catalysts

Article
Article
Glycerol Dehydration to Acrolein over Supported
Glycerol Dehydration to Acrolein over Supported
Vanadyl Orthophosphates Catalysts
Vanadyl Orthophosphates Catalysts
Giovanna Ruoppolo 1 , Gianluca Landi 1, * and Almerinda Di Benedetto 2
Giovanna Ruoppolo 1, Gianluca Landi 1,* and Almerinda Di Benedetto 2
1 Institute for Researches on Combustion—CNR P.le Tecchio 80, 80125 Naples, Italy; ruoppolo@irc.cnr.it
1
2 Institute for Researches on Combustion—CNR P.le Tecchio 80, 80125 Naples, Italy; ruoppolo@irc.cnr.it
Dipartimento di Ingegneria Chimica, dei Materiali e della Produzione Industriale, University of Naples
2 Dipartimento di Ingegneria Chimica, dei Materiali e della Produzione Industriale, University of Naples
Federico II, P.le Tecchio 80, 80125 Naples, Italy; almerinda.dibenedetto@unina.it
Federico II, P.le Tecchio 80, 80125 Naples, Italy; almerinda.dibenedetto@unina.it
* Correspondence: gianluca.landi@cnr.it; Tel.: +39-08-1768-2235
* Correspondence: gianluca.landi@cnr.it; Tel.: +390817682235




Received: 21 May 2020; Accepted: 11
11 June
June 2020;
2020; Published:
Published: date
15 June 2020


Abstract: Biodiesel
Biodiesel has
has been
been identified
identified as one of the notable options for at least complementing
conventional fuels.fuels.FromFrom
a transesterification reaction,reaction,
a transesterification crude glycerolcrudeisglycerol
producedisasproduced
the main by- as
product.
the mainGiven the difficultly
by-product. Givenintheupgrading to in
difficultly high-grade
upgrading glycerin and glycerol
to high-grade market
glycerin saturation,
and glycerol
alternative routes to
market saturation, more value-added
alternative products
routes to more have aroused
value-added significant
products interest.
have aroused In this work,
significant we
interest.
proposed supported
In this work, vanadyl
we proposed orthophosphates
supported (VOP) as catalysts
vanadyl orthophosphates for the
(VOP) glycerol for
as catalysts dehydration
the glycerolto
acrolein. VOP
dehydration to supported
acrolein. VOPon γ-Al 2O3, TiO
supported on2,γ-Al
and2 ZrO 2 were
O3 , TiO2 , andprepared,
ZrO2 were characterized by inductively
prepared, characterized by
coupled
inductivelyplasma
coupledmass spectrometry
plasma (ICP-MS),
mass spectrometry X-ray diffraction
(ICP-MS), (XRD),(XRD),
X-ray diffraction N2 physisorption
N2 physisorptionand
temperature-programmed
and temperature-programmed desorption of ammonia
desorption (NH3-TPD),
of ammonia (NH3and tested
-TPD), andunder
testeddifferent
underoperating
different
conditions. All the samples
operating conditions. All theshowed
sampleslow cokelow
showed formation in the presence
coke formation of molecular
in the presence oxygenoxygen
of molecular in the
feed.
in theAcrolein is the main
feed. Acrolein is thecondensable product,
main condensable with carbon
product, balance
with carbon being being
balance satisfactory underunder
satisfactory most
operating conditions.
most operating VOP supported
conditions. VOP supportedonto alumina provided
onto alumina the bestthe
provided catalytic performance,
best catalytic due to
performance,
adue
good
to abalance betweenbetween
good balance the acid the
(weak and
acid medium
(weak and acid
mediumsites)acid
and sites)
redoxandsites,redox
thereby appearing
sites, thereby
as a good candidate
appearing as a good for glycerolfor
candidate dehydration to acrolein.to acrolein.
glycerol dehydration

Keywords: glycerol; acrolein; vanadyl orthophosphate; alumina; titania; zirconia; biodiesel

1. Introduction
Biodiesel hashas been
been identified
identifiedasasa anotable
notableoption
optionforfor complementing
complementing conventional
conventional fuels.
fuels. Its
Its production
production is from
is from renewable
renewable biological
biological sources,
sources, mainly mainly vegetable
vegetable oils soybean,
oils (rape, (rape, soybean,
palm) andpalm)
an
and an alcohol
alcohol (usually (usually methanol)
methanol) used used to break
to break downdown fatty
fatty acids
acids from
from glycerolvia
glycerol viaaatransesterification
transesterification
reaction, according to the reaction
reaction reported
reported in
in Figure
Figure 1.
1.

Figure 1. Transesterification reaction of fatty acids for the production of biodiesel. (R1 , R2 , and R3 are
Figure
hydrocarbons 1. Transesterification
chains containing 15–21reaction
C atomsof fatty acids for the production of biodiesel.
[1–4].)

R1, RGlycerol accounts

2, and R3 are for about
hydrocarbons 10 wt.%
chains of the15–21
containing biodiesel produced
C atoms [1–4]. [5]. Crude glycerol should
be upgraded to obtainfor
Glycerol accounts “technical
about 10grade”
wt.% ofglycerol and, by
the biodiesel a further
produced [5].purification, United
Crude glycerol States
should be
upgraded to obtain “technical grade” glycerol and, by a further purification, United States
Catalysts 2020, 10, 673; doi:10.3390/catal10060673 www.mdpi.com/journal/catalysts
Catalysts 2020, 10, x; doi: FOR PEER REVIEW www.mdpi.com/journal/catalysts
Catalysts 2020, 10, 673 2 of 15

Catalysts 2020, 10, x FOR PEER REVIEW 2 of 14

Pharmacopeia (USP; appropriate for food and pharmaceutical products) and Food Chemicals Codex
(FCC; appropriate
Pharmacopeia for appropriate
(USP; use in food)for glycerin,
food andboth requiring ≈100%
pharmaceutical products) purity. However,
and Food the Codex
Chemicals glycerol
(FCC;together
surplus appropriatewithfor itsuse in food)
difficult glycerin,inboth
upgrading the requiring
presence ≈100% purity.[6]
of methanol However, the glycerol
makes crude glycerol
surplus together
upgrading with its difficult
disadvantageous upgradingif in
[7–9], especially thethe presence
price of methanol
decrease [6]ismakes
of glycerol crude [9–11].
considered glycerol
upgrading disadvantageous
For the above reasons, several[7–9], alternative
especially ifroutes
the price decrease
have of glycerol is to
been investigated considered
upgrade [9–11].
glycerol to
more value-added products [6,7,11–23]. Among these routes, glycerol dehydration to acrolein to
For the above reasons, several alternative routes have been investigated to upgrade glycerol has
more value-added
received productsdue
significant interest [6,7,11–23]. Among
to the broad usethese routes, in
of acrolein glycerol dehydration
the chemical to acrolein
industry. has is
Acrolein
receivedmainly
converted significant interest
to acrylic acid,due
butto theacrylic
also broadacid
use esters,
of acrolein in the chemical
glutaraldehyde, industry.polyurethanes,
methionine, Acrolein is
converted mainly to acrylic acid, but also acrylic acid esters, glutaraldehyde, methionine,
and polyester resins [24].
polyurethanes, and polyester resins [24].
Several catalysts have been proposed for glycerol dehydration, including heteropolyacids,
Several catalysts have been proposed for glycerol dehydration, including heteropolyacids,
zeolites, metal oxides, mixed metal oxides, phosphates and pyrophosphates, and mixed systems
zeolites, metal oxides, mixed metal oxides, phosphates and pyrophosphates, and mixed systems
thereof [5,18,25–46]. Given the vast number of reactions potentially occurring during glycerol
thereof [5,18,25–46]. Given the vast number of reactions potentially occurring during glycerol
dehydration, the proper choice of catalyst is paramount. A non-exhaustive reaction scheme is
dehydration, the proper choice of catalyst is paramount. A non-exhaustive reaction scheme is
reported
reportedin in
Figure
Figure2. 2.
This
Thisscheme
schemehas hasbeen
beenderived
derived from
from schemes suggestedby
schemes suggested byKatryniok
Katrynioketetal.al. [47]
[47]
andand
Jiang et al. [48], and the references within. The occurrence of each reaction depends
Jiang et al. [48], and the references within. The occurrence of each reaction depends on the on the reaction
conditions
reaction (temperature, oxidizing oxidizing
conditions (temperature, or reducing environment)
or reducing and the catalytic
environment) active sites.
and the catalytic active sites.

OH O OH
OH
HO O O OH OH OH
n H2C H3C H3C
HO OH

polyglycols hydroxyacetone 1-2 propanediol

Intermediate enols

OH
HO HO
OH
OH
glycerol

n
O

CH3 O
O O
OH
HO CH2
HO CH2
Acetic acid O
3-hydroxy-propionaldehyde acrolein
CH3 + O Acrylic acid
acetaldehyde CH2
+ glycerol
formaldehyde
HO
O CH2
CO+H2
H3C OH HO
Allylic alcohol
O CH3
2-methyl-1.3-dioxolane-4-methanol
methanol
→ Dehydration → Isomerization
→ Oxidation → Hydrogenation
→ Cracking/decomposition → Condensation/polymerization

Figure 2. Reaction scheme of glycerol dehydration (derived from References [47,48]).

Figure 2. Reaction scheme of glycerol dehydration (derived from References [47,48]).

The key point for the development of catalysts is the balance of the acid sites. For instance,
The key point for the development of catalysts is the balance of the acid sites. For instance, in H-
in H-ZSM5 based catalysts the co-presence of acid sites of different types (Lewis/Brønsted) and strength
ZSM5 based catalysts the co-presence of acid sites of different types (Lewis/Brønsted) and strength
both improved
both improved thethe
acrolein
acrolein yield
yieldand anddecreased
decreasedcokecoke formation [5]. Coking
formation [5]. Cokingisisthe
themajor
majordeactivating
deactivating
phenomenon, and it is still an open issue [48], despite several efforts to
phenomenon, and it is still an open issue [48], despite several efforts to develop coking-resistantdevelop coking-resistant
catalysts [49–51].
catalysts Coke
[49–51]. is formed
Coke is formed by cyclization, condensation,
by cyclization, and polymerization
condensation, reactionsreactions
and polymerization occurring
on occurring
acid sites (see Figure
on acid 2).(see
sites A strategy
Figure 2). to Areduce coking
strategy is to oxidize
to reduce cokingcoke
is to precursors
oxidize cokebyprecursors
adding oxygen
by
in the feed stream and by doping the catalyst with redox sites
adding oxygen in the feed stream and by doping the catalyst with redox sites [48]. [48].
Vanadyl
Vanadyl orthophosphates
orthophosphates(VOPO (VOPO4 4)) have
have been
been proposed
proposed for for the
the oxidative
oxidativedehydrogenation
dehydrogenation
(ODH)
(ODH) of of
ethane
ethane andandpropane
propane[52,53],[52,53],andandthey
they both
both have
have acid and redox
acid and redoxproperties.
properties.InIn particular,
particular,
VOPOVOPO4 4 supported
supported on on γ-Al
γ-Al O
2 32 O,3 , TiO
TiO 2 ,
2, and
and ZrO
ZrO 2
2 showed
showed the
the best
bestcatalytic
catalytic properties
propertiestowards
towards propane
propane
ODH ODHdue due
toto goodactive
good activephase
phase dispersion
dispersionand andimproved
improved redox properties,
redox the best
properties, catalyst
the best beingbeing
catalyst the
TiO2-supported sample. In vanadyl phosphorus oxides [54–57], different vanadyl phosphate phases
Catalysts 2020, 10, 673 3 of 15

the TiO2 -supported sample. In vanadyl phosphorus oxides [54–57], different vanadyl phosphate
phases (mainly related to V4+ and V5+ , but also to V3+ ) are typically detected in both as-prepared
and used catalysts. In particular, V4+ species have been detected in vanadyl orthophosphates under
reducing reaction conditions [58].
In this work, VOPO4 supported on γ-Al2 O3 , TiO2 , and ZrO2 were tested in the gas-phase glycerol
dehydration. The catalyst performances were related to the site acid properties. Despite the possible
co-presence of different vanadyl phosphates, in this work, the catalysts were labelled as VOP (vanadyl
orthophosphate).

2. Results

2.1. Catalysts Characterization

Table 1 shows the specific surface areas (SSA) of the bare supports. Al2 O3 has the largest surface
area (190 m2 ·g−1 ), while the lowest exposed surface corresponds to ZrO2 (49 m2 ·g−1 ). Accordingly,
the active phase load corresponding to the monolayer was directly related to the SSA and steadily
increased from 3.6 to 14.0 wt. %. After the VOP deposition, the samples showed SSA values close to
the corresponding supports, suggesting a good dispersion of the active phase.

Table 1. Nominal vanadyl orthophosphate (VOP) content (wt. %), surface area (m2 ·g−1 ) of supports
and catalysts, and H2 /V as calculated by the temperature-programmed reduction in hydrogen (H2 -TPR).

Catalyst Nominal VOP Content Support Surface Area Catalyst Surface Area H2 /V a
VOP/Ti 9.6 125 125 0.71
VOP/Al 14.0 190 183 0.67
VOP/Zr 3.6 49 43 1.07
a as reported by Casaletto et al. [53].

XRD spectra of both fresh and used samples (not reported) showed only the signals corresponding
to the supports, and no peak due to vanadyl orthophosphate was detected, which was in agreement
with previous results [53]. Thus, no VOP phase segregation occurs in these samples, suggesting
a good active phase dispersion onto the support and no segregation phenomena occurring under
the reaction conditions.
The results in terms of NH3 -TPD profiles and the quantitative analysis are shown in Figures 3
and 4, respectively. The profile shapes are similar, suggesting that the same acid sites are detectable on
each sample. This also suggested the negligible contribution of the supports (characterized by very
different acidity) to overall acidity of the samples. This agreed with the good dispersion of the active
phase. However, it is worth noting that the interaction between the VOP and support strongly affects
the active phase features [59]. As shown in Figures 3a and 4, VOP/Al is characterized by the largest
amount of acid sites. This sample was characterized by the highest VOP amount, too. Figure 3b shows
the desorbed ammonia per VOP weight. Profiles of VOP/Al and VOP/Ti were similar but they did
not overlap. The zirconia supported sample showed a larger ammonia desorption per VOP amount.
This could be addressed to the higher coordination between ammonia and the acid sites. However,
due to the low VOP content, the uncertainty of the ICP analysis could be higher. Nevertheless, VOP/Zr
showed the lowest catalytic activity (see Section 2.2.2), and thus, further investigations were not
carried out.
 Catalysts 2020, 10, x FOR PEER REVIEW 4 of 14

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Catalysts 2020, 10, 673 4 of 15
4x10-5
a)
VOP/Al 500

1
4x10-5-5

min
3x10
a) 400
VOP/Al 500

11
cat
molmin
3x10-5-5 300

g
2x10
VOP/Ti 400

1
NH g, cat
200
2x10-5-5 300

3
10 VOP/Ti

°C
NH3, mol 100
200

Temperature,
VOP/Zr
10-5

°C
0 0
100
b)

Temperature,
VOP/Zr
VOP/Zr 500
1

4x10-4
min

0 0
b) 400
11

3x10-4-4
4x10 VOP/Zr 500
VOP
min

300
VOP/Ti
mol g

400
1

2x10-4-4
3x10
NH g, VOP

200
300
VOP/Ti
3

10-4-4
NH3, mol

2x10 100
VOP/Al 200

100-4 0
VOP/Al 40 100
0 20 60 80 100

0 Time, min 0
0 20 40 60 80 100
Figure 3. NH3-TPD profiles of the VOP/x catalysts
Time, minfor the catalyst (a) and VOP weight (b).
Figure 3. NH3 -TPD profiles of the VOP/x catalysts for the catalyst (a) and VOP weight (b).
Figure 3. NH3-TPD profiles of the VOP/x catalysts for the catalyst (a) and VOP weight (b).
0.0010

weak
medium
0.0008
0.0010 strong

weak
medium
-1
cat

0.0006
0.0008 strong
gcat , mol g
-1
3

0.0004
0.0006
NH3, mol NH

0.0002
0.0004

0.0000
0.0002
VOP/Al VOP/Ti VOP/Zr

Figure 4. Overall and partial

0.0000ammonia amounts desorbed from the VOP/x catalysts during NH -TPDs.
3
Figure 4. Overall and partial ammonia amountsVOP/Ti
VOP/Al desorbed from the VOP/x catalysts during NH3-
VOP/Zr
TPDs.the quantitative point of view (Figure 4), VOP/Al showed the most significant amounts of
From
Figureand
both weak 4. Overall
medium andacid partial
sites,ammonia
while theamounts desorbedoffrom
highest amount theacid
strong VOP/x catalysts
sites during in
was detected NH 3-
VOP/Ti.
2.2. Catalytic
TPDs. Activity
Acrolein formation has been related to the acid sites and, in particular, to the weak and the medium
acidity [27,31,35,36,60,61]. It is worth noting that the strong acid sites can be related to the catalyst
2.2.1.
2.2. Effect of
Catalytic the Reaction Conditions.
Activity
deactivation by coking [27,35,36,60,61].
VOP/Ti showed
Redox properties of thethebest catalytic
samples wereproperties
previouslytowards
studiedpropane
[53], andoxidative dehydrogenation
the corresponding results
2.2.1. Effect of the Reaction Conditions.
(ODH)
are given[53], and 1thus,
in Table as Hit 2 /V.
was used
VOP/Al as the
shows reference
the lowest H 2 /V
catalyst to
ratio,evaluate the
suggesting effect
that of
vanadiumthe reaction
is less
conditions
VOP/Ti on the
showedcatalytic
the performance.
best catalytic properties
reducible. Conversely, the VOP/Zr sample was the most reducible. towards propane oxidative dehydrogenation
(ODH) The effect
[53], andof thus,
the furnace
it wastemperature
used as thewas investigated
reference catalystin to
theevaluate
range 210–255 °C atofa fixed
the effect contact
the reaction
time τ = 0.057
conditions g·s·cm
on the −3 and feed composition Gly/H2O/O2/N2 = 2/41/6/51 vol. %.
catalytic performance.
The effect of the furnace temperature was investigated in the range 210–255 °C at a fixed contact
time τ = 0.057 g·s·cm−3 and feed composition Gly/H2O/O2/N2 = 2/41/6/51 vol. %.
 Catalysts 2020, 10, 673 5 of 15
Catalysts 2020, 10, x FOR PEER REVIEW

2.2. Catalytic Activity

In Figure 5, the glycerol conversion (Figure 5a) and the yields of several products (Fig
areofshown
2.2.1. Effect as a Conditions
the Reaction function of temperature.
VOP/Ti showed the best catalytic properties towards propane oxidative dehydrogenation
(ODH) [53], and thus, it was used as the reference catalyst to evaluate the effect of the reaction
the Catalysts
conditions on Catalysts 2020,2020,
catalytic
Catalysts 2020, 10, x FOR PEER100
x 10, x FOR
PEERPEER
performance.
10,
REVIEW
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6 of 514of 14
5 of 14 ◦
The effect of the furnace temperature was investigated in the range 210–255 C at a fixed contact
−3In Figure 5,downthe glycerol conversion (Figure 5a) time.
and the yields of several productsCO(Figure 50.0
5b–d)
time In 0.057acid
τ =Figure yield
g·s·cm
5, the dropped
and
glycerol feed to
composition
conversion zero at5a)
Gly/H
(Figure the highest
O/O
2and the contact
2 /Nyields
2 = 2/41/6/51
These
vol.
of several %. results
products suggested
(Figure 5b–d)that oxidation
nd the yields of several productsof (Figure
are
acids 5b–d)
shown
toof
CO as a function
was significantlyof temperature.
In Figure
are shown as a5,function
80
the glycerol x conversion
temperature. (Figurefaster than
5a) and theacrolein oxidation,
yields of while acrolein
several products (Figureformation
5b–d) was faster
than its oxidation at this temperature. Coke formation was still negligible. 40.0
are shown as a function of temperature.
Conversion, %

CO2
100 100
60 30.0
100
50.0
CO CO 50.0
CO 50.0 20.0
CO 50.0 80 80
40 40.0
80 40.0
Conversion, %
Conversion, %

40.0
CO 10.0
40.0 2 CO2
Conversion, %

CO2 30.0

Yield, %
60

Yield, %
CO2 60 30.0
60 30.0

Yield, %
20
Yield, %

30.0
20.0 20.0
0.8
40 40 20.0
20.0
40
a) b) C 0.4
10.0 10.0
0 10.0 0.0
10.0
20 20
20 16 c) d) 0.8 16
0.8
a)b) b) 0.8 C
C 0.4 0.4
0.8
a) b) a) C
C 12 0 0 0.4 0.0 0.0 12
0.4
0 Acr c) d) 0.0
0.0 16 16 c) d) 16 16
16 8 c) d) 16 8
16
Yield, %

12 12 12 12
12 Acr Acr AcA 12
12
Acr 6 8 8 8 8
6
Yield, %

Yield, %
Yield, %

Yield, %
8 8
8
Yield, %

Yield, %
6 6
AcA
Yield, %

4 6 AcA 6 4
6 AcA 6
AcA 6
4 4
4 4
4 2 4 2
4
AA GA
2 2 2 2
2 FA FA
GA 2
AA AA GA
2
AA
0 GA FA
0
GA
0 2100 220 230 FA
240 250 210 220 230 240 0 0250
FA 0 0.05
210 0.06
220 0.07
230 0.08
240 250 0.05
210 0.06
220 0.070
230 0.08
240 250
0
210 220 230 240 250 210 220 230 240 250
220 230 240 250 Temperature, °C
-3
ContactTemperature,
time, g s cm°C
Temperature, °C
°C
Figure 5. Figure
(a) Figure 5. 6.(a)(a)
Figure
Glycerol Glycerol
5.Glycerol
conversion,
◑acrylic
conversion,
(a) Glycerol
(b) conversion,
conversion,
yields (b)
( ⬒),
⬒),
to (b)
), ⬒),
(b)yields
yields
yields
CO to CO
(9), to
to CO(⬡),
CO
2(⬡),
(^),CO(⬡),
2 CO
and CO
(◇), and
coke
Figure 5. (a) Glycerol conversion, (b) yields to CO (⬡), CO2 ( ), and coke (C, △), (c) yields to acrolein
2 (◇),
2 (◇),

◓),
and4),
coke
(C,
◓),
and
coke △),
(C,(c)
◓),
coke
(C, (c)
yields
◇
(C,
△),yields △), (c)
(c) yields
⬓),
toyields
acroleinto ac
to acrolein
⬓),(FA, ⬓), and gl
▽
CO2 (◇), and coke (C, △),to (c)acrolein
yields to(Acr,
(Acr, ◑)(Acr,
acrolein
(Acr, )◑and
) and
and )acrylic
and acrylic
acrylic acid acid
(AA,
acid(AA,
acid (AA,(AA, (d) (d) yields
yields
(d)(d) toto
yields
yields to
toacetic
acetic acid
acidacid
acetic
acetic (AcA, (AcA,
acid
(AcA, ), formic
formic
(AcA, acid
formic acid
acid(FA,
(FA,
formic and
acid and glycolic
glycolic
(Acr, ◑) and acrylic acid (AA, (⬒), (d) yields to acetic acid (AcA, ◑), formic acid (FA, ⬓), and−3glycolic
cid (AcA, ◓), formic acid (FA, ⬓), ), andacidglycolic
acid
glycolicacid
(GA,
acid(GA,)
(GA,
▽)ofasthe▽)
as a as
5) a function
function
as a of of
the
function the temperature
contact
of the time on
temperatureon VOP/Ti;
VOP/Ti;
on τ = 0.057
temperature
VOP/Ti; τ = g∙s∙cm
=
0.057 , Gly/H −3 2O/O22O/O
/N 2= 2/41/6/51
g∙s∙cm , Gly/H2O/O2 2=/N2 = 2/41
230 °C,
g·s·cm Gly/H
, 2/N
acid (GA, ) as a (GA, a temperature
function ofon the temperature on VOP/Ti; τ2O/O
= 0.057 −3
function VOP/Ti; τ = 0.057 g·s·cm −3, Gly/H 2/N2 = 2/41/6/51
i; τ = 0.057 g∙s∙cm−3, Gly/HGly/H
2O/O22/N /N22/41/6/51
= 2/41/6/51
2 = 22/41/6/51
O/O vol. %. vol.vol.
%. %.
vol. %. vol. %.
Glycerol conversion The Glycerol was high
combined and of
conversion
effect quite wascomplete
high and
temperature in quite
and the whole
complete
contact temperature
time in the
on range
whole
glycerol investigated.
temperature
conversion andrange investigated.
acrolein yield
Glycerol conversion was high and quite complete in the whole temperature range investigated.
Acrolein was
in the whole temperature range isGlycerol
the most
investigated.
Acrolein
shown in conversion
abundantwas the
Figure 7.most was
condensable abundant
Independently high
product, and quite
while
condensable
from the the complete
acrylic
product,
contact acid
time, inyield
while the
thewas
temperatures wholevery
acrylic temperature
low.yield
acid
higher thanwas 200 veryrange
°C low.inv
were
Acrolein was theresults,
most abundant condensable product, while the acrylic acid yield was poorly
very low.
, while the acrylic acid From these
yieldAcrolein
wasneeded
very low. to it
getappeared
complete that
(or in the
almost presence
appeared
complete) of
that molecular
was the most abundant condensable product, while the acrylic acid yield was
From these results, it in the oxygen,
presence
conversion. of VOP
molecular
Moreover, was
at low oxygen, active
VOP
temperatures, was poorly
incomplete ver
active
From
towards these results,
acrolein oxidation it appeared
to acrylic that
acid inor,the presence
more probably,of molecular
too active oxygen,
towards VOP wasacid
acrylic poorly active
oxidation.
e of molecular oxygen, VOP wascarbon poorly
Fromtowards active
balance acrolein
these results,was oxidation
obtained
it acid due
appeared to
to acrylic
the acid
formation
thatprobably, or,
of
in the presence more
unknown probably,
products
oftowards too
molecular (not active towards
reported).
oxygen, The acrylic
reaction acid
towards
This behavioracrolein
has oxidation
been acid previouslyto acrylic
reported or, vanadyl
on more pyrophosphate too active[62]. on The maximum acrylic acid VOP was poo
yield
e probably, too active towardstemperatures
acrylic
oxidation. This behavior
providing the best has been previously
acrolein production reported
decreased. This vanadyl
behavior pyrophosphate
was less prominent[62]. The
oxidation. towards
Thisobtained acrolein
behavior has◦ C. oxidation
been previously to acrylic
reported acid or,
on vanadyl more probably,
pyrophosphate too
[62]. active
The towards ac
orted on vanadyl(16%) has been
pyrophosphate [62].
maximum
for other at
The235
products yield(notDetected
(16%) by-products
has been but
reported), obtained included acetic
at 235 °C. the
by decreasing acid,
Detected formic
contact acid,
by-products and
time fromincluded glycolic
0.088 g∙s∙cm acetic to
−3 acid, formic
0.043
maximum yield (16%)
oxidation. has
This been obtained
behavior athas235 °C.beenDetected by-products
previously included on
reported acetic ifacid, formic
ected by-productsacid. Among
included these
acetic acid,
g∙s∙cm species,
−3,formic
acid, and
the only
glycolic
production theacid.
production
peak Among
shifted ofthese
thehigher
at acetic
species, acidonlywasthe
temperatures. significant,
production evenof vanadyl
the itsacetic
highest pyrophosphate
acid was significant,
acid, and glycolic
maximum acid.yieldAmong these
(16%) species,
has been only the production
obtained atnegligible
235 of the
°C. acetic 5b),
Detected acid wasto
by-products significant, included(Figure acetic5b),
ac
production of theyield
aceticwas
acid lower
was thaneven7%
significant, (Figure
if its highest 5d). Coke
yield wasformation
lower thanwas 7% (Figure (Figure
5d). Coke formationdue the
wasgood negligible
even if
oxidation its highest
properties
2.2.2. yield
of
Effectthewas VOP
of lower
the than
catalyst.
Support. 7%
As (Figure
reported 5d).
in Coke
Section formation
1, resistance wasto negligible
coking is a (Figure
major 5b),
issue
d). Coke formation was negligible acid, and (Figure to 5b),
dueglycolic the good acid. Among
oxidation these of
properties species,
the VOPonly catalyst.theAsproduction
reported in Section of the1,acetic resistance acidto was
cokings
due to the good oxidation properties of the VOP catalyst. As reported in Section 1, resistance to coking
t. As reported in Section 1, resistance istoa coking
major issue to be solved [48] and the intimate contact between the acid sites, related to phosphate,
is a major even
issue toif be
its
The highest
effect[48]
solved of yield thewas
the support
and intimatelower
has contact
beenthan 7% (Figure
studied
between at the
fixed acid5d).
sites,Coke
contact time formation
related (τto= phosphate,
0.057 g∙s∙cm was−3negligible
) and feed (F
ct between the acid sites, related to phosphate,
and the redox sites, related to vanadium, provides fast conversion of coke precursors into COx, which
and the redoxduecomposition
to the
sites, good(Gly/H
related tooxidation2O/O2/N
vanadium, 2 = 2/41/6/51
properties
provides fastof vol.
the %).
conversionVOPAs for VOP/Ti,
ofcatalyst.
coke acrylic
As
precursors acid,CO
reported
into formic
in acid, and
Section
x, which 1, glycolic
resistance
conversion of coke precursors into CO x, the
which
acidare
are the mostaabundant were most abundant
detected.
products However,
to be(Figure
products
5b). due
CO
(Figure
to their
increases
5b). CO
very lowincreases
at temperatures amounts, atthe
above
temperatures
corresponding
235 °C,the while
above
CO
235 °C,
yields werewhile CO2
notto
ases at temperatures aboveis 235 major issue solved [48] and the intimate contact between acid sites, related p
2
°C, slightly
while CO decreases; therefore, oxidation of acrolein and acetic acid (where the acetic acid, and by
yields decrease
2
reported.
slightly decreases; In Figure
therefore, 8, the glycerol
oxidation of acroleinconversion
and aceticandacidthe (where
yields to theacrolein,
yields CO, CO2, by
decrease
nd acetic acid (where the yields and the redoxby
decrease sites, related to vanadium, °C)provides fast conversion of coke precursors into C
cokeincreasing
obtained on thethetemperature
VOP/x catalysts above are 235compared. mainly produces carbon monoxide.
Catalysts 2020, 10, 673 6 of 15

Catalysts 2020, 10, x FOR PEER REVIEW

to be solved [48] and the intimate contact between the acid sites, related to phosphate, and the redox
sites, related to vanadium, provides fast conversion of coke precursors into COx , which are the most
In Figure 5, the glycerol conversion (Figure 5a) and the yields of several products (Figure
abundant products (Figure 5b). CO increases at temperatures above 235 ◦ C, while CO2 slightly
are shown
decreases; therefore, asoxidation
a function of temperature.
of acrolein and acetic acid (where the yields decrease by increasing
the temperature above 235 ◦ C) mainly produces carbon monoxide.
The effect of contact time on the catalytic properties is shown in Figure 6, at 230 ◦ C. Glycerol
conversion Catalysts
Catalysts
slightly
Catalysts 2020,
2020, 10,10,
2020, 10,xxFOR
increases
x FOR FORbyPEER
PEER
PEER REVIEW
REVIEW the contact time. As expected, acrolein yield increased,
increasing
REVIEW 6 5of
5 ofof
141414
100
Catalysts 2020, 10, x FOR PEER REVIEW 6 of 14
while acrylic acid, acetic acid, and glycolic acid yields showed a maximum. In particular, the acetic
In
InFigure
Figure 5,5,the
the glycerol
glycerol conversion
conversion (Figure
(Figure 5a)
5a)and
andthe yields
theThese of
ofseveral
yieldsresults
several products
products CO
(Figure
(Figure5b–d)
5b–d)
acid yieldacid
droppedyield dropped
down down
to zero to zero
at the at the
highest highest
contact contact
time. Thesetime.
results suggested thatsuggested
oxidationthatofoxidation50.0
acid yield dropped
are
are shown
shown down
asasa ato zero
function
function atofthe
of highest contact
temperature.
temperature. time. These results suggested that oxidation
acids to CO of xacids to CO
80 x was significantly
was significantly faster than
faster than acrolein acrolein
oxidation, oxidation,
while acroleinwhile acrolein
formation wasformation
faster thanwas faster
of acids to CO x was significantly faster than acrolein oxidation, while acrolein formation was faster 40.0
than its oxidation at this temperature. Coke
its oxidation at this temperature. Coke formation was still negligible. formation was still negligible.
Conversion, %

than its oxidation at this temperature. Coke formation was still negligible. CO2

Yield, %
100
60100
100 30.0
100
CO
CO 50.0
CO
50.0 50.0
50.0
CO 20.0
8080
80
80 40 40.0
40.0 40.0
40.0
Conversion, %
%
Conversion, %

CO
CO
CO 10.0
Conversion, %

2 22
CO2
Conversion,

30.0

Yield, %
6060

%
Yield, %
60 30.0 30.0
30.0
60

Yield, %

Yield,
20
20.0
20.0
20.0
20.0 0.8
4040
40
40 a) b) C 0.4
10.0
10.0
10.0
0 10.0 0.0
2020
20
20 16 c) d) 0.80.8 16
0.8
a) b)b)
b) C CC 0.8
a)a) C 0.4
0.40.4
0.4
120 00 a) b) 0.00.0
0.0 12
0 Acr c) d) 0.0
1616
16 c) d) c) d)
c) d) 1616
16
16 8 16 8
%

Yield, %
1212
12 1212
12
12 Acr 12
Yield,Yield,

Acr
Acr AcA
Acr
68 8 88 6
88
8 8
%

Yield, %
%

%
Yield, %

Yield, %
Yield, %

Yield, %
6 6
Yield,

Yield,
6 4 66 AcA AcA
AcA 6 66 4
AcA
4 4
4 44 4 44
2 2
AA GA
2 22 2 22
2 FA GAFA
GA 2
AA
AA
AA GA
AA0 FA GA
FA
FA
0
210
0 00 220 230 240 250 210 220 230 2400 00 250
0 0
2100.05 220
210 2200.06 230
2300.07 240
2400.08 250
250 2100.05 220
210 2200.06 230
2300.07 240
2400.08 250
250
0.05 0.06 0.07 0.08 0.05 0.06 0.07 0.08
Temperature, °C
Temperature,
Temperature,
Contact time, g s cm°C-3
°C
Contact time, g s cm-3
Figure 6.FigureFigure
Figure
(a) 5.6.(a)
Figure 5.
Glycerol(a) Glycerol
5.(a)
(a)Glycerol
Glycerol
Glycerol
conversion, conversion,
conversion,
conversion,
conversion,
(b) yields (b)
(b)(b)(b)
to yields
yields
yields
yields
CO to to
(9),to
COCO to
CO CO
(⬡),
2(⬡),
(⬡), CO
(^),
◇
CO(⬡),
CO (◇),
2 and CO
2 2(◇),
(◇),
Figure 6. (a) Glycerol conversion, (b) yields to CO (⬡), CO2 ( ), and coke (C, △), (c) yields to acrolein
(Acr,
(Acr,
(Acr,
acrolein(Acr,
(Acr, ◑)and
◑and
◑)◑)and ))and
and acrylic
acrylic
acrylic
acrylic
acrylic acid
acid
acid
acidacid (AA,
(AA,
(AA, (⬒),
(AA,
(AA, ⬒),
⬒),
⬒),
), (d)(d)
(d) yields
yields
yields
(d)
yields toto
to
yields acetic
toacetic
acetic
acetic acid
toacidacid
(AcA,
acetic
acid (AcA,
acid
(AcA,
and
andand
coke
◓),
◓),
(◇),
◓),
coke
2 coke
(C,coke
formic
(AcA,
),
and
(C,
4), (C,
◓),
formic
formic
formic
(C,
acid
coke
△),△),
(cr)
acid
△),
acid
(c)
(c) (c)
yields
(FA,
(FA,
(FA,
formic
acid
(C,
⬓),⬓),
to△),
yields
yields
yields
⬓),
toto
),and
and
acid and
to(c) yields to acrole
acrolein
acrolein
acrolein
⬓), and glyco
glycolic
glycolic
glycolic
(FA,
(Acr, ◑) and acrylic acid (AA, (⬒), (d) yields to acetic acid (AcA, ◑), formic acid (FA, −3⬓), and glycolic
and glycolic acid
acid
acid acid (GA,
(GA,
(GA,
acid )
(GA, ▽)
▽)
asas
X)as
aaa function
function
function
as a
▽) as aoffunction of
of
function the
the
theoftemperature
temperature
contact
the time
contact on
on VOP/Ti;
VOP/Ti;
timeVOP/Ti;
on ττ = =0.057
0.057g∙s∙cm
temperature
VOP/Ti; g∙s∙cm =
temperature ,
−3 Gly/H
,
230 =
Gly/H
°C, O/O
O/O
2Gly/H
2230
◦2/N
/N
2C, 2 2==2/41/6/51
2O/O 2/41/6/51
2/N2 =
Χ) (GA, of the
timetemperature on VOP/Ti; τ = °C,
0.057 g∙s∙cm , Gly/H2O/O2/N2 = 2/41/6/
−3
acid (GA, as a function the contact on VOP/Ti; temperature = 230 Gly/H 2O/O2/N2 =
/N 2=
2vol.
vol.
Gly/H2 O/O2/41/6/51 %.
%.2/41/6/51
vol. %. vol. %.
2/41/6/51vol.
vol.%.%.
The combined The effectconversion
Glycerol
Glycerol
combined of temperature
effect ofwas
conversion was and
highcontact
high
temperature and
andquite time
quite
and on glycerol
complete
complete
contact time in
inon conversion
the
the whole
glycerol and acrolein
wholetemperature
temperature
conversion rangeyield
range
and investigated.
investigated.
acrolein yield
The combined
Glycerol effect of
conversiontemperature was and
fromhigh contact
andthe time
quite on glycerol
complete conversion
in and acrolein ◦ yield
is shown is inAcrolein
Figure in
Acrolein
shown 7.
wasIndependently
was the
Figurethemost
most abundant
abundant
7. Independently the contact
condensable
condensable
from time, temperatures
product,
product,
contact while
while
time, thethe
the higherwhole
acrylic
acrylic
temperatures than
acid
acid temperature
200
yield
higher yield Cwas
than were
was very
200 °Crange
very were invest
low.
low.
is showntoin
needed getFigure
complete 7. Independently
(or almost from the
complete) contact time,
conversion. temperatures
Moreover, at low higher than 200
temperatures, °C were
incomplete
Acrolein was the most abundant condensable product, while the acrylic acid yield active
needed From
From
to getthese
these results,
completeresults, (or it
itappeared
appeared
almost that
that
complete) in
in the
the presence
presence
conversion. of
of molecular
molecular
Moreover, at oxygen,
lowoxygen, VOP
VOP
temperatures, was
was poorly
poorly
incomplete was
activevery l
needed to get complete
carbon balance was (or almost
obtained due complete)
to the conversion.
formation of Moreover,
unknown at low
products temperatures,
(not reported). incomplete
The reaction
towards
towards
carbon
From balance acrolein
acrolein
was oxidation
oxidation
obtained dueto
totoacrylic
acrylic
the that acid
acid
formationinor,
or,ofmore
more
unknownprobably,
probably,
productstoo
too(notactive
active towards
towards
reported). Theacrylic
acrylic
reactionacid
acid
carbon balance
temperatures wasthese
providing obtained results,
the best toitthe
dueacrolein appeared
formation
production
the
of decreased.
unknown presence
products
This
of molecular
(not
behavior reported).
was Theoxygen,
reactionVOP was poorly
lesspyrophosphate
prominent
oxidation.
oxidation.
temperatures This
This behavior
providing behavior has
the besthas been
been previously
acrolein previously
production reported
reported
decreased. on vanadyl
on This
vanadylbehavior was lessfor
pyrophosphate [62].
[62]. The
prominent The
towards
temperatures
other products (not
acrolein
providing the oxidation
reported), best
but acrolein
by
to
decreasing
acrylic
production
the
acidtime
decreased.
contact
or,from more
This probably,
behavior
0.088 g·s·cm was
−3 tolesstooprominent
0.043
active−3−3,towards acryl
g·s·cm
formaximum
maximum
other products yield
yield(16%) (not has
(16%) hasbeenbeenobtained
reported), but by at
obtained at235
235°C.
°C.Detected
decreasing Detected
the contactby-products
by-products
time from included
included acetic
0.088 g∙s∙cmaceticacid,
acid, formic
formic
to 0.043
for
the other products
oxidation.
production peak (not
This reported),
shifted behavior
atacid.
higher buttemperatures.
by decreasing
has been the contact time
previously reportedfrom 0.088onthe g·s·cm−3 to 0.043
vanadyl pyrophosphate [62
acid,
acid,
g∙s∙cm and
−3,and
the glycolic
glycolic
production acid. Among
Among
peak shiftedthese
these
at species,
species,
higher only
only the
the
temperatures. production
production of
of the acetic
acetic acid
acid was
was significant,
significant,
g·s·cmmaximum
−3, the production peak shifted at higher temperatures.
yield (16%) has been obtained
even
evenififits itshighest
highest yield
yield was
was lower
lower than
than7% 7%at 235 °C.
(Figure
(Figure 5d).Detected
5d). Coke
Cokeformation by-products
formation was
wasnegligible included
negligible (Figure
(Figureacetic
5b), acid,
5b),
2.2.2.
acid,due and Effect of the Support.
the glycolic
Support. acid. Among these species, only the production of the acetic acid was sign
due to
tothe
thegoodgoodoxidation
oxidationproperties
propertiesof ofthe
theVOPVOPcatalyst.
catalyst.As Asreported
reportedin inSection
Section1,1,resistance
resistanceto tocoking
coking
2.2.2. Effect of
is
even ifTheisaa major
major issue
its highestissue
effect of the to
to bebe
yield solved
solved [48]
was has
support [48] and
and
lower the
the
beenthan intimate
intimate
studied7% at contact
contact
(Figure between
between
5d). Coke
fixed contact the
the
time (τacid
acid sites,
sites,
formation
= 0.057 related
related
g∙s∙cm to
to phosphate,
phosphate,
was−3)negligible
and feed (Figu
The effectand
and of
the
the the
redox support
redox sites,
sites, has
related
relatedbeen to
to studied
vanadium,
vanadium, at provides
fixed contact
provides fast
fast time (τ = 0.057
conversion
conversion of
of coke
cokeg·s·cm −3) and feed
precursors
precursors into
into CO
CO x,x,which
which
duecomposition
composition
to(Gly/H
the good (Gly/H
O/O /N =
2O/O2/Nproperties
oxidation 2/41/6/51
2 = 2/41/6/51 vol.
vol. %). As
offor %).VOP
the As forcatalyst.
VOP/Ti,
VOP/Ti, acrylic
acrylic acid,
Asformic acid, formic
reported acid,
acid, and1,glycolic
in Section
and glycolic
resistance to
are the
themost
arewere most
2 abundant
abundantproducts
2 2 products due(Figure
(Figure 5b).
5b). CO increases
COlow increases at
attemperatures
temperatures above
above235 235°C, while
°C,were
whilenotCO
CO22
is aacid
acid were major
detected.
detected.
issue to beHowever,
However, solved
due to their [48] to their
and
very the
low
very
intimate
amounts,
amounts,
contact
the
the corresponding
between
corresponding thethe
yields acid
were
yields
sites, related
notdecrease to pho
reported. In Figure 8, the glycerol conversion and the yields to acrolein, CO, CO2, acetic acid, andby
slightly
slightly decreases;
decreases; therefore,
therefore, oxidation
oxidation ofof acrolein
acrolein and
and acetic
acetic acid
acid (where
(where the yields
yields decrease by
Catalysts 2020, 10, 673 7 of 15
Catalysts 2020, 10, x FOR PEER REVIEW 7 of 14

100 20
a) b)

80 16

Conversion, %
60 12

Yield, %
40 8

20 4
Catalysts 2020, 10, x FOR PEER REVIEW 7 of 14

0 100 20 0
160 a)180 200 220 240 260 280 160
b) 180 200 220 240 260 280

80
Temperature, °C 16
Conversion, %

Figure 7. (a)
Figure Glycerol
7. (a) Glycerolconversion, (b)
conversion, (b) yields
yields to acrolein
to acrolein as a function
as a function of temperature
of temperature at different
at different contact
60 12

Yield, %
times:
contact 0.043 (full
times: 0.043symbols), 0.057 (semi-filled
(full symbols), symbols), 0.088
0.057 (semi-filled (open symbols)
symbols), (open−3; symbols)
0.088 g·s·cm Gly/H2O/Og·s·cm
2/N2 −3 ;

Gly/H O/O2 /N2vol.

= 22/41/6/51 = 2/41/6/51
%. 40 vol. %. 8

2.2.2. Effect of the Support

100 20 4 40
a) b)
The effect of the support 0 has been studied at fixed contact time (τ =0 0.057 g·s·cm−3 ) and feed
80 160 180 200 220 240 260 280 160 180 200 220 240 260 280
composition (Gly/H2 O/O2 /N2 = 2/41/6/51 vol. Temperature,
Conversion, %

%). As for°CVOP/Ti, acrylic acid, formic 30 acid, and glycolic

Yield, %
acid were detected. 60However, due to their very low amounts, the corresponding yields were not
Figure 7. (a) Glycerol conversion, (b) yields to acrolein as a function of temperature at different contact
reported. In Figure 8, the
times: 0.043 (fullglycerol conversion
symbols), 0.057 and
(semi-filled the yields
symbols), to acrolein,
0.088 (open CO,−3;CO
symbols) g·s·cm , 2acetic
220
Gly/H O/O2/N2acid, and coke
obtained on the VOP/x 40vol.
= 2/41/6/51 catalysts
%. are compared.
10
20 100 40
a) b)

0 80 0
Conversion, %

30
c) d)
50 60 Yield, %
50
20
40 40 40
Yield, %

Yield, %

10
30 20 30

20 0 0 20
c) d)
10 50 50 10

0 40 40
0
Yield, %

Yield, %

8 30e) f) 30 2.0

20 20
6 1.5
Yield, %

Yield, %

10 10

4 0 0 1.0
8 e) f) 2.0
2 0.5
6 1.5
Yield, %

Yield, %

0 0.0
4 200 250 300 350 200 250 300 3501.0

2
Temperature, °C
0.5

Figure 8. Glycerol conversion (a), yields to acrolein (b), to CO (c), to CO2 (d), to acetic acid (e), and to
0 of temperature on different VOP catalysts: VOP/Ti (full symbols),
coke (f) as a function 0.0 VOP/Zr (semi-
200 250 300 350 200 250 300 350
filled symbols), VOP/Al (open symbols). τ = 0.057 g·s·cm ; Gly/H2O/O2/N2 = 2/41/6/51 vol. %.
−3

Temperature, °C

Figure 8. Figure 8. Glycerol

Glycerol conversion
conversion (a),yields
(a), yields toto
acrolein (b), to
acrolein CO to
(b), (c), CO
to CO(c),
2 (d), to acetic acid (e), and to
to CO2 (d), to acetic acid (e),
coke (f) as a function of temperature on different VOP catalysts: VOP/Ti (full symbols), VOP/Zr (semi-
and to coke (f) as a function of temperature on different −3VOP catalysts: VOP/Ti (full symbols), VOP/Zr
filled symbols), VOP/Al (open symbols). τ = 0.057 g·s·cm ; Gly/H2O/O2/N2 = 2/41/6/51 vol. %.
(semi-filled symbols), VOP/Al (open symbols). τ = 0.057 g·s·cm−3 ; Gly/H2 O/O2 /N2 = 2/41/6/51 vol. %.
 Interestingly, significant peak production of acrolein was obtained (35% yield) at about 300 °C, with
about 30% yield in the temperature range 265–325 °C. Yield to acetic acid showed a maximum at 285
°C. The CO yield continuously increased while increasing the temperature, while the CO2 yield
showed a sharp increase between 200 and 265 °C, and then it increased moderately. Coke formation
was 2020,
Catalysts higher than that obtained on the other samples, but it was still very low, being below 0.4%
10, 673 8 ofin
15the
whole temperature range. Carbon balance is reported in Figure 9. It increased by increasing the
temperature; however, it never reached 100%, with the highest value being 95%. This meant that i)
Glycerolproducts
unknown conversion was aboutin60%
are produced on both
the whole VOP/Zr and
temperature VOP/Al
range (in low 180 ◦ C. starting
atamounts By increasing
from 300
the°C)
temperature, glycerol conversion became quite complete at 200 ◦ C for VOP/Zr, while higher
and ii) the CO yield mainly increases due to the oxidation of the unknown species.
temperatures were needed for catalytic
VOP/Al (250 ◦ C).
The behavior of the performance in terms of glycerol conversion and products
distribution as a function of the reaction temperature isanot
On VOP/Zr yields to acrolein and acetic acid show maximum
directly (7.4%
relatedand 3.3%,
to the VOP respectively)
amount. This
at about 200 ◦ C. Their decrease is mainly compensated by a corresponding increase of the CO yield,
result suggests the role of the support, as evidenced by NH3-TPD characterization in terms of the acid
in agreement with the results on VOP/Ti. Coke yield is very low in the whole temperature range,
sites distribution.
becoming entirely negligible above ◦ C. Carbon balance (not reported) is about 100% except at 180 ◦ C,
In this sample, the effect of200
oxygen concentration in the feed was studied (Figure 10) at 325 °C.
where itWithis about 40%.
respect to It
theis reaction
worth noting that no
conditions COx production
reported above (O2 was detected
= 6 vol. at thisoxygen
%), a slight temperature.
decrease
Thus, VOP/Zr could activate and convert glycerol into condensable species, but
provided improved performance, with the yield to acrolein increasing to about 40%, while a decrease oxidation activity was
negligible. As stated above, VOP/Al needs higher temperatures to convert glycerol
in the acrolein yield was found when increasing O2 concentration, mainly due to acrolein oxidation. fully. Interestingly,
significant peak
In the production
presence of acrolein
of oxygen in thewas obtained
feed, glycerol(35% yield) at about
conversion 300 ◦ C,
was 100%, withcarbon
while about 30% yieldwas
balance
in the temperature range 265–325 ◦ C. Yield to acetic acid showed a maximum at 285 ◦ C. The CO yield
>90%, reaching 100% at 10 vol. % O2 in the feed. On the contrary, in the absence of oxygen in the feed,
continuously increased while
glycerol conversion increasing the
was incomplete, wheretemperature,
the yieldwhile the COdecreased
to acrolein 2 yield showeddowna to sharp increase
15.7%, no COx
between 200 and ◦
265detected
C, and(not thenreported)
it increased moderately.
production was and the carbonCoke formation
balance declined wastohigher
about than
30%.that Coke
obtained on the other samples, but it was still very low, being below 0.4%
formation significantly increased, with coke yield being 1.5%. These results suggest that in the in the whole temperature
range. Carbon
absence balance isoxygen,
of molecular reportedoxygenated
in Figure 9.compounds
It increasedotherby increasing the temperature;
than acrolein, however,
acetic acid acrylic acid,
it never reached 100%, with the highest value being 95%. This meant that (i) unknown
glycolic acid, and formic acid, and high boiling point compounds, such as glycerol oligomers, acrolein products are
produced
oligomers,in the
andwhole
aldoltemperature
condensation range (in loware
products, amounts from 300 ◦ C) and (ii) the CO yield
startingproduced.
preferentially
mainly increases due to the oxidation of the unknown species.

1.0
Carbon balance

0.8

0.6

0.4

0.2

0.0
160 200 240 280 320 360

Temperature. °C
Figure 9. Carbon balance as a function of temperature on VOP/Al. τ = 0.057 g·s·cm−3 ;
Figure 9. Carbon balance as a function of temperature on VOP/Al. τ = 0.057 g·s·cm−3; Gly/H2O/O2/N2
Gly/H2 O/O2 /N2 = 2/41/6/51 vol. %.
= 2/41/6/51 vol. %.

The behavior of the catalytic performance in terms of glycerol conversion and products distribution
as a function of the reaction temperature is not directly related to the VOP amount. This result suggests
the role of the support, as evidenced by NH3 -TPD characterization in terms of the acid sites distribution.
In this sample, the effect of oxygen concentration in the feed was studied (Figure 10) at 325 ◦ C.
With respect to the reaction conditions reported above (O2 = 6 vol. %), a slight oxygen decrease
provided improved performance, with the yield to acrolein increasing to about 40%, while a decrease
in the acrolein yield was found when increasing O2 concentration, mainly due to acrolein oxidation.
In the presence of oxygen in the feed, glycerol conversion was 100%, while carbon balance was
>90%, reaching 100% at 10 vol. % O2 in the feed. On the contrary, in the absence of oxygen in the feed,
glycerol conversion was incomplete, where the yield to acrolein decreased down to 15.7%, no COx
production was detected (not reported) and the carbon balance declined to about 30%. Coke formation
significantly increased, with coke yield being 1.5%. These results suggest that in the absence of
 Catalysts 2020, 10, 673 9 of 15

molecular oxygen, oxygenated compounds other than acrolein, acetic acid acrylic acid, glycolic acid,
and
Catalysts formic
2020, acid,
10, x FOR PEERand high boiling point compounds, such as glycerol oligomers, acrolein9 oligomers,
REVIEW of 14
Catalysts 2020, 10, x FOR PEER REVIEW 9 of 14
and aldol condensation products, are preferentially produced.
Conversion, acrolein yield,

Conversion, acrolein yield,

100 100
carbon balance, %

carbon balance, %
80 80

60 60

40 40

20 20

0 0
0 02 24 46 68 810 10
O2 concentration, % %
O concentration,
2
FigureFigure
10. Conversion
concentration in on
in the feed
(▼),(H),
Conversion
10. 10.
Figure
theVOP/Al.
feed on T
yield
Conversion
to acrolein
yield
(▼), to
= 325 C;
VOP/Al. ◦
acrolein
yield
T τ= =325
(⬤), andcarbon
( ), and
to acrolein
°C;g·s·cm
0.057 −3
carbon
(⬤), and
τ = 0.057; Glycerol
−3
balance
balance
carbon
g∙s∙cm ;=Glycerol
(◇) as a function
(^) balance
as a function
( ) of
O = 41
2 vol. %;=H22vol. %;vol.
H2O%; =N
of O2
◇
asOa2 concentration
function of O2
= balance.
41 vol.
concentration in the feed on VOP/Al. T = 325 °C; τ = 0.057 g·s·cm−3; Glycerol = 2 vol. %; 2H2O = 41 vol.
%; N2 = balance.
%; N2 = balance.
3. Discussion
3. Discussion
In this work, the dehydration of glycerol to acrolein over supported VOPO4 (VOP) catalysts was
3. Discussion
studied.
In this work, A theoretical VOP monolayer was supported overon TiO2 , AlVOPO2 O3 , and ZrO2 catalysts
; where deposition
In thisthe dehydration
work, of glycerol
the dehydration to acrolein
of glycerol to acroleinsupported
over supported4 (VOP) VOPO4 (VOP) catalysts was was
onto
studied. A these supports
theoretical VOPguaranteed
monolayer was goodsupported
active phase dispersion.
on TiO All the samples show low coke
2, Al2O3, and ZrO2; where deposition
studied. A theoretical VOP monolayer was supported on TiO2, Al2O3, and ZrO2; where deposition
formation
onto these in theguaranteed
presence ofgood molecular oxygen in the feed, due All to their redox show properties. coke However,
ontosupports
these supports guaranteedactive goodphase activedispersion.
phase dispersion. the samples
All the sampleslow show low coke
the
formation higher the
in the presence redox ability,
of molecularthe lower the
oxygen in acrolein
the feed,yield
due due to
to theirthe oxidation of the desired product
formation in the presence of molecular oxygen in the feed, due redox
to theirproperties. However,
redox properties. However,
to COthe
the higher x . Acrolein
redox is thethe
ability, main condensable
lower the acrolein product,
yield and to
due low theyields to acrylic
oxidation of the acid, formic
desired acid, acetic
product
the higher the redox ability, the lower the acrolein yield due to the oxidation of the desired product
to COacid, and glycolic acid were measured. Unknown products are rarely detected; the corresponding
x. Acrolein is the main condensable product, and low yields to acrylic acid, formic acid, acetic
to COx. Acrolein is the main condensable product, and low yields to acrylic acid, formic acid, acetic
reaction
acid, and glycolic conditions
acid were aremeasured.
not interestingUnknown due products
to incomplete are rarelyglycerol conversion and/or negligible
acid, and glycolic acid were measured. Unknown products aredetected; the corresponding
rarely detected; the corresponding
acrolein
reactionreaction production.
conditions are not are interesting due to incomplete glycerolglycerolconversion and/or negligible
conditions not interesting due to incomplete conversion and/or negligible
VOP supported onto alumina provided the best catalytic performances. Dehydration activity is
acrolein production.
acrolein production.
related
VOP to the abundance
supported onto alumina of weak
providedand themedium best theacid sites,
catalytic while its lowest
performances. redox activity
Dehydration activity preserves
is
VOP supported onto alumina provided best catalytic performances. Dehydration activity is
acrolein
related to from
the abundance oxidation.of weakof Theandcatalysts
medium investigated
acid sites, exhibit
while excellent resistance to coke formation,
related to the abundance weak and medium acid sites,itswhile
lowest itsredox
lowestactivity preserves
redox activity preserves
thereby
acrolein from suggesting
oxidation. itTheas acatalysts
good candidate
investigated for the glycerol
exhibit dehydration
excellent to acrolein.
resistance to coke to formation,
acrolein from oxidation. The catalysts investigated exhibit excellent resistance coke formation,
Our
thereby thereby
suggesting best it catalyst
as a good (VOP/Al)
candidate shows
for the performance
glycerol dehydration comparable
to acrolein. to catalysts reported in
suggesting it as a good candidate for the glycerol dehydration to acrolein.
the literature
Our bestOur catalyst [27,28,31,37,58].
(VOP/Al) Better
shows performanceperformances are
comparable reported with
to catalysts yields to
reportedreportedacrolein in the range
in the literature
best catalyst (VOP/Al) shows performance comparable to catalysts in the literature
70–90% [5,25,33,43,63].
[27,28,31,37,58]. Better performances However, deactivation
are reported withphenomena
yields to acrolein due to in coking are usually
the range 70–90%found.
[27,28,31,37,58]. Better performances are reported with yields to acrolein in the range 70–90%
For instance,
[5,25,33,43,63]. Katryniok
However, et
deactivational. [64] defined
phenomena a stable yield
due to coking to acrolein equal to 60–65% in a two-zone
[5,25,33,43,63]. However, deactivation phenomena due to are usually
coking found. For
are usually found. instance,
For instance,
fluidized
Katryniok bed as
et al. [64]etdefinedvery promising.
a stable ayield to yield
acrolein equal toequal60–65% in a two-zone fluidizedfluidized
bed as bed as
Katryniok al. [64] defined stable to acrolein to 60–65% in a two-zone
Differently from the literature tested samples, the VOP/Al catalyst has shown very high resistance
very promising.
very promising.
to coking.
Differently As
from a consequence,
the literature it istested
a goodsamples,
candidate forVOP/Al
the the glycerol dehydration
catalyst has shown to acrolein, provided
Differently from the literature tested samples, the VOP/Al catalyst has veryshownhigh very high
that
resistance the active
to coking. phase loading and the operating conditions are not optimized.
resistance to As a consequence,
coking. it is a good
As a consequence, it iscandidate for the glycerol
a good candidate dehydration
for the glycerol to acrolein,
dehydration to acrolein,
provided Future
that the works
active will beloading
devotedand to the
the optimization of the active phase loading and the operating
provided that thephase
active phase loading operating
and conditions
the operating are not
conditions optimized.
are not optimized.
conditions to maximize the acrolein yield. Moreover,
Future works will be devoted to the optimization of the active phase loading and the the effect of crude glycerol, containing
operating several
Future works will be devoted to the optimization of the active phase loading and the operating
organic
conditions and inorganic
to maximize impurities,
the acrolein yield. will be investigated.
Moreover, the effect Meanwhile,
ofeffect the presence
crudeofglycerol, containing of other
severalorganic
conditions to maximize the acrolein yield. Moreover, the crude glycerol, containing several
organic organic
and inorganicand inorganic impurities, will be investigated.
impurities, will be investigated.Meanwhile, the presence
Meanwhile, of otheroforganic
the presence other organic
compounds can affect
compounds can the reaction
affect pathway,
the reaction and the and
pathway, inorganic compounds
the inorganic (mainly (mainly
compounds alkali metal alkaliions,
metal ions,
such as Na + and K+) can poison the catalyst by affecting the number and the strength of the acid sites.
such as Na and K ) can poison the catalyst by affecting the number and the strength of the acid sites.
+ +
Catalysts 2020, 10, 673 10 of 15

compounds can affect the reaction pathway, and the inorganic compounds (mainly alkali metal ions,
such as Na+ and K+ ) can poison the catalyst by affecting the number and the strength of the acid sites.

4. Materials and Methods

4.1. Catalysts Preparation

Vanadyl orthophosphate, VOPO4 ·2H2 O (VOP), was prepared as described in References [52,53].
γ-Al2 O3 (CK-300 AKZO), anatase TiO2 (Eurotitania), and ZrO2 (prepared by conventional precipitation
method [53]) were used as supports.
Each support was loaded with a VOP amount corresponding to a theoretical monolayer and,
thus, depended on the support specific surface area, as reported in Table 1. The VOP was loaded onto
the supports by the impregnation method, as described in Reference [53].
All these catalysts were indicated as VOP/M, where M was the metal ion of the oxide support.

4.2. Physico-Chemical Characterizations

The actual composition of the investigated samples was determined using inductively coupled
plasma mass spectrometry (ICP-MS) analysis using an Agilent 7500CE instrument (Agilent, Santa Clara,
CA, USA). Results showed differences with the nominal content within the experimental error (± 5%).
The specific surface areas (SSA) of supports and catalysts were measured by N2 adsorption at
77 K with a Quantachrome Autosorb-1C instrument (Quantachrome, Boynton Beach, FL, USA) after
degassing the samples at 150 ◦ C for 1.5 h and calculated according to the Brunauer–Emmett–Teller
(BET) method. No significant differences were detected between fresh and used samples.
X-ray diffraction (XRD) patterns of calcined catalysts were recorded using a Philips PW
1100 diffractometer (Philips, Eindhoven, Netherlands) with Ni-filtered Cu Kα radiation. Angular
measurements (2θ) were accurate to 0.05◦ .
Temperature programmed desorption of ammonia (NH3 -TPD) were carried out using a
Micromeritics Autochem II 2020 (Micromeritics, Norcross, GA, USA) equipped with a TC detector
(Norcross, GA, USA). The samples (≈ 150 mg) were pre-treated in helium for 15 min at 450 ◦ C,
then saturated with a 5 vol. % NH3 /N2 mixture for 1 h at 30 ◦ C and washed in nitrogen for 0.5 h.
The reactor was then heated at 10 ◦ C/min up to 550 ◦ C. NH3 -TPD profiles were deconvoluted using
Origin software (OriginPro 2015 version) (OriginLab Corporation, Northampton, MA, USA, 2015).
Three contributions were detected and assigned to weak, medium, and strong acid sites. NH3 -TPD
tests were carried out on both the fresh and the used samples. No significant differences were detected.
Temperature programmed reduction in hydrogen (H2 -TPR) are reported in Reference [53], and here,
they were used to discuss the relationship between catalytic activity and redox properties.

4.3. Catalytic Tests

Catalytic tests were conducted in a lab-scale test rig. The experimental apparatus was developed
to carry out activity tests under stationary conditions, varying several operating parameters, such as
temperature, reactant flow rates, and concentrations.
The flow rates of permanent gases (O2 and N2 ) were independently controlled using mass flow
controllers (Brooks model SLA5850S), while a liquid 20 wt. % glycerol-water solution [5,18,31,64,65]
was fed through a volumetric pump (KNF SIMDOS® 02), vaporized using a heating tape, set at about
160 ◦ C, and mixed with the permanent gases before entering the reactor. Pure glycerol (Sigma-Aldrich,
purity ≥ 99.5%) was used as purchased. Crude glycerol from an alkali transesterification plant contains
some impurities, such as methanol, soap, free fatty acids (FFAs), fatty acid methyl ester (FAMEs),
glycerides. In addition, alkali metal ions (as Na+ and K+ ) are generally found in crude glycerol [66];
these alkali metals can poison the catalyst [66].
Catalysts 2020, 10, 673 11 of 15

The catalyst (180–300 µm) was placed in a vertical quartz tube. The reaction temperature was set
using a heating jacket (Tyco Thermal Controls) equipped with a PID controller. A K-type thermocouple
was placed inside the reactor, thereby providing the reaction temperature.
Downstream the reactor, condensable species were separated from the gas mixture in three flasks
in series placed in an ice bath. The collected liquid was analyzed off-line in a high-pressure liquid
chromatography (HPLC) system (Agilent1100), provided with a refractive index detector (RID) and a
diode Array type of UV/VIS Detector (DAD). Measurements were repeated three times, and the average
values were used for the mass balance. However, values differed within the experimental error (±3%).
Incondensable species (CO, CO2 , O2 ), dried by a CaCl2 trap, were analyzed in a continuous
analysis system (ABB AO2000), provided with a paramagnetic detector for O2 measurement and a
nondispersive infrared (NDIR) detector for CO and CO2 measurements. The absolute uncertainty of
the analyzer depends on the measurement range and corresponds to 50 ppm, 250 ppm, and 1000 ppm
for CO, CO2 , and O2, respectively. These values are much lower than the corresponding measurements
during the reaction tests, thereby suggesting good reliability and accuracy of the measurements.
Gas-phase glycerol concentration was set at 2 vol. %, while oxygen concentration was in the range
0–10 vol. %. Nitrogen was used as a balance. The temperature was in the range 170–360 ◦ C
and the contact time in the range 0.04–0.09 g·s·cm−3 . It is worth noting that glycerol concentration was
below its lower flammability limit (3 vol. %).
After each catalytic test, temperature-programmed oxidation (TPO) was carried out to (i) verify
the formation of carbonaceous deposits onto the catalyst surface and (ii) clean the catalyst surface for
the following catalytic test.

5. Conclusions
Supported vanadyl orthophosphate (VOP) were tested in the glycerol dehydration to acrolein.
VOP supported onto γ-alumina showed the best performance, related to the highest amount of weak
and medium acid sites. The oxygen co-feeding provides a good resistance to coking, which is, indeed,
the main open issue of the catalytic systems for this reaction. The main by-products are CO and CO2 ;
while high selectivity towards acrolein is detected among the condensable products.
Catalytic performance is comparable to the performance of other catalytic systems but lower than
that of the best catalysts. In this work, no reaction conditions nor active phase loading were optimized,
suggesting that VOP supported onto γ-alumina are good candidates for glycerol dehydration to acrolein.

Author Contributions: Conceptualization, G.L. and A.D.B.; data curation, G.L. and G.R.; investigation, G.L., G.R.
and A.D.B.; methodology, G.L., G.R., and A.D.B.; writing—original draft, G.L.; writing—review and editing, G.L.,
G.R., and A.D.B. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Acknowledgments: The authors gratefully acknowledge Andrea Bizzarro for the BET analysis, Fernando
Stanzione for the ICP-MS measurements and Luciano Cortese for the XRD measurements.
Conflicts of Interest: The authors declare no conflict of interest.

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