Sulfated SnO2 as a high-performance catalyst for alkene oligomerization

Article abstract of DOI:10.1134/S0020168512100147

Nanoparticulate (3-5 nm) sulfated tin dioxide shows high catalytic activity for the oligomerization of isobutylene, hexene-1, and cyclohexene. The acidity (Hammett acidity function H₀) of sulfated stannia reaches H ₀ = -16.04. We have studied the effect of synthesis conditions on the physicochemical and functional properties of sulfated SnO₂.

Full text of DOI:10.1134/S0020168512100147

ISSN 0020ꢀ1685, Inorganic Materials, 2012, Vol. 48, No. 10, pp. 1012–1019. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © L.L. Yurkova, S.A. Lermontov, V.P. Kazachenko, V.K. Ivanov, A.S. Lermontov, A.E. Baranchikov, L.P. Vasil’eva, 2012, published in Neorganicheskie
Materialy, 2012, Vol. 48, No. 10, pp. 1139–1146.
Sulfated SnO As a HighꢀPerformance Catalyst
2
for Alkene Oligomerization
a
a
a
b,c
b
L. L. Yurkova , S. A. Lermontov , V. P. Kazachenko , V. K. Ivanov , A. S. Lermontov ,
b
d
A. E. Baranchikov , and L. P. Vasil’eva
a
Institute of Physiologically Active Compounds, Russian Academy of Sciences,
Severnyi proezd 1, Chernogolovka, Noginskii raion, Moscow oblast, 142432 Russia
b
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia
c
Moscow State University, Moscow, 119899 Russia
d
Institute of Problems of Chemical Physics, Russian Academy of Sciences,
pr. Akademika Semenova 1, Chernogolovka, Noginskii raion, Moscow oblast, 142432 Russia
eꢀmail: van@igic.ras.ru
Received February 13, 2012
Abstract—Nanoparticulate (3–5 nm) sulfated tin dioxide shows high catalytic activity for the oligomerizaꢀ
tion of isobutylene, hexeneꢀ1, and cyclohexene. The acidity (Hammett acidity function H0) of sulfated stanꢀ
nia reaches H0 = –16.04. We have studied the effect of synthesis conditions on the physicochemical and funcꢀ
tional properties of sulfated SnO2
.
DOI: 10.1134/S0020168512100147
INTRODUCTION
and SnO2 under pressure at room temperature has
been the subject of several studies [23–25].
Sulfated metal oxides possessing highly acidic
properties are an environmentally safe alternative to
sulfuric acid, which is widely used in industrial proꢀ
cesses [1, 2]. The acidity of sulfated oxides depends on
many parameters: the nature of the metal, oxide prepꢀ
aration procedure, sulfation method, calcination temꢀ
perature, particle size, and surface area [3].
The purpose of this work is to analyze the influence
of synthesis conditions on the physicochemical propꢀ
erties of sulfated nanocrystalline tin dioxide and its
catalytic activity for the oligomerization of alkenes
(
isobutylene, hexeneꢀ1, and cyclohexene).
Sulfated zirconium and tin dioxides are thought to
have large Hammett acidity functions (Н0) compared
to other sulfated oxides, for example TiO , Fe O3, and
EXPERIMENTAL
Catalyst synthesis. SnCl4 5H O (50 g, 0.14 mol)
⋅
2
2
2
was dissolved in water (300 mL) and then 30% aqueꢀ
ous ammonia was added dropwise with stirring until
pH 10 was reached. The precipitate was washed with
water until the test for chloride was negative, and dried
Al O [1]. In particular, Arata et al. [4] determined the
2
3
H0 of sulfated ZrO2 and SnO2 to be –16.1 and –18.0,
respectively. As shown in detailed studies of acid cenꢀ
ters in sulfated ZrO2 and SnO2 using temperatureꢀproꢀ
at 120 C for 2 h. After cooling, the powder was thorꢀ
°
grammed ammonia desorption [5], sulfated tin dioxꢀ oughly ground and treated with a sulfuric acid solution
ide contains a smaller amount of strong acid centers (0.3 M or 3 M) for 1 h on a magnetic stirrer (30 mL of
(
14%) than does sulfated zirconium dioxide (42%), the H SO solution for 2 g of Sn(OH4). The precipitate
2 4
but their relative strength is far higher.
was then dried at 120
°
C for 5 h.
Sulfated tin dioxide is successfully used in laboraꢀ
The phase composition of the solid samples was
tory applications as a catalyst for many reactions, determined by Xꢀray diffraction on a Rigaku D/MAX
including hydrocarbon isomerization [6, 7], heptane 2500 diffractometer (Cu
radiation, scan rate of
/min). The crystallite size of the tin dioxide samples
K
2
θ
α
polymerization [8], alkane alkylation [9, 10] and oxiꢀ
2
°
dation [11, 12], phenol methylation [13], Friedel– was determined using the Scherrer formula, with
Crafts acylation, etherification and esterification [5, instrumental broadening taken into account.
1
4–18], and some other processes [19–22].
Specific surface areas (
Oligomerization of alkenes catalyzed by sulfated temperature nitrogen adsorption measurements with
tin dioxide has not yet been investigated. At the same an ATXꢀ06 analyzer (KATAKON, Russia). Prior to
time, isobutylene oligomerization on sulfated ZrO2 measurements, the samples were outgassed at 200
S) were determined by lowꢀ
°
C
1012

SULFATED SnO AS A HIGHꢀPERFORMANCE CATALYST
1013
2
CH3
t
catalyst
+
+ C + C
12 16
2
H C
2
CH3
Fig. 1. Isobutylene oligomerization reaction.
in flowing dry nitrogen for 30 min. The specific surface
of the powders was evaluated using Brunauer–
Emmett–Teller (BET) analysis (six points).
RESULTS AND DISCUSSION
Isobutylene oligomerization. The isobutylene oliꢀ
gomerization process is of practical interest because
1H and C NMR spectra in CDCl3 were measured the resulting isooctenes are easy to hydrogenate to
13
on a Bruker DPXꢀ200 spectrometer at 200 and isooctane, which is one of the most important and
5
0.3 MHz, respectively, using tetramethylsilane as an environmentally safe components of modern gasoꢀ
external standard.
lines. We attempted to synthesize isobutylene oligoꢀ
mers at different temperatures in the range 18–180 C
with solid acids without pressure (Fig. 1).
°
Mass spectra were obtained on a Finnigan MATꢀ
INCOS 50 quadrupole mass spectrometer (direct
insertion, 70ꢀeV electron impact ionization) and a
PerkinElmer Model Clarus 500 gas chromatoꢀ
graph/mass spectrometer (SEꢀ30 column).
We used two types of catalysts: tin dioxide treated
with 0.3 M and 3 M sulfuric acid solutions (catalysts I
and II, respectively). The results are summarized in
Table 1. It is seen that, at 18
С8 isomers was small: on the order of 2%. At 120
the sum content of С8 and С12 reached 96%, with C8 :
C = 1 : 1 (run 2). Running the reaction at 150
°
C (run 1), the fraction of
Chromatographic analyses were carried out using
LKhMꢀ2000 (1ꢀmꢀlong column, 3% Dexsil 300–
Chrom WꢀAW) and Kristallyuksꢀ4000M (ZBꢀ1 colꢀ
umn (Zebron) 100ꢀm long) chromatographs.
°
C,
°
C
12
increased the content of C + C oligomers to 98–
8
12
Thermogravimetric analysis (TGA) was performed
in the range 50–950
C using a PerkinElmer Model
PYRIS 6 TGA thermoanalytical system.
9
9%, with C : C ~ 3 : 2 (run 3). Raising the temperꢀ
8 12
°
ature to 180
whereas the С16 content was very low (run 4). At
10 , the reaction ceased (run 5), probably because
°
C increased the С8 content to 73%,
Oligomerization of alkenes. Prior to experiments,
the catalyst was calcined at 400–600 C in flowing dry
2
°
C
°
of the resinification of the organic compounds on the
surface of the catalyst.
air for 2 h and then cooled in a dry atmosphere.
Next, the catalyst (1 g) was placed in a waterꢀcooled
flask, an alkene (0.1 mol) was added, and the mixture (500 and 400
C) had no significant effect on the comꢀ
was agitated on a magnetic stirrer at constant temperaꢀ position or yield of the reaction products (runs 8 and 9).
Calcination of the catalysts at other temperatures
°
ture. Samples of the reaction mixture (0.2 mL) were
To examine the effect of water on the isobutylene
taken at intervals for analysis by NMR spectroscopy
oligomerization reaction, isobutylene was initially
and chromatography. The degree of conversion of the
passed through water in a bottle (run 6). The presence
1
alkene was evaluated from H NMR spectra.
of water vapor at a reaction temperature of 150 C had
°
A cyclohexene dimer was isolated by distillation no effect on the composition of the reaction products.
(
tb
=
150
°
C).
The catalysts can easily be regenerated by recalcinꢀ
ing them in flowing dry air, and the calcined catalyst
does not loose its activity (run 7).
Isobutylene was oligomerized as described elseꢀ
where [26].
Thermal desorption of pyridine. Catalyst samples
0.1 g) were calcined in dry air in a tubular reactor at
00, 500, and 600 . The temperature in the reactor
was then lowered to 150 , and the catalyst sample
was exposed to flowing dry air, which was bubbled
The present results lead us to conclude that, by
varying the temperature of the catalytic reaction, one
(
4
can tune the relative amounts of С , С12, and С16 in the
reaction mixture. The observed regular trends—the
increase in the percentage of С8 dimers and reduction
°
C
8
°
C
through pyridine (1 mL) until it completely vaporized. in the percentages of
С12 trimers and С16 tetramers
Samples weighing 30 to 40 mg were placed in an alunꢀ with increasing reaction temperature—can be
dum crucible under a dry pure argon atmosphere. The accounted for by the fact that, when isobutylene passes
heating rate in the range 390–460
°
C
was
5 C/min. through a catalyst at low temperatures, the liquid reacꢀ
°
The deviation of the reading of the thermobalance tion products are partially retained on the catalyst surꢀ
from zero was within
±
0.025 mg in the range 50– face and react with the alkene being fed, leading to the
0.01 mg in the range 300– formation of heavier fractions. Raising the reaction
temperature to above the boiling point of the reaction
9
50
°
C
.
and less than
±
7
00
°
C
INORGANIC MATERIALS Vol. 48
No. 10 2012

1014
YURKOVA et al.
Table 1. Composition of the isobutylene oligomerization products obtained with the use of SnO treated with 0.3 M (I) and
2
3
M (II) sulfuric acid solutions
t
,
°
C
Composition, %
C12
Catalyst operation
time, h
Percent
conversion
No.
Catalyst
I
calcination
600
reaction
C8
C16
1
2
18
2
68
48
30
4
4
–
120
48
2
4
6
53
65
70
3
150
180
57
73
42
27
1
2
4
6
90
90
90
4
5
tr
2
4
62
80
210
150
0
61
53
54
0
37
45
44
0
2
2
2
4
4
4
–
–
–
6
7
8
*
**
500
400
600
2
4
80
60
9
60
39
1
2
4
75
50
1
0
1
II
120
150
48
53
49
42
3
5
2
–
1
2
4
88
88
1
2
3
180
150
72
61
28
38
0
1
2
–
1
500
400
2
4
6
84
90
50
14
56
42
2
2
4
83
73
Note: We give averages of two to four experiments.
Isobutylene saturated with water vapor.
* Regenerated catalyst.
*
*
products causes the resultant vapor to skip through the reaction proceeded along two paths: migration of the
catalyst layer without reacting with the isobutylene.
terminal double bond, leading to the formation of
Similar results were obtained with catalyst II (runs hexeneꢀ2 and hexeneꢀ3, and the reaction of the carꢀ
1
0–14).
bocation with hexene molecules, leading to the formaꢀ
tion of oligomers (Table 2).
Oligomerization of hexene and cyclohexene. Isobuꢀ
tylene undergoes acid polymerization because of the
high stability of the forming tertiary cation. Hexene
and cyclohexene are considerably less capable of oliꢀ
gomerizing than is isobutylene. In view of this, we
studied the effect of sulfated tin dioxide on these subꢀ
stances. These alkenes were found to also undergo oliꢀ
gomerization.
The hexeneꢀ1 oligomerization products were charꢀ
acterized by gas–liquid chromatography (GLC), gas
chromatography/mass spectrometry, and H NMR
1
spectroscopy through comparison of the signal of the
CH =CH–R group in the parent hexeneꢀ1 to that of
2
the R–CH=CHꢀR/ group in the reaction products.
Hexeneꢀ1 was oligomerized in the presence of sulꢀ Figure 2 shows the overall reaction scheme and possiꢀ
fated tin dioxide at temperatures from 18 to 60
. The ble reaction products.
°
C
INORGANIC MATERIALS Vol. 48
No. 10
2012

SULFATED SnO AS A HIGHꢀPERFORMANCE CATALYST
1015
2
Table 2. Conversion of hexeneꢀ1 and cyclohexene with the use of SnO treated with 0.3 M (I) and 3 M (II) sulfuric acid
2
solutions
Percent
C converꢀ
sion
Percentage of C6–30
Reaction
time, h
No.
Catalyst tcalcin
,
°C
treaction, °
C6
C12
C18
C24
C30
1
2
3
4
5
6
7
8
9
I
600
500
400
600
500
400
1
24
1
18
18
60
18
18
60
18
18
60
18
18
60
18
18
60
18
18
60
83
83
75
46
26
22
–
32
47
51
–
18
21
22
–
4
5
0
1
100
5
0
1
57
–
1
–
0
24
1
100
41
31
–
46
54
–
12
14
–
1
0
1
14
27
–
–
1
–
–
0
24
1
–
–
–
34
78
60
28
29
57
27
22
79
–
13
30
54
47
32
57
61
14
–
8
1
1
1
1
1
1
1
1
1
1
2
0
II
1
71
10
14
19
10
14
15
6
0
0
1
24
1
100
4
0
2
5
0
3
1
100
1
0
4
24
1
2
0
5
2
0
6
1
37
1
0
7
24
1
100
–
–
1
–
0
8
41
–
44
–
14
–
9*
0*
I
600
600
7
43**
12**
–
–
–
–
II
7
–
–
–
Note: We give averages of two to four experiments.
Reaction with cyclohexene.
* 1ꢀCyclohexylcyclohexene yield.
*
*
Cyclohexene was found to dimerize under the Table 3. Specific surface area (S) and crystallite size of the
catalysts (SnO treated with 0.3 M (I) and 3 M (II) sulfuric
acid solutions) after annealing at different temperatures
action of sulfated tin dioxide, but the reaction yield
was lower in comparison with acyclic alkenes) (Fig. 3;
Table 2, runs 19, 20).
2
2
tann
,
°C
S
, m /g
Crystallite size, nm
The cyclohexene dimerization reaction was folꢀ
lowed using GLC and 1
Н
and C NMR. The dimer
13
I
45
was shown to be 1ꢀcyclohexylcyclohexene (Fig. 3).
25
–
13
The C DEPTꢀ135 NMR spectrum of the dimer conꢀ
tained two signals of C–H groups, and only one of
them was an alkene, in agreement with the structure
indicated above.
400
50
2.9
3.7
4.8
5
00
00
100
100
II
6
Thus, catalysts I and II showed rather high activity
for hexeneꢀ1 oligomerization. Catalyst I was more
active for cyclohexene dimerization.
2
5
50
–
Physicochemical characterization of the catalysts.
The specific surface area of samples I and II was deterꢀ
mined by lowꢀtemperature nitrogen adsorption meaꢀ
surements. The results are summarized in Table 3. It
5
00
00
105
90
3.3
4.0
6
INORGANIC MATERIALS Vol. 48
No. 10 2012

1016
YURKOVA et al.
catalyst
C + C + C + C + C
6
12
18
24
30
18–60°C
H C
2
CH2
CH2
CH
CH2
CH3
+
H+
H C
+
CH
C4H9
3
H2C
C4H9
–
H+
C
H
H
C
H C
C H
H C
C H
4 9
3
4
9
3
–
H+
H C
3
CH2
C
C
CH3
+
HC
CH2
CH
H
H
HC
1
) + H+
) – H+
C H
4
C H
4 9
9
2
H
C
H C
CH2
3
CH2
C
CH3
H
Fig. 2. Hexeneꢀ1 oligomerization reaction.
can be seen from these data that the H SO4 concentraꢀ
2
tion in the synthesis of the catalysts has little effect on
their surface area. At the same time, raising the calciꢀ
catalyst
83°C
2
nation temperature from 400 to 600
°
C considerably
increases the of the samples (by a factor of ~2).
S
It is worth pointing out that the particle size of
SnO2 inferred from Xꢀray diffraction data increases
systematically with increasing temperature. Thus, the
lowꢀtemperature nitrogen adsorption and Xꢀray difꢀ
fraction data indicate that the highꢀtemperature
growth of sulfated tin dioxide particles is accompanied
by an increase in their surface roughness because of
the partial decomposition of sulfate groups, accompaꢀ
nied by gas evolution.
A similar anomalous tendency for both the specific
surface area and particle size to increase with increasꢀ
ing annealing temperature was observed earlier in the
preparation of catalysts based on sulfated zirconium
dioxide [27].
Fig. 3. Cyclohexene dimerization reaction.
125
120
115
110
105
100
1
2
The density of acid centers on the surface of the
catalysts was assessed using thermal desorption of
pyridine (Table 4, Figs. 4, 5).
3
4
It follows from Figs. 4 and 5 and Table 4 that, in the
5
temperature range 400–550
C, the sample weight
°
decreases sharply, which is due to pyridine desorption
from strong acid centers [28]. Moreover, it is seen that,
on both catalysts, the largest amount of acid centers is
0
200
400
Temperature, °
600
C
800
activated during annealing at 400
annealing temperature to 600 sharply reduces the
amount of adsorbed pyridine, which points to a reducꢀ
°
C. Raising the
Fig. 4. TGA data for catalyst I exposed to pyridine vapor at
°
C
t
= (
1) 400, (2) 500, and (3) 600°C; (4) untreated catalyst I;
(5) parent SnO2.
INORGANIC MATERIALS Vol. 48
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2012

SULFATED SnO AS A HIGHꢀPERFORMANCE CATALYST
1017
2
116
112
108
104
100
1
2
3
4
5
0
200
400
600
800
Temperature, °C
Fig. 5. TGA data for catalyst II exposed to pyridine vapor at
) parent SnO2
t = (1) 400, (2) 500, and (3) 600°C; (4) untreated catalyst II;
(5
.
tion in the amount of acid centers. In particular, in the
case of sulfated SnO2 calcined at 400
, the amount of pyridine (Fig. 6) and spectra reported previously [5,
4] clearly indicates that the surface of sulfated tin
Comparison of the present IR spectra of adsorbed
°
C
2
adsorbed pyridine exceeds that on the sample calcined
at 600 by a factor of ~6. Pure tin dioxide adsorbs
dioxide has both Lewis and Brönsted acid centers.
°
C
very little pyridine, which suggests that there are no
strong acid centers on its surface.
The strength of acid centers (Hammett acidity
function Н0) on samples I and II was assessed by titratꢀ
ing with Hammett indicators in sulfuryl chloride. The
Н0 of the samples was found to vary considerably with
calcination temperature.
To gain further insight into the surface properties of
the catalysts, we used IR spectroscopy of adsorbed
pyridine, which allowed us to ascertain which types of
acid centers were present on the surface of sulfated
Table 5 presents the results of titration with 1,3,5ꢀ
SnO2
.
trinitrotoluene (Н0 = –16.04) as an indicator. It is seen
LC LC + BC BC
I
II
1400
1450
1500
1550
Wavenumber, cm
1600
1650
1700
–1
Fig. 6. IR spectra of pyridine adsorbed on catalysts I and II calcined at 400
°C.
INORGANIC MATERIALS Vol. 48 No. 10 2012

1018
YURKOVA et al.
Table 4. Weight loss (
Δ
m
) of the catalysts (SnO treated with
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2
°
C
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11. Wang, X. and Xie, Y.ꢀC., LowꢀTemperature CH Total
4
Oxidation on Catalysts Based on High Surface Area
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We have studied the effect of synthesis conditions
on the physicochemical properties of nanocrystalline
sulfated tin dioxide and its catalytic activity for the oliꢀ
gomerization of alkenes (isobutylene, hexeneꢀ1, and
cyclohexene).
1
1
1
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ACKNOWLEDGMENTS
This work was supported by the Russian Foundaꢀ
tion for Basic Research (grant no. 11ꢀ03ꢀ00981ꢀa), the
RF Ministry of Education and Science (grant
no. 14.740.11.0281), and the Presidium of the Rusꢀ
sian Academy of Sciences (Support to Basic
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