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The effect of cesium and antimony promoters on the performance of Ti-

phosphate-supported vanadium(V) oxide catalysts in selective oxidation of o-
xylene to phthalic anhydride

Article  in  Chemical Engineering Research and Design · June 2015

DOI: 10.1016/j.cherd.2015.06.030

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 chemical engineering research and design 1 0 2 ( 2 0 1 5 ) 286–296

Contents lists available at ScienceDirect

Chemical Engineering Research and Design

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

The effect of cesium and antimony promoters on

the performance of Ti-phosphate-supported
vanadium(V) oxide catalysts in selective oxidation
of o-xylene to phthalic anhydride

A. Akbari, S.M. Alavi ∗

Chemical Engineering Department, Iran University of Science and Technology, Narmak, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: In this work, the effect of vanadium loading as an active phase, cesium and antimony as
Received 21 January 2015 promoters for the performance of Ti-phosphate-supported vanadium(v) oxide catalysts by
Received in revised form experiment design method has been investigated. To find out the effects of parameters on
15 June 2015 the selectivity to phtalic anhydride, Taguchi approach with L16 array and ANOVA analysis
Accepted 17 June 2015 was utilized. The catalyst samples were characterized by BET ‘XRD’ ‘TGA’ ‘SEM’ NH3 -TPD. In
Available online 25 June 2015 addition, the catalytic measurements were carried out under continuous flow conditions in
fixed-bed reactor. The results show that cesium improves not only activity but also selectiv-
Keywords: ity to phtalic anhydride, while antimony just improves the activity. Meanwhile, the antimony
Selective oxidation o-xylene itself has a negative effect on the selectivity to phthalic anhydride. By taking into account
Phthalic anhydride main factor effect plot, the sample with composition of 15 wt% vanadium, 0.35 wt% cesium
Vanadium(V) oxide catalysts and 1 wt% antimony was chosen as the optimum sample. Finally, this catalyst demonstrated
Ti-phosphates support 70.9% selectivity to phthalic anhydride and 100% conversion of o-xylene at 410 ◦ C.
Cesium and antimony promoters © 2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction vanadium oxide. With introduction of o-xylene as the feed-

Phthalic anhydride (PA) is an important chemical intermediate
used in the synthesis of plasticizers for PVC, phthalocyanine
dyes, polyester and alkyd resins (Weissermel and Arpe, 2008;
Nikolov et al., 1991; Cavani et al., 2012). The selective oxidation
of o-xylene under nearly atmospheric pressure, temperature
ranges of 300–450 ◦ C and the o-xylene concentration in range
of 0.5–1.8 mol% within a fixed bed tubular reactor is the major
process for the production of PA over the world since 1960s
(Weissermel and Arpe, 2008; Gütlhuber, 2007; Marx et al., 2011).
The vanadia over the anatas phase of titania (V2 O5 /TiO2 ) is the
main catalyst for this process (Cavani et al., 2012; Gütlhuber,
2007; Marx et al., 2011).
The catalyst content for production of phthalic anhydride
from naphthalene in old processes was composed only of
stock, triggered new generation of spherical titania supported
catalyst with a thin layer of vanadium(v) oxide. Nowadays,
all industrial catalysts form from titania supported catalysts
which are in anatase phase beside the other elements as pro-
moters. Due to active phase required for inhibition of reaction
and because of thermal stability issue, a large amount of sup-
port is needed. In industrial applications a small amount of
titania supported vanadia is placed on neutral base (spherical
or ring) made of ceramic (Nikolov et al., 1991; Marx et al., 2011).
One of the problems under process which can occur for
vanadia catalysts supported on titania is the phase change
from anatase to rutile (Dias et al., 1997, 2002). In high tem-
peratures, this phase is changed with presence of vanadia
aggravates and can cause permanent deactivation of the cata-
lyst and also decrease in conversion and selectivity to phthalic

∗
Corresponding author. Tel.: +98 21 77240496; fax: +98 21 77240495.
E-mail address: alavi.m@iust.ac.ir (S.M. Alavi).
http://dx.doi.org/10.1016/j.cherd.2015.06.030
0263-8762/© 2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
 chemical engineering research and design 1 0 2 ( 2 0 1 5 ) 286–296 287

anhydride (Vejux and Courtine, 1978; Weckhuysen and Keller,

Table 1 – Factors and levels.
2003; Anastasov, 2003, 2005; Mongkhonsi and Kershenbaum,
Factor Level 1 Level 2 Level 3 Level 4
1998). One method for avoiding this phase change is to add
acidic elements such as phosphorus to titania (Jones et al., %wt V2 O5 2 7 12 15
2000). The addition of phosphorus causes better distribution %wt Cs2 O 0 0.35 0.7 1
of vanadia on the support resulting in the better catalyst acti- %wt Sb2 O3 0 1 2 4
vation (Nikolov et al., 1991; Jones et al., 2000). Jiménez-Jiménez
et al. (2005) studied behavior of vanadium(v) oxide supported
on titanium phosphate catalysts in the selective oxidation of each factor four levels were chosen. The control factors and
o-xylene. They found out that titanium phosphate improves their levels are summarized in Table 1. According to Taguchi
the catalytic behavior since it increases specific surface area, method, the L16 orthogonal array with three main factors at
appropriately distributes vanadium on the catalyst surface four levels each, were adopted for the study. It signifies that
and provides more reaction sites. Taguchi procedure suggested sixteen tests for applying the
Another factor which affects the performance of PA synthe- desired responses (Roy, 2001). Taguchi L16 statistical design
sis catalyst is the shape of vanadia which is appeared on the array which indicates the combination of factors and levels
surface of TiO2 (Cavani et al., 2006; Nobbenhuis et al., 1992; for sample preparation is given in Table 2.
Luciani et al., 2009). The most common shapes of vanadia
on the surface of TiO2 are isolated, polymeric and crystalline 2.2. Catalyst preparation
vanadium oxide (Weckhuysen and Keller, 2003; Cavani et al.,
2006). Vanadia structure on the support is transformed from The synthesis of vanadia/titanium phosphate catalyst with
isolated to vanadate crystal by increasing in vanadia loading, cesium and antimony as promoters can be summarized in two
so that the varying causes the selectivity to PA to be decreased steps:
(Cavani et al., 2006).
Various promoters are used to improve the catalytic activity (1) Preparation of titanium phosphate
and selectivity to PA. The alkali metals, cesium and anti- (2) Wet impregnation of the support with different amounts
mony are the most common promoters, applied to improve of vanadium and promoters
the V/Ti/O catalyst in the selective oxidation of o-xylene
to PA (Ballarini et al., 2009; Grzybowska-Świerkosz, 2002; Catalyst support Produced by the sol gel method (Jones
Anniballi et al., 2003; Wu et al., 2011). Cesium improves the et al., 2000). Surfactant molecules were eliminated by mixture
catalyst performance by changing the oxidation–reduction of HCl and ethanol, and calcined at 550 ◦ C.
behavior of the catalyst. It reduces the reduction ability of The Sb-Cs-doped V-Ti-P catalysts were prepared by wet-
vanadium and also increases the re-oxidation ability of vana- impregnation. An aqueous solution containing the desired
dium (Anniballi et al., 2003). In addition, antimony improves amount of ammonium monovanadate (Merck), cesium nitrate
the dispersion of the active phase on the support surface (Merck) and antimony fluoride (Merck) was prepared. The tita-
and also increases the stability of the V2 O5 (Cavani et al., nium phosphate support was added to the solution and the
2006). water was evaporated at 70 ◦ C in a rotavapor. The obtained
Taguchi method of orthogonal array experimental design wet solid was dried at 150 ◦ C for 3 h and calcined at 550 ◦ C for
can be used to handle any given system by a set of 5 h in static air. Amounts of salts needed for the synthesis of
independent variables (factors) over specific levels. This catalysts are summarized in Table 3.
approach not only helps in saving time and reducing
cost but also leads to a robust and more fully developed 2.3. Catalyst characterization
process by providing a systematic, simple and efficient
methodology for the optimization of the optimum design The catalyst samples were characterized by X-ray diffrac-
parameters with only a few well defined experimental tion (XRD). It was performed on the samples for phase
sets (Norouzbeigi and Edrissi, 2011).
One of topics which has not been studied yet includes the
effect of vanadia loading as an active phase, cesium oxide
Table 2 – L16 orthogonal design matrix.
and antimony oxide as promoters on the performance of cata-
lysts based on titanium phosphate-supported vanadium oxide Sample A B C
in the selective oxidation of o-xylene to PA (Jiménez-Jiménez 1 1 1 1
et al., 2005; Cavani et al., 2006; Anniballi et al., 2003). Therefore, 2 1 2 2
in the following work, to study the effect of factors for selec- 3 1 3 3
tivity to phthalic anhydride, Taguchi L16 statistical design is 4 1 4 4
employed. 5 2 1 2
6 2 2 1
7 2 3 4
8 2 4 3
2. Materials and methods 9 3 1 3
10 3 2 4
2.1. Design of experiments 11 3 3 1
12 3 4 2
In this study, Taguchi experimental design was employed for 13 4 1 4
14 4 2 3
analyzing the effect of vanadia content, cesium oxide and
15 4 3 2
antimony oxide loading in the selectivity to phthalic anhy- 16 4 4 1
dride. Therefore, three control factors were considered and for
288 chemical engineering research and design 1 0 2 ( 2 0 1 5 ) 286–296

Table 3 – Amounts of salts needed for the synthesis of 3. Results

catalysts.
3.1. X-ray diffraction (XRD)
Sample NH4 VO3 (gr) CsNO3 (gr) sbF3 (gr) Support (gr)

1 0.108 0 0 4 XRD patterns of all sixteen samples are shown in Fig. 1. Based
2 0.106 0.02 0.05 4 on the observed patterns, there is crystalline anatase phase
3 0.108 0.04 0.103 4
in the samples. This phase is appropriate for selective oxi-
4 0.11 0.06 0.21 4
5 0.39 0 0.053 4
dation of o-xylene to phthalic anhydride (Lange et al., 2012;
6 0.38 0.02 0 4 Castillo-Araiza and López-Isunza, 2011; Gimeno et al., 2008;
7 0.4 0.45 0.2 4 Schimmoeller et al., 2006). In the samples with 2, 7 and 12
8 0.4 0.06 0 4 wt% vanadium, peaks related to vanadium oxide are not seen.
9 0.71 0 0.11 4 It shows there is no crystalline vanadia phase on the sur-
10 0.73 0.025 0.23 4
face of the catalyst. In the samples with 15% vandia, peaks
11 0.7 0.045 0 4
related to vanadium pentoxide obtained which by increasing
12 0.71 0.065 0.05 4
13 0.95 0 0.24 4 percentages of vanadium are exhibited, place on the surface
14 0.93 0.025 0.11 4 of support in the form of crystal. In the samples 4, 8, 12,
15 0.92 0.045 0.6 4 16 containing 1 wt% cesium, due to additional incorpora-
16 0.91 0.065 0 4 tions between cesium and vanadium, weak peaks related to
Cs2 V4 O11 are observed.

3.2. BET surface area

characterization, at the rate of 0.02◦ /sec, using nickel filtered
Cu K␣ radiation ( = 1.5418 A◦ ) in the 2 range 4–60◦ , on a
PW-1800Philips diffractometer. The specific surface areas
of the samples were measured by nitrogen gas adsorption
at 77 K with a BELCAT-Ainstrument. The catalyst samples
were degassed at 150 ◦ C for 1 h before measurements. The
surface area was obtained by the Brunauer–Emmett–Teller
(BET) method. The morphologies of the samples were studied
using a Philips XL 30 scanning electron microscope (SEM).
Thermal analysis was carried out on NETZSCH TG 209 F1 up
to 850 ◦ C under static air, with a heating rate of 10 ◦ C/min.
The NH3 -TPD spectra were recorded in a fixed-bed reac-
tor system equipped with a gas chromatograph. The catalyst
(100 mg) was pretreated at 700 K under Ar flow (60 ml/min) for
2 h and then cooled to 373 K. Then NH3 was introduced into the
flow system. The TPD spectra were recorded at a temperature
rising rate of 10 K/min from 373 to 873 K.
2.4. Catalytic test
BET and SEM tests were carried out to assess the effect of
vanadium loading on the catalyst structure. The results of spe-
cific BET areas of the samples are given in Table 4. According
to the data presented in Table 4, with incorporation of vana-
dium, due to high porosity and high specific surface area of
titanium phosphate, specific surface area is decreased. Indeed
by adding vanadium, the pores are filled and samples would
have lower porosity. SEM images proved this hypothesis. In
the samples with same amount of vanadium, adding cesium
and antimony as promoter, the specific surface area has not
changed significantly.
3.3. SEM
SEM images of the samples 4, 8, 12 and 16 containing different
amounts of vanadium are shown in Fig. 2. The average pore
diameter for all the samples is more than 50 nm, so all samples
have macropore structure (Zdravkov et al., 2007).

Catalytic tests were performed in a continuous-flow, fixed- 3.4. TGA data

bed reactor at atmospheric pressure and temperature range of
350–450 ◦ C. The reactor is a 550 mm long, vertically mounted,
stainless steel tube with an internal diameter of 8 mm and an
external diameter of 12 mm, which has been placed inside an
electrical furnace.
The feed composition was 1% mol of o-xylene in air
(injected into the air stream using a syringe pump). The
total flow of air was 90 cm3 min−1 and the amount of the
catalyst was 0.5 g which was diluted seven times in silicon
carbide (particle size 0.42–0.50 mm), were held in the middle
of the reactor between two portions of glass wool. Before each
run, the catalyst was kept at 400 ◦ C for 1 h under flowing air
(90 cm3 min−1 ), after which it was cooled to the reaction tem-
perature. O-xylene was fed to the system after stabilization of
the temperature.
An ice bath was placed between the reactor outlet and the
gas chromatograph to condense part of the reaction products
and part of the unreacted o-xylene. Total oxidation products
were analysed by the TCD detector, whereas the organic reac-
tant and selective oxidation products were sensed by the FID
detector.
TGA is a method which measures mass changes of a sample
as a function of temperature in scanning mode, or as a func-
tion of time in isothermal mode. Thermo gravimetric analysis
can be used to evaluate optimum calcination temperature and
determine stable state temperature of a material. In this sur-
vey, the TGA method was used to evaluate the mass changes
in the support and the sample 7.
Fig. 3 shows the total weight loss of 33.89% in the sup-
port which occurred at four steps. The first step of weight
loss started from the room temperature and continued up to
120 ◦ C, which corresponded to the removal of the physisorbed
water or hydration which was remained in precursors. At the
second step, there was a weight loss resulting from decom-
position of the hydroxyl groups at the temperature range of
120–260 ◦ C. The maximum weight loss of the support occurred
in the temperature range of 260–620 ◦ C corresponding to the
elimination of surfactant. The last step happened in the tem-
perature range of 620–850 ◦ C resulting from the removal of
absorbed ethanol in the surfactant extraction process (Jones
et al., 2000; del Val et al., 2001; Tran et al., 2006).
 chemical engineering research and design 1 0 2 ( 2 0 1 5 ) 286–296 289

Fig. 1 – XRD patterns of the samples ( TiP2 O7 ,  Anatase, ♦ Cs2 V4 O11 , 䊉 V2 O5 ).

Table 4 – BET surface area of samples.

Sample P 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
Surface area (m2 /g) 237 162 166 170 173 108 108 116 110 77 75 71 70 36 30 29 26

Fig. 2 – The SEM photograph of: (a) sample P, (b) sample P, (c) sample 4, (d) sample 8, (e) sample 12 (f) sample 16.
290 chemical engineering research and design 1 0 2 ( 2 0 1 5 ) 286–296

Fig. 3 – TGA curve of sample P.

As mentioned before, for the synthesis of the final cat-
alyst the wet impregnation method with water and three
salts including NH4 VO3 , SbF3 and CsNO3 was employed. The
decomposition of these salts in water produced NH3 , HF and
NOx , respectively (Biedunkiewicz et al., 2012; Tang et al., 2014;
Zemnukhova et al., 2013). According to Fig. 4 the TGA curve of
the sample 7 had a total weight loss of 25.11% which occurred
at three steps. The first step began from the room tempera-
ture and continued up to 120 ◦ C corresponding to the removal
of water from the catalyst structure. The weight loss at the
second step occurred at the temperature range of 120–450 ◦ C
attributed to the elimination of ammonia and NOx produced
from the decomposition of salts in water. At the third step, the
maximum weight loss happened at the temperature range of
450–850 ◦ C and was caused by the removal of produced hydro-
gen fluoride (del Val et al., 1999; Bentrup et al., 2003).
3.5. Surface acidity
Thermo-programmed desorption of ammonia (NH3 -TPD) was
used for the evaluation of the number of surface acidic
sites. Table 5 shows the total acidity and the number of
acid sites desorbed at temperature range of 100–600 ◦ C for
the six samples. The total acidity value of Ti-phosphate sur-
face is 1262 ␮mol NH3 /gr relating to POH, P(OH)2 and Ti(OH)
groups with a Brønsted nature and also Ti sites with a Lewis
nature (Jones et al., 2000; Ramadan et al., 2009). Nearly 65% of
ammonia is desorbed between 100 and 300 ◦ C referring to the

Fig. 4 – TGA curve of sample 7.

 chemical engineering research and design 1 0 2 ( 2 0 1 5 ) 286–296 291

Fig. 5 – Conversion of o-xylene (filled symbols) and Fig. 6 – Conversion of o-xylene (filled symbols) and
selectivity to PA (open symbols) as functions of temperature selectivity to PA (open symbols) as functions of temperature
for the Samples 1 to 4. for the Samples 5 to 8.

preference of surface POH, P(OH)2 and Ti(OH) groups in this

temperature range (Turco et al., 1996), while in the tempera-
ture range of 400–600 ◦ C, strong acid sites are present due to
the 15% of desorbed ammonia.
By increasing vanadium loading, the amount of total acid-
ity decreases from 648 for the sample with 7% vanadium
to 364 ␮mol NH3 /g for the sample with 15% vanadium. This
reduction is not uniform for the different temperature range
and for the weaker acid sites (200–400 ◦ C) is more signif-
icant (Lietti and Forzatti, 1994; Sun et al., 2009). Adding
antimony as promoter, acidity increased uniformly for strong
and weak acid sites (Ieda et al., 2005). Cesium, due to having
high strength of base, neutralizes the acid sites significantly:
364 ␮mol NH3 /g for the sample with 15 wt% vanadium to
36 ␮mol NH3 /g by adding 0.35 wt% of cesium. It was found Fig. 7 – Conversion of o-xylene (filled symbols) and
out that adding antimony independently as a promoter, acid- selectivity to PA (open symbols) as functions of temperature
ity of catalyst surfaces is increased, while exposure to cesium, for the Samples 9 to 12.
acid sites are reduced significantly (Cavani et al., 2012; Bentrup
et al., 2003). The results show that when antimony and
cesium are utilized simultaneously, acidic sites are signifi-
cantly reduced by neutralizing the strong and weaker acid
sites.

3.6. Catalyst performance

The results of catalytic test for oxidation of o-xylene in the

temperature range of 350–450 ◦ C are shown in Figs. 5–8. Since
the desired product in this process is phthalic anhydride,
the appropriate catalyst must have a high selectivity to this
product. In this survey the conversion of o-xylene and the
selectivity to phthalic anhydride have been calculated using
Eqs. (1) and (2) respectively.

Fig. 8 – Conversion of o-xylene (filled symbols) and

(Molar o-xylenein ) − (Molar o-xyleneout )
%Conversion = selectivity to PA (open symbols) as functions of temperature
(Molar o-xylenein )
for the Samples 13 to 16.
× 100 (1)

Table 5 – Number of acidic centers (␮mol NH3 /gr) determined from NH3 -TPD analysis.
Sample 100–200 ◦ c 200–300 ◦ c 300–400 ◦ c 400–500 ◦ c 500–600 ◦ c Total acidity

Support 390 457 207 111 97 1262

7%V 118 219 167 78 66 648
15%V 42 98 94 73 57 364
15%V,1%Sb 51 115 125 89 68 448
15%V,0.35%Cs 4 6 14 7 5 36
15%V,0.35%Cs, 1%Sb 2 3 13 4 3 25
292 chemical engineering research and design 1 0 2 ( 2 0 1 5 ) 286–296

According to the Fig. 9, selectivity to phthalic anhydride

Table 6 – Taguchi L16 array response.
is maximum at A4, B2 and C2 levels. It is observed that
Sample Factor and level combination Response
the selectivity is increased by increasing vanadium load-
Yi Selectivity ing. NH3 -TPD analysis shows the acidic sites are decreased
to PA (%) with incorporation of vanadium to the surface of support.
Due to high number of acidic sites at lower values of vana-
1 A1 B1 C1 Y1 26.4
2 A1 B2 C2 Y2 57.6
dium, selectivity to phthalic anhydride is lower. Whilst, due
3 A1 B3 C3 Y3 43.5 to the decreasing of acidic sites by increasing percentage
4 A1 B4 C4 Y4 25.5 of vanadium, the formation of selective oxidation prod-
5 A2 B1 C2 Y5 21.7 ucts are decreased and selectivity to phthalic anhydride is
6 A2 B2 C1 Y6 62.4 increased (Jiménez-Jiménez et al., 2005). The values of selec-
7 A2 B3 C4 Y7 56.9
tivity increase with the average slope from level 1 to 2, but
8 A2 B4 C3 Y8 48.1
increase from level 2 to 3 and 4 very slowly. The slow increase
9 A3 B1 C3 Y9 21.9
10 A3 B2 C4 Y10 70.2 of the selectivity may be due uneven distribution of vana-
11 A3 B3 C1 Y11 49.3 dium on the support surface. In fact at the higher values of
12 A3 B4 C2 Y12 54.4 vanadium, the excess incorporation of vanadium results in
13 A4 B1 C4 Y13 28.4 the formation of V2 O5 crystals.
14 A4 B2 C3 Y14 70.8 By increasing percentage of cesium, the values of selec-
15 A4 B3 C2 Y15 57.4
tivity increase considerably to level 2 and then decrease to
16 A4 B4 C1 Y16 44.7
levels 3 and 4. The interaction between cesium and vanadium
has a significant effects on the redox properties of vanadium
(Ballarini et al., 2009; Anniballi et al., 2003; Bentrup et al., 2003),
so that cesium results in decreasing the vanadium reducibility
Molar productivity and increasing the re-oxidizability of the reduced vanadium
%Selectivity = sites. According to the previous studies (Anniballi et al., 2003;
(Molar o-xylenein ) − (Molar o-xyleneout )
Bentrup et al., 2003), the rate determining step in the selective
× 100 (2)
oxidation of o-xylene is vanadium re-oxidation step. There-
fore cesium improves this step and promotes the catalytic
behavior. According to Fig. 9, cesium content up to a certain
Based on the reactor test results, the conversion of o-xylene level (0.35 wt %) has a positive effect on the selectivity, and
for almost all the catalysts is near to completion in the temper- increasing more than 0.35 wt% has a negative effect due to the
ature range of 430–450 ◦ C, therefore no o-xylene was observed domination of the undesired effect (decreasing the reduction
in the reactor outlet. The selectivity to phthalic anhydride is capability) on the desired effect (re-oxidation of the reduced
increased by increasing temperature, however it is decreased vanadium). Thus, there’s an optimum value of 0.35 wt% for
after reaching a maximum value. The maximum value of cesium as the catalyst promoter. The observation of weak
selectivity was observed at 410 ◦ C for most of the samples. peaks of Cs2 V4 O11 in the samples containing 1 wt% cesium
Figs. 5–8 show that the presence of each cesium and anti- may be another factor in decreasing the selectivity to phthalic
mony or the combination of both have a significant effect anhydride (Anniballi et al., 2003).
on the catalytic activity. The presence of each of these ele- The neutralization of the acidic sites results in decreasing
ments improves the activity, although the affection of their deep oxidation of o-xylene and increasing the tendency
combination is more significant. Also, cesium improves not to selective oxidation products such as phthalic anhydride.
only activity but also selectivity to phtalic anhydride, however Based on the results of NH3 -TPD analysis, the total acidity of
antimony has a negligible effect on the selectivity. the sample with 15 wt% vanadium is 364 ␮mol NH3 /g, however,
it reaches 36 ␮mol NH3 /g by adding 0.35 wt% cesium. Jiménez-
4. Discussion Jiménez et al. (2005) reported that incorporation of potassium
remarkably suppresses the acidity of the surface by neutral-
Taguchi L16 with three factors and four levels for each factors, izing the whole strength range of the acid sites resulted in a
and with a repetition coefficient of 1 was used to investigated considerable increase in the selectivity to phthalic anhydride.
%wt V2 O5 , %wt Sb2 O3 and %wt Cs2 O parameters. The aim of The base strength of cesium is greater than potassium,
this survey is to choose appropriate catalyst combination in therefore the effect of cesium on the neutralization of acidic
order to maximize selectivity to phthalic anhydride and o- sites is higher than potassium and also the selectivity to PA is
xylene conversion. The results show that for the most catalyst increased more by cesium than potassium. Fig. 9 shows that
samples, selectivity to phthalic anhydride is maximum at the antimony has a roughly constant effect on the response and
temperature of 410 ◦ C, and in this temperature o-xylene con- just selectivity slightly is increased in level 2. The results of
version is more than 90%. Therefore, the values of selectivity to NH3 -TPD show that the total number of acidic sites for the
phthalic anhydride at the temperature of 410 ◦ C are chosen as sample with 15 wt% vanadium is 364 ␮mol NH3 /g, whereas the
selected responses for analyzing the results and determining total acidity increases to 448 ␮mol NH3 /g by adding 1 wt% anti-
the optimum condition. Table 6 shows the values of selectivity mony. Thus, by adding antimony independently as a promoter,
to phthalic anhydride at 410 ◦ C for 16 experiments. the tendency to selective oxidation products is decreased due
The main effects analysis was employed to study the trend to the increase of the catalyst surface acidity. Cavani et al.
of the each factors’ variations. Main effects plots for the three (2006) reported that if antimony is added independently to
factors considered (%wt V2 O5 , %wt Cs2 O, %wt Sb2 O3 ) versus V2 O5 /TiO2 , it has a negative effect on the selectivity to PA.
selectivity to phthalic anhydride in the selective oxidation of Based on the results of NH3 -TPD by adding antimony to the
o-xylene to phthalic anhydride are shown in Fig. 9. sample with 15 wt% vanadium and 0.35 wt% cesium, the acidic
 chemical engineering research and design 1 0 2 ( 2 0 1 5 ) 286–296 293

Fig. 9 – The main factor effect plot.

Table 7 – Analysis of Variance for Means (ANOVA).

Factor DOF SS Adj SS Adj MS F P

A 3 357.98 357.98 119.33 1.84 0.240

B 3 3476.39 3476.39 1158.80 17.92 0.002
C 3 15.88 15.88 5.29 0.08 0.967
Error 6 388.06 388.06 64.68
Total 15 4238.31

sites decrease from 36 to 26 ␮mol NH3 /g. Therefore it can be
said that when antimony and cesium are used simultaneously
then the conditions improve and the negative effect of anti-
mony disappears.
Statistical data are analyzed based on variance analysis
(ANOVA table). ANOVA table constitutes of square summation
(Eq. (3)), degree of freedom (DOF) and mean square of the vari-
ables (Eq. (4)). The F test (square of effects/square of residues)
and the probability of significance or value (Eq. (5)) are cal-
culated to evaluate the significant effects. If the F-value is
greater than the F0 -value belonging to a confidence domain ˛,
then the corresponding effect is accepted from statistical view.
Usually the level of significance or the confidence domain ˛ is
considered to be equal to 0.05 (Rutherford, 2001). The p-value
designates the probability of reaching to a specific value in the
F distribution with K − 1 variables and K(n − 1) degree of free-
dom, is greater or equal to F0 By using the p-value it is possible
In the selective oxidation of o-xylene to phthalic anhydride,
the ranks indicate that wt% Cs2 O has the greatest influence
followed by wt% V2 O5 and then wt% Sb2 O3 which can be
observed in Table 8. The optimum condition in this case where
in the percentage selectivity to phthalic anhydride is maxi-
mum at 0.35 wt% Cs2 O, 15 wt% V2 O5 and 1 wt% Sb2 O3 .
The last objective step of the Taguchi statistical design is
prediction of the selectivity to phthalic anhydride at the opti-
mum condition. Whenever the optimum combination of the
factors and levels are gained from the factor effect analysis,
the prediction of the optimized selectivity to phthalic anhy-
dride will be obtained from the Eqs. (6) and (7) (Roy, 2001):
¯ − Ȳ) = 70.94%
¯ − Ȳ) + (B̄2 − Ȳ) + (C2
Yopt = Ȳ + (A4 (6)

16

to evaluate variables and their effects. Yi

i=1
Ȳ = = 46.2% (7)
⎛ ⎞2 16

n 
n n 
n

SS = ⎝ xij − 1/nk xij ⎠ (3)

In Eq. (6) the Yopt is the predicted selectivity to phthalic
i=1 j=1 i=1 j=1
anhydride at optimum condition and Ȳ in Eq. (7) is the grand
average of the responses. The mean value of the response
SS
MS = (4)
df

P − value = P[F(k − 1), k(n − 1) > F0 ] (5)

Table 8 – Response table for mean (Larger is better).
Level A B C
ANOVA table is presented in Table 7. From F results of
ANOVA, percentages of influence of each factor were com- 1 38.25 24.60 45.70
puted and those are shown in Table 8. According to ANOVA, 2 47.27 65.25 47.88
3 49.05 51.77 46.08
wt% V2 O5 and wt% Sb2 O3 are not significant due to their P
4 50.33 43.27 45.25
values (P values greater than 0.05), therefore they do not con- Rank 2 1 3
tribute to the evaluation of the response.
294 chemical engineering research and design 1 0 2 ( 2 0 1 5 ) 286–296

Table 9 – Conversion of o-xylene for sample 17.

Temp (◦ C) Run 1 (%) Run 2 (%) Run 3 (%) Average (%)

350 34.89 32.02 33.18 33.36

370 73.12 74.75 75.02 72.29
390 80.27 83.72 82.35 82.11
410 100 100 98.17 99.39
430 100 100 100 100
450 100 100 100 100

Table 10 – Selectivity to PA for sample 17.

Temp (◦ C) Run 1 (%) Run 2 (%) Run 3 (%) Average (%)

350 30.12 30.08 28.7 29.63

370 34.06 32.12 31.8 32.66
390 68.12 68.29 67.71 68.03
410 70.9 73.2 68.57 70.89
430 70.38 68.02 70.17 69.52
450 44.05 45.19 43.16 44.13

Table 11 – Selectivity to COx for sample 17.

Temp (◦ C) Run 1 (%) Run 2 (%) Run 3 (%) Average (%) Fig. 11 – XRD patterns of fresh and used sample 17 (
TiP2 O7 ,  Anatase, 䊉 V2 O5 ).
350 52.18 54.09 51.89 52.72
370 53.97 55.69 53.37 54.34
390 22.59 23.7 25.61 23.96
410 11.49 12.19 14.35 12.67
430 13.71 11.51 11.84 12.35
450 48.26 46.83 49.91 48.34

at optimum condition (A4, ¯ C2)

¯ B2, ¯ should be computed. The
calculations are as follows:
Y13 + Y14 + Y15 + Y16
¯ =
A4 = 50.32
4
Y2 + Y6 + Y10 + Y14
¯ =
B2 = 65.25
4
Y2 + Y5 + Y12 + Y15
¯ =
C2 = 47.77
4
In this step a sample was prepared under optimum condi-
Fig. 12 – Stability test of the optimal catalyst.
tion (A4, B2, C2) and named sample 17. Catalytic test of the
sample 17 was done three times under the same conditions
and results are presented in Tables 9–11. The average selectiv-
temperature range between 430 and 450 ◦ C. The maximum
ity to phthalic anhydride was 70.89%. The difference between
value of selectivity to PA was observed at the temperature of
predicted (70.94%) and the achieved values (70.89%) is negli-
410 ◦ C with 70.89% in this temperature, the value of selectivity
gible and the obtained error 0.07% confirms the predictability
to COx was minimum and equal to 12.67%. Regarding the
of the process and accuracy of the experiment results. Fig. 10
results, by decreasing the number of acidic sites, selectivity to
shows the average results of catalytic test for the optimal sam-
PA increases and the production of carbon oxides decreases.
ple.
Fig. 11 shows the XRD pattern for sample 17 before and
According to Fig. 10, o-xylene conversion is increased
after the catalytic test. The crystal phase of titania has
by increasing temperature and it is equal to 100% in the
not been changed during the reaction and the rutile crystal
phase has not been formed. This is due to the stability of
the catalyst support during the reaction. According to using
the Debye–Scherrer equation, the size of the titania crystals
was calculated before and after the reaction, so that it was
observed no significant change and sintering of titania did not
occur during selective oxidation of o-xylene. It shows there is
crystalline phase V2 O5 on the surface of the catalyst. Specific
surface area of the optimal sample before the reaction is equal
to 33 m2 /gr. According to Table 5, the total number of acidic
sites of sample 17 is 25 ␮mol NH3 /g. The stability test of the
optimal catalyst was carried out for 105 h under atmospheric
pressure and 410 ◦ C. The flow rate of air, concentration of o-
xylene in inlet flow and weight of catalyst were 90 ml/min,
1% mol and 0.5 g, respectively. Fig. 12 shows that there is no
Fig. 10 – Average results of optimum sample (Sample 17). decrease in conversion of o-xylene, therefore the activity is
 chemical engineering research and design 1 0 2 ( 2 0 1 5 ) 286–296
reasonably acceptable. It also shows that the selectivity to
phthalic anhydride almost remains stable.
5. Conclusions
In this experimental study, the effect of vanadia content,
cesium oxide and antimony oxide loading on the performance
of Ti-phosphate-supported vanadium(v) oxide catalysts, in
the selective oxidation of o-xylene to phthalic anhydride was
investigated using Taguchi experiment design approach. Fac-
tor effect analysis and ANOVA indicated that the cesium oxide
loading is the most important parameter in selectivity to
phthalic anhydride. According to the Taguchi method, the best
vanadia content, cesium oxide and antimony oxide loading
for the most values of selectivity to phthalic anhydrid are
15 wt%, 0.35 wt% and 1 wt%, respectively. The optimal cata-
lyst demonstrated 70.9% selectivity to phthalic anhydride and
100% conversion of o-xylene at 410 ◦ C. By increasing vanadium
loading on the support, the selectivity to phthalic anhydride
increased. At higher vanadium loading, due to the formation
of V2 O5 crystals, influence of vanadium on the selectivity to
phthalic anhydride reduced. Addition of cesium to neutral-
ize the acid sites still exposed at the surface of the catalysts
resulting in a remarkable increase in the selectivity to phthalic
anhydride and conversion of o-xylene. In addition, by adding
antimony independently as the promoter, the tendency to
selective oxidation products is decreased due to the increase
of the acidity of catalyst surfaces. Once antimony and cesium
are used at the same time, the conditions are improved and the
negative effect of antimony is disappeared. The XRD patterns
of fresh and used optimal catalysts illustrated that the anatase
phase of titania remained stable during selective oxidation of
o-xylene without any sintering. The 105 h stability test of opti-
mal catalyst approved which the activity and selectivity stay
approximately constant.
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