW/Al2O3 Weak 49 - 3.0% (Y); 46.2% (Y) Liu et al.[41]
Medium -
Strong 282
V-Mo-O Total 510 - 15% Ac (S); 32% (AA) Possato et al.[97]
MoVW Total 485 - 8.2% Ac (S); 30.5% AA (S) Yun et al.[34]
Co/AlPO4 Total 143 0.11 (B/L + B) 27.0% Ac (S) Lopez-Pedrajas et al.[113]
H3PO4/WVNb Total 250 25.6 (B/L) 0.5% Ac (Y); 59.2 AA(Y) Omata et al.[114]
Abbreviations: AA, acrylic acid; Ac, acrolein; B, Brønsted; L, Lewis; S, selectivity; Y, yield.
also studied. The MoV/SiW/Al2O3 catalyst calcined at spectra for the case of the MFI zeolite catalyst is shown
350 C showed a total acidity of 401 μmol/g. On increas- in Figure 10A.[135] The peaks obtained at 63, 72, and
ing the catalyst calcination temperature, a reduction in 77 ppm were ascribed to polyglycols, whereas those at
the acidity was recorded. The total acidity reported at 13, 20, 32, and 130 ppm were ascribed to polyaromatics.
450, 550, and 650 C calcination temperatures were The coke formation and deposition mechanism on inter-
331, 88, and 42 μmol/g, respectively. nal and external catalyst sites are depicted in Figure 10B.
In conclusion, catalyst acidity is crucial in deciding the In other studies for ZSM-5 zeolite, carbonaceous deposi-
acrolein selectivity. However, for acrylic acid selectivity, a tions of up to 30 wt.% have been reported.[37,136] Hence,
trend could not be established based on the available data. catalyst coking is a severe issue. Therefore, to utilize the
Classic characterization techniques such as NH3-TPD and full potential of the catalyst and maximize the catalyst
Py-FTIR are widely used to determine the surface acidity economy, it is necessary to avoid the accumulation of
of the catalytic materials. Strong acid catalysts (Hammet these detrital substances.
acidity between 3 and 8.2) favours acrolein production;
however, high acidity also results in faster coking. There-
fore, the catalyst acidity must be adjusted and tuned since 5.1 | Factors affecting coke formation
too strong acidity caused quick deactivation, while too
weak acidity showed low acrolein selectivity.[123,129] Catalyst coking mainly occurs during the glycerol dehy-
dration step. Hence, most of the decoking techniques are
also investigated for this step. The acidity of the catalyst
5 | DEACTIVATION AND is an essential parameter in deciding the coking of the
REGENERATION OF THE CATALYS T catalyst. Though Brønsted acid sites favour acrolein pro-
duction, they also promote coking. It is observed that the
Catalyst deactivation is of great concern as it hinders the increase in the formation of coke is proportional to
industrial realization of the glycerol oxydehydration pro- the increase in the Brønsted acidity.[56,135] This was fur-
cess.[130] The activity of the catalyst usually diminishes ther confirmed from the study on an FePO4 catalyst,
with the progress of the glycerol oxydehydration reaction. where less coke deposition was recorded because of its
The reduction in activity is mainly due to the change in weak acidic nature.[112]
catalyst structure, deposition of harmful or poisonous Similarly, high temperature is also detrimental to the
substances, and fouling due to coke formation. Other fac- catalyst. Deactivation increases at high temperatures.[130]
tors may include phase change (such as MoV2O8 to Other factors include glycerol-water concentration, resi-
Mo4V6O25),[52] attrition/crushing, and thermal degrada- dence time, and oxygen concentration. Less deactivation
tion. Some catalysts also deactivate because of ageing, on increasing water concentration was observed. This
owing to their crystallographic structure.[131] Deactiva- could be due to the increase in surface oxidation. Kim
tion may be permanent or, in many cases, only reduces et al.[137] observed an increase in CO and CO2 selectivity
the catalyst activity, and the catalytic activity can be and less deactivation with an increase in water concen-
restored through appropriate regeneration methods.[132] tration. It was also reported that the introduction of air
For the glycerol oxydehydration reaction, two types of or oxygen reduced deactivation and improved the life
carbonaceous deposits were mainly reported: (i) non- span of the catalyst in the reaction.[79] Hence, the param-
reactive polyaromatics and (ii) bulky polycondensed eters that affect deactivation were found to follow the
polyglycol (polyethers) molecules. Polyaromatic forma- order of glycerol concentration > residence time-
tion occurs through monomers formation (inter- > oxygen concentration > water concentration.[138]
molecular condensed dehydration of glycerol) on the
catalyst surface, which then travels inside the catalyst
and forms polyaromatics. They usually get transported 5.2 | Coking inhibition and regeneration
into the pores, thus blocking the micropores, conse- of the catalyst
quently restricting the activity of the reactants. The
formation of the latter (polyethers) is more damaging In general, it is observed that a larger surface area is ben-
as they cover the outer surface of the catalyst and eficial for less deactivation. In the case of microporous
obstruct any contact of the reactant with the active zeolite, increasing the pore size could be efficient to pre-
species.[37,133,134] vent coking.[138] Possato et al.[50] synthesized micro–
The formation of these two coke species is evident mesoporous MFI zeolites. For the case of microporous
from nuclear magnetic resonance (NMR) spectra zeolite, coke deposition occurred in micropores. But for
obtained by studying the spent catalyst. The NMR the case of micro-mesoporous zeolites, deposition
F I G U R E 1 0 (A) Typical 13C NMR curves of the used zeolite catalysts for glycerol dehydration after coking for Al-L, Al-S, Ga-L, and
Ga-S MFI zeolites, and for aluminium and gallium oxides, (TOS: 6 h). (Reprinted from Vieira et al.,[135] copyright (2016), with permission
from Elsevier.) (B) Mechanism of coke formation on catalysts: (a) external surface and (b) internal surface
occurred in internal sites (pockets), whereas the micro- et al.[125] studied the effect of pore size on SiO2-
pores remained accessible as active sites. Rapid deactiva- heteropoly acid. As expected, significant deactivation was
tion for microporous zeolite was observed. Tsukuda observed for small pore size catalysts.
Park et al.[130] studied HZSM-5 and ASPN-40 catalysts observed during the dehydration step. Though some tech-
for glycerol dehydration to acrolein; ASPN-40 exhibited niques have proven to be effective, still more effective
less deactivation than HZSM-5. In the case of ZSM-5, nar- strategies are required. The solutions to avoid or limit cat-
row pore structure leads to rapid deactivation, mainly alyst deactivation can be summarized as (i) O2 feed),
due to the condensation of coke precursors. According to (ii) optimal catalyst acidity, (iii) tuning the pore size,
the 13C NMR spectra for time on stream (TOS) of 70 h, (iv) optimum reaction temp, (v) catalyst doping (precious
the increase in coke content was observed with time. Sig- metals such as Ru, Pd, and Pt), (vi) ideal feed glycerol-
nificant coke deposition was observed for the micropo- water concentration, and (vii) burning of the catalyst in
rous structure of ZSM-5. In contrast, ASPN-40 showed an oxidative environment. Other methods reported in the
less coke deposition initially. Martinuzzi et al.[138] studied literature for coke removal, which can also be tested for
the deactivation of industrial heteropoly acid ZR-24 dur- the glycerol oxydehydration process catalyst regenera-
ing acrolein production from glycerol. Further, a global tion, are O3 (ozone) oxidation, CO2 gasification, steam
kinetic equation was developed to model the gasification, hydrogenation, use of moving bed reactors,
deactivation. and alternate coke burning cycles.[104,107,132,142,143]
Apart from these strategies, some other approaches
include modifying the internal structure of the catalyst.
Ren et al.[65] synthesized hybrid acid sites on meso 6 | SUSTAINABILITY ANALYSIS
ZSM-5 using metal hydrogen phosphate (Cu, Mo, Zn, Ni,
and Mn) for glycerol dehydration. NiHPO4/meso- For a new green process to be commercially feasible, the
HZSM-5 exhibited the highest acrolein yield (80.2 mol%) techno-economic factor plays a significant role.[144] In a
and 4.6 wt.% coking. The mechanism of less coke deposi- study by Lari et al.,[145] the prospects of a glycerol bio-
tion using hybrid acid sites is shown schematically in refinery were evaluated. The study demonstrated glyc-
Figure 11. In another study by Ali et al.,[66] less coke erol as a promising renewable raw material. To
deposition and deactivation were reported upon reducing determine the feasibility of a glycerol-based plant,
the length of the b-axis channels of HZSM-5. Dimian and Bildea[146] performed a process simulation
For the case of glycerol oxydehydration, Li and (Aspen plus version 11) for 87 600 ton/year glycerol feed
Zhang[107] demonstrated catalyst regeneration by calcina- (85% pure) to produce 45 000 ton/year acrylic acid
tion in the air for 4 h. For Fe-BEA catalyst, by loading (99.95% purity) along with other products. In terms of
1.2 wt.% Fe into BEA zeolite, deactivation of the catalyst sustainability indices, almost zero water and energy
occurred, but interestingly, after the reaction progressed consumption were obtained. A substantial decrease in
for 4 h, reactivation of the catalyst was observed. A simi- the values of greenhouse gases compared to propylene
lar trend was also observed at 4 wt.% Fe loading. The feedstock-based plants was observed. Figure 12 shows
authors believe that the reactivation of the catalyst was the proposed process flowsheet for the glycerol
mainly due to the reduction of metal (Fe) from +III to + oxydehydration process.
II oxidation state. As a result, these sites served as active In another study by Song et al.,[19] a conceptual water
sites for glycerol conversion.[49] For the case of HPA, separation process for glycerol-acrylic acid production
Cs(VO)0.2(PMo)0.25(PW)0.75, improved resistance to coke was proposed. The authors suggest employing toluene as
deposition and regeneration even at high temperatures an appropriate solvent. Significant reductions in fixed
was attributed to the salt characteristic and moderate cost (52.0% decrease) and operating expense (39.3%
acidity of the catalyst.[107] Further, it is reported that decrease) of the proposed plant were reported. Braga
vanadium incorporation reduces non-volatile compounds et al.[147] performed a techno-economic analysis for an
and carbonaceous deposits.[37] The vanadium oxides acrylic acid plant using crude glycerol as a feedstock. The
work by acting as a co-catalyst for the acid sites. They study showed promising results for the industrial realiza-
restrict the coke-forming monomers and prevent their tion of the oxydehydration process.
oligomerization through their oxidation by the Mars-van
Krevelen mechanism.[141] The use of vanadosilicates as
weak acid catalysts can also be beneficial for suppressing 7 | RECOMMENDATIONS A ND
coke deposition.[55,56] Table 7 (column 8) shows the cata- PRO SPECTS
lyst deactivation percent reported for the glycerol
oxydehydration process. The glycerol oxydehydration process to produce acrylic
In summary, catalyst deactivation is a major obstacle acid is still at the laboratory scale only. Good yield
for the glycerol oxydehydration process. Catalysts are eas- acrylic acid yield demonstrated over some catalysts is
ily deactivated by coking, and large coke formation was encouraging. However, some areas need to be further
F I G U R E 1 1 (A)(a) Mechanism of coke formation on Meso HZSM-5 Brønsted acid site and (b) transition metal hybrid acid site of the
catalyst. (B)(a), (b) Mechanism of creation of new hybrid acid sites. (B) Reprinted from Ren et al.,[65] copyright (2019), with permission from
Elsevier
F I G U R E 1 2 Proposed process flowsheet for the oxydehydration of glycerol to acrylic (reprinted from Dimian and Bildea,[146] copyright
(2021), with permission from Elsevier)
addressed. In the future, the following areas can be fur- zeolite-based catalysts, mixed metal oxides, heteropoly
ther explored: acids, and phosphate-containing catalysts has been stud-
ied so far for the glycerol oxydehydration process. Vana-
1. Use of crude glycerol as a feedstock. The use of crude dium was the most suitable oxidant agent for the
glycerol will surely provide a less costly feedstock. oxidizing species, whereas zeolites such as ZSM-5 and
However, impurities present might interfere with the BEA were suitable for acid catalysis. However, an iron-
catalyst. Hence, an appropriate system needs to be containing catalyst in place of vanadium was less toxic
developed. and environmentally beneficial. Heteropoly acids
2. Detailed kinetic study and a suitable model to deter- exhibited the best acrylic acid yield (up to 60%), but their
mine the effect of induvial species (such as water, synthesis is challenging and costly. Also, they suffer from
glycerol concentration, O2/air/H2O2 concentration) rapid deactivation and lack of regeneration through high-
need to be evaluated for the liquid and gas phase. temperature calcination due to unstable structure at ele-
3. The effect of varying temperatures on acrylic acid vated temperatures. On the other hand, mixed metal
selectivity and yield for the liquid phase has not been oxides are readily available and cheap. For the case of
thoroughly investigated. Hence, this study can be metal oxides, significant features such as active species
undertaken in the future. framework, composition of crystal phase, proper Mars-
4. Improvement in the reactor design and hydrodynamic van Krevelen mechanism, and sufficient metal valence of
properties of the catalytic reactor or the use of differ- the neighbouring species must be ensured. However,
ent reactors (membrane reactors, microfluidic reac- loading more than one type of metal or metal combina-
tors) can be further explored. tion may increase the yield but does not necessarily lead
5. Further, proper heat management and heat integra- to a sustainable catalytic activity. In contrast to HPAs
tion is needed to make the process more economical and mixed metal oxides, phosphate-containing catalysts
as the first step of the reaction is endothermic while are low-cost and have a simple synthesis.
the latter is exothermic. To conclude, the glycerol oxydehydration process is a
6. Tailored zeolites (with optimized b axis length)[148] cost-effective and environmentally friendly alternative to
have shown improved reactant mass transfer, high energy-consuming and polluting processes. Moreover, it
acrolein selectivity, and coking inhibition for the glyc- is a potentially sustainable and green acrylic acid produc-
erol dehydration process. Hence, the impregnation of tion process. However, some significant drawbacks, such
vanadium or iron (oxidizing catalysts) on tailored zeo- as moderate acrylic acid selectivity and coking, must be
lites can be explored for acrylic acid production. addressed for industrial realization and successful scale-
7. To make the process entirely green, the development up. In addition, strategies such as the co-feeding of oxy-
of metal-free catalysts, such as carbon nanotubes gen and burning of coke in alternate cycles are advanta-
(CNTs) doped catalysts, for the glycerol geous to some extent. Finally, to compete with the
oxydehydration process can be investigated. CNTs conventional propylene-based process, highly efficient
have been previously studied for the oxidation of catalysts need to be developed, and drawbacks must be
acrolein.[149,150] overcome.
8. A thorough techno-economic feasibility model to
compare the various acrylic acid production (glycerol- ACKNOWLEDGEMENT
based) routes using software such as Aspen can be The authors gratefully acknowledge Universiti Sains
explored. Further, the development of a pilot plant Malaysia for the RUI grant (8014059) to support
can also be considered. Finally, the prospects of modi- this work.
fying conventional acrylic acid production plants for
employing glycerol as feedstock needs to be evaluated. PE ER RE VI EW
The peer review history for this article is available at
https://publons.com/publon/10.1002/cjce.24295.
8 | C ON C L U S I ON S
RE FER EN CES
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Received: 25 January 2021 Revised: 1 July 2021 Accepted: 15 July 2021

A review on bi/multifunctional catalytic oxydehydration of

Anas Abdullah1 | Ahmad Zuhairi Abdullah1 | Mukhtar Ahmed1 |

1 | INTRODUCTION esters of long-chain fatty acids) is now recognized glob-

FIGURE 1 Glycerol production routes, intermediate chemicals, and applications

TABLE 1 Acrylic acid conventional and renewable production routes

(b) Lactic acid Liquid phase (160–250 C) GLA, GLYCA,

(d) Allyl alcohol Liquid phase (140–240 C) AT, 1,2-prop,

(f) Direct conversion Vapour phase AC, AA, AD,

and energy advantages over the other routes. The forma-

Parameters Two-step Single-step Reference

Bottom WHSV Glycerol Acrylic acid

Abbreviations: TOS, time on stream; WHSV, weight hourly space velocity.

TABLE 4 Zeolite-based catalysts studied for the glycerol oxydehydration process

Fe-BEA 1.2 275 7.6 50 - - 10 8 Diallo

3 | C AT A L Y S T S FO R G LY C E R O L maximum acrylic acid yield of 23% was recorded at 4 wt.%

Nibonium-vanadium catalyst (Nb-V) Molybednum- vanadium-tungsten catalyst (Mo-V-W)

FIGURE 7 Mars-van Krevelen mechanism for acrolein oxidation to acrylic acid[24,30,119]

TABLE 7 Properties of catalysts studied for the oxydehydration reaction

Carrier gas, Total acid

NH3-TPD (μmol/g) Py-FTIR (μmol/g)

Catalyst Type Acidity Brønsted Lewis Catalyst activity Reference

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