Sulfated Zirconia and Its Modified Versions As Promising Catalysts For Industrial Processes

Microporous and Mesoporous Materials 33 (1999) 148
www.elsevier.nl/locate/micmat
Review
Sulfated zirconia and its modied versions as promising
catalysts for industrial processes
Ganapati D. Yadav, Jayesh J. Nair
Chemical Engineering Division, University Department of Chemical Technology, University of Mumbai, Matunga, Mumbai 400 019, India
Received 27 August 1998; received in revised form 1 December 1998; accepted for publication 6 July 1999
Abstract
Zirconium oxide, or zirconia, when modied with anions such as sulfate ions forms a highly acidic or superacidic
catalyst depending on the treatment conditions. This catalyst is found to be well suited for catalyzing reactions of industrial
importance, e.g. hydrocarbon isomerization, methanol conversion to hydrocarbons, alkylation, acylation, esterication,
etherication, condensation, nitration, cyclization, hydrationdehydration, carbonylation, oligomerization, FischerTropsch
reaction, cracking and hydrocracking reactions, methane oxidative coupling, thioacetalization, adamantylation, manufacture
of hydrogen peroxide, etc. The surface properties of these catalysts can be further modied in conjunction with noble or
transition metals as promoters as well as with carbon molecular sieves. This review highlights the chemistry and engineering
aspects of sulfated zirconia catalyst and its modied forms. 1999 Elsevier Science B.V. All rights reserved.
Keywords: Acylation; Alkylation; Carbon molecular sieves; Carbonylation; Catalyst; Condensation; Cracking; Cyclization;
Esterication; Etherication; Isomerization; Methanol conversion; Nitration; Oligomerization; Sulfated zirconia; Superacid
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2. Preparation of S-ZrO
2
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1. Eect of various preparation parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1.1. Eect of precursor and sulfating agent . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1.2. Eect of activation temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3. Nature of active sites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4. Modied S-ZrO
2
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4.1. Eects of Pt modication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.2. Eect of carbon coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.3. Mechanism for acidity generation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.4. Eect of water of hydration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.5. Eect of calcination temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.6. Modication of zirconia with other mineral acids . . . . . . . . . . . . . . . . . . . . . . . 17
5. Applications of S-ZrO
2
catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
5.1 Alkylations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
5.1.1 Benzylation of substituted benzene . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
5.1.2 Inversion in rates and selectivities in benzylations . . . . . . . . . . . . . . . . . . 20
* Corresponding author. Tel.: +91-22-4145616; fax: +91-22-4145614.
E-mail address: gdy@udct.ernet.in; gdyadav@bol.net.in (G.D. Yadav)
1387-1811/99/$ - see front matter 1999 Elsevier Science B.V. All rights reserved.
PII: S1387-1811 ( 99 ) 00147- X
2 G.D. Yadav, J.J. Nair / Microporous and Mesoporous Materials 33 (1999) 148
5.1.3 Alkylation of cresols with isobutylene and methyl tertiary butyl ether
(MTBE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
5.1.4. Alkylation of phenol and hydroquinone with MTBE . . . . . . . . . . . . . . . . 22
5.1.5. Alkylation of o-xylene with styrene . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
5.1.6. Manufacture of gasoline alkylates . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
5.1.7. Preparation of alkyl phenols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
5.1.8. Propylation of naphthalene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
5.1.9. Trans-alkylation of di-isopropylbenzene (DIPB) . . . . . . . . . . . . . . . . . . . 24
5.1.10. Alkylation of aromatics with olens . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
5.1.11. Alkylation of diphenyl oxide with 1-decene . . . . . . . . . . . . . . . . . . . . . . 24
5.2 Isomerizations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
5.2.1 Isomerization of epoxides to aldehydes . . . . . . . . . . . . . . . . . . . . . . . . . . 25
5.2.2 Hydroisomerization-cracking of n-octane . . . . . . . . . . . . . . . . . . . . . . . . 25
5.2.3 Isomerization of methyl cyclopentane to cyclohexane . . . . . . . . . . . . . . . . 26
5.2.4 Isomerization of d-citronellal to isopulegol . . . . . . . . . . . . . . . . . . . . . . . 26
5.2.5 Isomerization of straight-chain alkanes to branched isomers . . . . . . . . . . . . 28
5.2.6 Isomerization of terpinolene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
5.3 Condensation reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
5.3.1 Condensation of hydroquinone with aniline and substituted anilines . . . . . . . 29
5.3.2 Cyclocondensation of aniline with acetone . . . . . . . . . . . . . . . . . . . . . . . 31
5.4 Etherication and dehydration of alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
5.4.1 Etherication of tert-butanol with methanol . . . . . . . . . . . . . . . . . . . . . . 31
5.4.2 Etherication of isobutylene with methanol . . . . . . . . . . . . . . . . . . . . . . . 32
5.4.3 Etherication of b-naphthol with methanol . . . . . . . . . . . . . . . . . . . . . . . 32
5.5 Acylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
5.5.1 Acylation of benzene and chlorobenzene with p-chlorobenzoyl chloride . . . . . 32
5.5.2 Acylation reactions with carboxylic acids. . . . . . . . . . . . . . . . . . . . . . . . . 33
5.6 Esterication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
5.6.1 Esterication of phenethyl alcohol and cyclohexanol . . . . . . . . . . . . . . . . . 35
5.6.2 Esterication of phthalic anhydride with alkanol . . . . . . . . . . . . . . . . . . . 35
5.6.3 Esterication of phthalic anhydride with n-butanol and iso-amyl alcohol . . . . 35
5.7 Nitration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
5.7.1 Nitration of chlorobenzene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
5.7.2 Nitration of toluene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
5.8 Oligomerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
5.8.1 Oligomerization of 1-decene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
5.8.2 Oligomerization of butanebutene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
5.8.3 Oligomerization of trans-butene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
5.8.4 Dimerization of fatty acids, unsaturated straight chain aliphatic acids and
their esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
5.8.5 Preparation of synthetic lubricating base oils . . . . . . . . . . . . . . . . . . . . . . 40
5.9 FischerTropsch reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
5.10 Methanol to lower olens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
5.11 Cracking reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
5.12 Methane oxidative coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
5.13 Thioacetalization of carbonyl compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
5.14 Adamantylation of substituted benzenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
5.15 Manufacture of hydrogen peroxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
5.16 Decomposition of commingled waste plastics . . . . . . . . . . . . . . . . . . . . . . . . . . 43
5.17 Carbonylation reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
1. Introduction ively either as such or as supports in conjunction
with other active components for many industrial
oxidation, reduction and acidbase-catalyzed reac- Owing to environmental restrictions on emis-
sions covered in several legislations throughout the tions. The surface of zirconium oxide is known to
possess all these catalytic activities. Zirconium world, non-polluting and atom-ecient catalytic
technologies are much sought after. The use of oxide, or zirconia, when modied with anions,
such as sulfate ions, forms a highly acidic or acid catalysts is very rampant in the chemical and
renery industries, and those technologies employ- superacidic catalyst that exhibits superior catalytic
activity to catalyze many reactions. It has been ing highly corrosive, hazardous and polluting
liquid acids are being replaced with solid acids; widely used to catalyze reactions such as hydro-
carbon isomerization, methanol conversion to for instance, acid-treated clays, zeolites, zeotypes,
ion-exchange resins and metal oxides. Of late, a hydrocarbons, alkylation, acylation, esterication,
etherication, condensation, nitration, cyclization, number of organic syntheses have been conducted
with solid acids leading to better regio- and stereo- etc. Thus, S-ZrO
2
and modied S-ZrO
2
form an
important class of catalysts, as is evident from the selectivity. Not only the strength of the acid, but
also the type of acidity (Bronsted or Lewis) matters voluminous research that has appeared in the last
decade. Moreover, these catalysts show a promis- for enhanced activity and selectivity. The incorpo-
ration of superacidity in solids has attracted con- ing future in that they can provide environmentally
clean processes for the chemical industry of the siderable attention. Amongst these, sulfated
zirconia (abbreviated as S-ZrO
2
) has found several next millennium.
The objective of this review is to highlight the applications and holds great promise in a number
of reactions of industrial importance. importance of zirconia, particularly the modied
or treated form, in industrial reactions; some In general, metal oxides have been used extens-
Fig. 1. Acid strengths of liquid and solid superacids.
Table 1
Preparation procedure for S-ZrO
2
Starting material Precipitating Sulfating agent Calcination Nature of Surface Ref.
agent temperature (C) phasesa area (m2 g1)
ZrOCl
2
8H
2
O/ZrO(NO
3
)
2
Liq. NH
3
H
2
SO
4
/(NH
4
)
2
SO
4
350 M A [ 3]
650 M T
Urea H
2
SO
4
/(NH
4
)
2
SO
4
850 M T+M
ZrCl
4
Liq. NH
3
H
2
SO
4
/(NH
4
)
2
SO
4
200 A A 241 249 [ 4,5]
400 M A+C 115 159
SO
2
, SO
3
, CS
2
600 M+C A+C 19.6 97
ZrOCl
2
8H
2
O Liq. NH
3
H
2
SO
4
650 T 34 [ 6]
a A: amorphous; M: monoclinic; C: cubic; T: tetragonal.
aspects of S-ZrO
2
as catalysts have been reviewed the presence of 100% sulfuric acid, implying that,
based on the competition of water, it is a stronger by Song and Sayari [1]. The various methods of
preparation, characterization and mechanistic acid. It is also suggestive of the superacidity of
S-ZrO
2
, since 100% H
2
SO
4
is itself a strong dehyd- models have also been discussed. The pore struc-
ture of S-ZrO
2
can be modied in conjunction rating agent. Moreover, S-ZrO
2
exhibits a
Hammett acid strength of H
o
=16.04, whereas with other materials to impose shape selectivity.
There has been rapid progress on the develop- for 100% sulfuric acid it is only 11.99.
Although S-ZrO
2
shows higher strength, it ment of solid superacids, which include (i) sup-
ported acids (e.g. liquid acid such as SbF
5
on high suers from deactivation due to coke formation
at high temperature. The deactivation of S-ZrO
2
surface-area solids), (ii) synergism of metal halides
and metal salts (e.g. AlCl
3
CuCl
2
; AlCl
3
has, to a large extent, been overcome by modifying
it with various transition metals, like platinum, CuSO
4
); (iii) sulfate-promoted metal oxides
(S-ZrO
2
), (iv) metal-promoted superacids and (v) nickel, etc., of which platinum-promoted S-ZrO
2
has been widely studied for alkane polymeric superacid, Naon H. There are several
liquid superacids, for which typically the Hammett transformations.
acidity function H
o
11.99, corresponding to
100% sulfuric acid [2] (see Fig. 1). The S-ZrO
2
behaves as a solid superacid, depending on its 2. Preparation of S-ZrO
2
method of preparation and activation ( Table 1).
A considerable amount of debate is centered on The catalytic properties of S-ZrO
2
signicantly
depend upon the preparation method and the the application of the term Superacid to the
S-ZrO
2
catalysts. Umansky et al. [ 7] have sug- activating treatment. A variety of methods have
been reported for the preparation of S-ZrO
2
. These gested that S-ZrO
2
does not fall in the family of
superacids since its acidity is not stronger than methods dier mainly in the type of precursor,
type of precipitating agent, type of sulfating agent, that of 100% H
2
SO
4
. S-ZrO
2
, however, is known
to catalyze reactions such as n-butane isomeriza- method of impregnation, calcination temperature,
etc. ( Table 1). Various methods have been used tion even at low temperatures [8,9]. The fact that
this isomerization requires highly acidic catalysts, for the characterization of these catalysts.
The method of preparation signicantly aects when coupled with the above observation, suggests
that S-ZrO
2
is superacidic. Keogh et al. [10] have the activity of S-ZrO
2
. Major factors that aect
the catalyst performance are pH of the solution observed that the activated S-ZrO
2
catalyst
appears to be able to adsorb sucient water to during solgel precipitation, solution concen-
tration, drying and calcination temperatures. eliminate the measurable catalytic activity even in
Table 2
surface area obtained by sulfating precrystallized
Properties of S-ZrO
2
obtained with dierent sulfur compounds
zirconia is somewhat lower than that obtained by
in the percolating solution and after heating for 3 h in nitrogen
sulfating amorphous hydrous zirconia [13].
at 893 K [12]
Moreover, catalysts obtained by sulfating the
Sulfur Sulfur concentration Surface area
amorphous hydrated ZrO
2
possess a signicantly
compound (wt%) (m2 g1)
higher activity than that obtained by sulfating the
microcrystalline samples [14]. Sohn and Kim [4]
H
2
SO
4
1.48 104.1
have studied the eect of using various sulfating
(NH
4
)
2
SO
4
0.81 95.3
(NH
4
)
2
S
2
O
3
0.45 45.4 agents, such as H
2
SO
4
, (NH
4
)
2
SO
4
, H
2
S, SO
2
and
(NH
4
)
2
S 0.16 45.6
CS
2
. The eects of dierent sulfating gents, and
their post-treatment with oxygen and hydrogen,
have been studied for 1-butene isomerization
( Table 3). These authors have observed that the The type of precursor for preparing S-ZrO
2
plays a vital role in the nal texture and, hence, superacidity obtained in these catalysts is indepen-
dent of the sulfur source used for the sulfation of in the performance of the catalyst. Various zirco-
nium compounds, such as Zr(NO
3
)
4
, ZrCl
4
, zirco- the metal oxide precursor. It has been also found
that, for sulfate concentrations above an average nium isopropoxide, zirconyl chloride, zirconium
oxychloride and sometimes zirconia itself, are used half monolayer, sulfation with H
2
SO
4
leads to
contents of sulfate that are appreciably lower than to prepare these catalysts. Various precipitating
agents, like aqueous ammonium hydroxide and the nominal concentration. On the other hand,
sulfation with ammonium sulfate produces high urea, have been reported [11]. The type of
hydrolyzing agent also has a signicant eect on nominal sulfate concentration. Parera [12] has
compared the surface sulfate concentration and the catalyst activity. Amorphous zirconium
hydroxide obtained by the alkaline hydrolysis of the surface area of the catalysts when the sulfation
is accomplished using sulfuric acid and ammonium the zirconia precursor is usually sulfated before it
is crystallized by thermal treatment. Although this sulfate. It is seen that higher sulfate concentrations
and surface area are obtained with sulfuric acid is the general way of preparing the catalyst, some-
times hydrous zirconia is rst crystallized by ther- than ammonium sulfate. The somewhat lower rate
constant obtained with the latter, for the isomeriza- mal treatment and then sulfated. The sulfating
species most commonly used are H
2
SO
4
and tion of 1-butene ( Table 3) is thus explainable on
the basis of surface area. This catalyst also shows (NH
4
)
2
SO
4
[4]. Some sulfur compounds, like
H
2
S and SO
2
, have also been used. The sulfated
species is then thermally crystallized, whereby it
Table 3
undergoes a phase transformation, the tetragonal
Catalytic activities for 1-butene isomerization [4]
phase being stabilized as a result of sulfate
Catalysta Rate constant k102 (s1 g1)
incorporation.
The eect of various sulfur compounds on the
ZrO
2
0
sulfur concentration and surface area is shown
ZrO
2
/SO2
4
(S) 2.48
ZrO
2
/SO2
4
(A) 2.41
in Table 2.
ZrO
2
/SO2
4
(S)H
2
b 0
ZrO
2
/SO
2
0
2.1. Eect of various preparation parameters
ZrO
2
/SO
2
O
2
c 2.38
ZrO
2
/H
2
S 0
2.1.1. Eect of precursor and sulfating agent
ZrO
2
/H
2
SO
2
c 2.35
ZrO
2
/CS
2
0
It has been found that the use of ammonia or
ZrO
2
/CS
2
O
2
c 2.32
urea for precipitation of hydrated zirconium diox-
ide signicantly aects the surface area of the nal
a Sulfating agent: (S), sulfuric acid; (A), ammonium sulfate.
catalyst [11]. Precipitation with ammonia yields
b Reduced with H
2
at 500C for 2 h.
c Oxidized with O
2
at 400C for 2 h. catalysts with higher surface areas. The specic
signicantly higher activity for the n-butane isom- on the Bronsted acidity of the catalyst. Their
results suggest an increase in the Bronsted acidity erization reaction at room temperature. Even typi-
cal solid acid catalysts, such as zeolites, show no with an increase in sulfate concentration up to a
certain maximum, after which the amount of activity at such low temperature. Zeng et al. [15]
have found that higher concentrations of the solu- Bronsted acidity remains constant. This trend has
also been reported by Nascimento et al. [18]. Thus, tions used for carrying out sulfation result in
higher tetragonal content of the catalyst. Higher sulfates present above this concentration are lost
during the thermal activation and represent the concentrations also increase the sulfur content of
the catalyst samples [16]. Most of the excess sulfate thermally more labile fraction.
is, however, lost during the thermal activation of
the catalyst. These sulfates thus represent the ther-
mally most labile forms of the grafted sulfates 2.1.2. Eect of activation temperature
Thermal treatment of the catalyst under vacuum [13]. With the use of high-resolution transmission
electron microscopy ( TEM) and X-ray diraction below 723 K aects only the surface hydration
degree, which in turn aects the covalency of the ( XRD) techniques, it has been found that the
nature of the surface sulfates grafted by any of surface sulfates, thus altering the Bronsted:Lewis
(B:L) site ratio [ 20]. This eect is depicted in the techniques on amorphous or precrystallized
zirconia is much the same. When monoclinic Table 4. Activation temperatures above 723 K
under vacuum start aecting the overall surface microcrystalline ZrO
2
is doped with sulfuric acid,
the rst doses of the acid selectively graft sulfate hydration degree as well as the concentration of
the surface sulfates [22,23]. At higher temper- groups on to the crystal defects [ 17]. The latter
doses react with the regular crystal faces of the atures, some of the sulfates decompose to form
SO
2
. A possible pathway for this decomposition crystallites. It has been found that the relative
amounts of the Lewis and Bronsted sites depend has been suggested by Chen et al [16] as:
largely on the surface concentration of the sulfates
and their nature [17,18]. At low sulfate loadings, 2Zr4++SO2
4
2Zr3++SO
2
+O
2
when only sulfates located in the crystallographi-
cally defective sites are present, there is a fair
Comelli et al. [ 24] have found that calcination amount of Lewis acidity formed, but no Bronsted
acidity is formed. Isolated sulfate species observed temperatures above 753 K lead to a reduction in
surface area. For instance, calcination at 663 K for higher sulfate loadings and the existence of
pyrosulfates on a few low index planes lead to the produces a surface area of 117 m2 g1, which
decreases to 104 m2 g1 at 893 K. Similar results formation of Bronsted acid sites. Morterra et al.
[19] have studied the eect of sulfate concentration have been reported by Chen et al. [16].
Table 4
Percentage of acid sites on the SO2
4
ZrO
2
catalysts that are of the Bronsted typea [ 21]
Treatment Bronsted acid sites (% of total )
temperature (C)
Pre- Post- 0 wt% SO2
4
1.17 wt% SO2
4
9.87 wt% SO2
4
13.6 wt% SO2
4
100 100 0 47 98 98 (97)c
100 400 0 49 93 95 (89)c
400 100 42 (45)b 63 68 (70)c
400 400 46 (52)b 80 83 (64)c
a All samples were calcined at 625C, exposed to air prior to the pretreatment in situ at 100 or 400C prior to pyridine adsorption.
b SO2
4
content of the precursor before 650C calcination.
c Numbers in parentheses are for Pt-containing material.
3. Nature of active sites
The various techniques used for the character-
ization of these catalysts to throw light on the
origin and nature of active sites activity, which
have been the subject of intense debate, are high-
lighted in Table 5. Technological advances to date
still seem to be inadequate for the complete charac-
terization of the complex nature of these solid
superacidic anion treated transition metal oxides.
As a result, the exact structure of the active sites,
as well as their nature (Lewis or Bronsted type),
is a subject of debate. Attempts have, however,
been made to unearth these features of the cata-
Fig. 2. Model proposed by Kumbhar et al. [6].
lysts. Kumbhar et al. [6] had speculated the struc-
ture of S-ZrO
2
as given in Fig. 2.
Chen et al. [ 16] have proposed a possible mech- area, increased sintering resistance and stability of
tetragonal phase and smaller crystallite size as a anism for the generation of the acid sites on the
surface of S-ZrO
2
. This mechanism suggests the result of presence of sulfate anions, support this
type of mechanism. The incorporation of the sul- formation of acid sites to be a two-step chemical
reaction between the supercial hydroxyl groups fate anions on the surface of ZrO
2
has been found
to probably increase the number and strength of and the sulfate anions being adsorbed. The rst
chemical reaction occurs during the impregnation the Lewis acid sites [2,12,22,27,28]. Yamaguchi [2]
has proposed a possible scheme for the formation with sulfates and the subsequent drying:
of acid sites (Fig. 3). According to this hypothesis,
Zr(OH)
4n
+xH
2
SO
4
PZr
n
(OH)
4n2x
(SO
4
)
x whatever the starting materials used for sulfation
are, the oxidation during the thermal treatment +2xH
2
O.
results in the formation of the structure II. This
The second part of the formation occurs during
structure is essential for the catalysis of reactions
the calcination of the catalyst:
by such catalysts. It has further been suggested
that such a structure may develop at the edge or Zr
n
(OH)
4n2x
(SO
4
)
x
Zr
n
O
2nx
(SO
4
)
x
corner of the metal oxide surfaces. This latter view
+(2nx)H
2
O.
is supported by the fact that the rst doses during
a stepwise loading of the acid on microcrystalline Several observations, such as higher surface
Table 5
Techniques used for characterization of S-ZrO
2
Technique Information Ref.
Structural and textural characteristics
XRD Nature of phases [5]
BET Surface area
X-ray photoelectron spectroscopy ( XPS) Oxidation state [25]
Dierential thermal analysis Phase changes [5]
Fourier transform infra-red ( FTIR) spectroscopy Surface hydroxyl groups and structure of catalytic species [26]
Acidity measurements
Benesi method Strength of acid sites [25]
IR spectroscopy of adsorbed bases Nature of acidity [26]
Fig. 3. Model proposed by Yamaguchi [2].
ZrO
2
selectively form sulfate groups on crystal strong Lewis sites associated with these highly
covalent sulfates are catalytically active. These defects such as corners and edges [20].
For an S-ZrO
2
sample dehydrated to a medium covalent sulfates in structure II of the Yamaguchi
model ( Fig. 3) possess a strong ability to accept to high degree, Morterra et al. [23] have observed
the surface sulfates to exhibit a highly covalent electrons from a basic molecule and hence are
responsible for the generation of superacidic sites. character. It has further been observed that the
adsorption of basic molecules, like pyridine, on Even though this model for the structure of active
sites explains the above-mentioned observations, the central metal cation causes a large shift in the
IR band for SNO from 1370 to 1330 cm1 [27]. it does not provide a possible explanation for the
decomposition of the sulfate species as SO
2
or Similar results have been presented by Morterra
et al. [23]. These observations suggest that the SO
3
from structure II at high temperatures (above
923 K). In this context, Davis et al. [29] suggested highly covalent surface sulfates tend, under the
inuence of basic molecules, to exhibit a lesser that the changes in the structure and valence
occurring during the catalyst preparation and ther- covalent character. Further, the partial rehydra-
tion (water acting as a weak Lewis base) of the mal activation do not seem to conrm with the
chemical bonding. Hence, they have proposed a catalyst initially tends to convert the surface sul-
fates to a lesser covalent form and then into an dierent scheme that is able to explain the loss of
surface sulfates as SO
3
on heating above 923 K ionic form [23]. This results in the transformation
of the strong Lewis sites to Bronsted acid sites. ( Fig. 4).
The model in Fig. 4, however, is incapable of The subsequent decrease in the catalytic activity
towards n-butane isomerization suggests that the providing an explanation for the loss of sulfates
Fig. 4. Model proposed by Davis et al. [ 29].
as SO
2
, because this involves the reduction of formation of Bronsted sites (Fig. 6). This model
is based on the assumption that the predominant S6+ to S4+ with a corresponding oxidation of
some Zr or O species. species in sulfuric acid media is the bisulfate ion,
which can displace a ZrMOHMZr bridge during Another model has been proposed by Arata
and Hino [30] for the structure of the active site, chemisorption on the surface of hydrated
zirconia(I). On heating, either the bisulfate ion wherein the sulfate bridges across two zirconium
atoms (Fig. 5). can react with an adjacent hydroxyl group or two
adjacent hydroxyl groups can react with each The Arata and Hino model [ 30] takes into
account the formation of Bronsted sites as a result other, liberating water and keeping the bisulfate
ion intact. The former results in to the generation of the uptake of water molecules as a weak Lewis
base on the Lewis acid site, as has been evidenced of Lewis-type acidity, whereas the latter leads to
the formation of a Bronsted-type site. The by the IR studies. This model has also been
accepted by Davies et al. [31]. Cleareld et al. model [32] thus describes the one-
step formation of both types of acidic site. The models mentioned in the foregoing discus-
sion for the structure of the active sites describe This type of Bronsted acidity generation has
also been proposed by Kustov et al. [33], who the formation of Lewis-type sites due to the highly
covalent character of the adsorbed sulfates and have postulated that the sulfate treatment of
hydrous zirconia results in the elimination of the the formation of Bronsted sites as a result of the
interaction of water molecules with these sulfates.
In fact, Morterra et al. [17] have, for low sulfate
loadings, claimed the presence of Lewis sites to be
predominant, depending on the degree of dehydra-
tion. Their study reveals the presence of a very
low number, though never null, of Bronsted sites
at high dehydration of the catalyst. Nevertheless,
it seems that the formation of these Bronsted sites
is due to the residual amounts of water.
Contrary to the above models, Cleareld et al.
[32] have proposed a model that allows for the
Fig. 6. Model proposed by Cleareld et al. [32]. Fig. 5. Model proposed by Arata and Hino [30].
silanol groups of silica gel, but weaker than the
bridging OH groups in HX zeolites.
Babou et al. [ 35] have postulated a dierent
structure for the active sites at the surface of
S-ZrO
2
(Fig. 8). They have proposed that the
interaction of the zirconia support with sulfuric
acid solution results in the trapping of the protons
by the zirconium hydroxide surface. Sulfate ions
then get trapped on this ionized surface.
Dehydration at temperatures below 473 K results
in the loss of a rst water molecule, leading to the
formation of the structure II. Further dehydration
at higher temperatures liberates a second water
molecule with the formation of (SO
3
)
ads
linked by
dative bonds to the support. Such a model is based
on quantum chemical calculations and describes
Fig. 7. Model proposed by Kustov et al. [ 33].
the acidity to be near that of sulfuric acid but not
to be superacidic. Similar arguments based on
P-NMR studies have been put forward by Adeeva
terminal ZrOH species [34] due to their substitu-
et al. [36] ( Fig. 9), who have proposed that the
tion by bisulfate anions and enhances the acid
acid strength of the Bronsted sites in S-ZrO
2
is
strength of the bridging ZrOH groups ( Fig. 7).
similar to that of the lower OH-frequency protons
They have proposed schemes for both an ionic
in HY, but is weaker than that of the protons in
structure with a proton forming a multicenter
HZSM-5.
bond with the SO2
4
anion and a covalent structure
It has also been speculated that the extraordi-
with hydrogen-bonded hydroxyl groups.
nary activity of these catalysts is not due to its
With this model Kustov et al. [33] have
superacidity, but it results from the stabilization
explained the modication of Lewis acid sites by
of the transition state complex as alkyl sulfates or
HSO
4
anions. The Lewis acidity enhancement was
surface alkoxy groups at the catalytic site. The
attributed to the increase of the electron-accepting
H MAS NMR shifts for S-ZrO
2
and HY zeolite
properties of three-coordinate zirconium cations
are given in Table 6. From spectroscopic studies,
via the inductive eect of SO2
4
anions, which
formation of such species has indeed been found withdraw electron density from the zirconium cat-
in the case of zeolite catalysts wherein the oxygen ions through the bridging oxygen atom.
from the zeolite framework is involved in the Furthermore, with the IR study of benzene adsorp-
stabilization of the chemisorption complex [37]. tion, they have reported that the strength of the
Bronsted sites of S-ZrO
2
is stronger than the Pinna et al. [38], and Morterra and co-workers
Table 6
1H MAS NMR shifts, d
H
(ppm), of S-ZrO
2
and zeolites and their shifts, Dd
H
, upon adsorption of bases [36]
Sample d
H
before ads. d
H
after CCl
3
CN ads. Dd
H
(CCl
3
CN) d
H
after CD
3
CN ads. Dd
H
(CD
3
CN)
ZrO
2
4.5 8.5 4
ZrO
2
/SO
4
6.2 8.5 2.3 10 3.8
HY 4.7 7.7 3 9 4.3
4.1 8.5 4.4 11 6.9
HZSM-5 4.1 9 4.9 11 6.9
HZSM-5 4.3 11.5 7.2
Fig. 8. Model proposed by Babou et al. [35].
[17,20,23] have proposed that the sulfates responsi- the crystallographically defective sites such as
edges and corners. Increasing surface sulfation ble for the Bronsted acidity of these catalysts
results in the shielding of the surface Zr4+ cations represent the most labile fraction of the overall
located on the low index planes. Most of these sulfates and no Bronsted acidity is irreversibly lost
sulfates have been proposed to induce Bronsted
for thermal activation temperatures above 923 K.
acidity, this eect being more pronounced if the
Lewis acidity is shown by the sulfates located in
sulfates are in the form of polynuclear pyrosulfates
resulting from high loadings of sulfates [20].
Yamaguchi and co-workers [27,39] have reported
the existence of only the Lewis type of acidity on
the surface of S-ZrO
2
catalysts. Microcalorimetric
studies of ammonia adsorption on the catalyst by
Fogash et al. [8] have revealed the presence of a
spectrum of acid sites with dierent acid strengths.
Fig. 9. Model proposed by Adeeva et al. [36]. Their study also reveals that the initial doses of
ammonia are coordinately bound to the support. strength than those on the parent S-ZrO
2
[ 44]. On
For higher amounts of ammonia dosed, IR the contrary, Adeeva et al. [36] have proposed
spectroscopy shows the presence of NH+
4
ions that the rate enhancement is not caused by an
adsorbed on the surface which points to the exis- increase in acid strength but rather by an increased
tence of Bronsted acidity in association with the
production of alkenes which may participate in
Lewis type acid sites. Lunsford and co-workers
the reaction. This mechanism, proposed by
[40] used P-NMR spectroscopy to probe the nature
Guisnet [45] involves the formation of intermedi-
of the sites and have provided evidence for the
ate C
8
carbenium ions by oligomerization of C
4
existence of both types of acidities. Similarly Arata
carbenium ions and butenes. Subsequently, the
and co-workers [3,41], Sohn and Kim [ 4], Guo
C
8
carbenium ion would undergo skeletal
et al. [14], and Cleareld et al. [32] have supported
rearrangement, and nally a b-scission would pro-
the view that both the Lewis and Bronsted types
duce an isobutane molecule and regenerate the
of acidity are present on the surface of S-ZrO
2
.
active C
4
carbenium ion. The high dehydrogena-
Babou et al. [35] have found from IR studies of
tion activity normally exhibited by transition
adsorbed bases, such as butane, CO, H
2
O and
metals would be responsible for the enhanced
pyridine, that two types of Lewis site and one type
isomerization activity of these catalysts.
of Bronsted site exist at the surface of sulfate-
Modication of S-ZrO
2
with Fe and Mn increases
modied zirconia. Of these active sites, one Lewis-
the reaction selectivity for isomerization by mini-
type site is associated with the zirconia support
mizing the disproportionation reactions [43,46].
and the rest exist due to the presence of surface
The presence of Mn in conjunction with Fe does
sulfates.
not modify the catalytic activity by itself, but it
The foregoing discussion is indicative of the
functions to increase the dispersion of Fe [ 47]. Ni
nature of acidic sites on the surface of S-ZrO
2
,
has also been used to modify S-ZrO
2
. Karles and
depending on the types of precursor and pretreat-
Ekerdt [48] have claimed that their Ni-modied
ment. S-ZrO
2
can be prepared with superacidity,
catalyst shows better activity than NiOSiO
2
which will be useful in certain types of reaction.

Al
2
O
3
for the liquid-phase dimerization of C
3
C
4
olens. Better dispersion of Ni has been proposed
to result in the higher activity of NiS-ZrO
2
. This
4. Modied S-ZrO
2 catalyst also shows increased resistance to deacti-
vation compared with Fe- and Mn-promoted
Although S-ZrO
2
is known to possess the high-
S-ZrO
2
. However, this nding is contradicted by
est acidity amongst all known solid superacids, a
the work of Gao et al. [49] who reported that
considerable amount of research is centered on
supporting Ni on S-ZrO
2
has a detrimental eect
further improvement of catalytic activity and sta-
on the catalyst. For the increased activity of the
bility towards deactivation. Corma et al. [42] have
Fe- and Mn-supported S-ZrO
2
catalysts, the
reported that S-ZrO
2
is more active than zeolites
authors have postulated an alternative hypothesis
for isomerization and alkylation reactions at low
related closely to that of Adeeva et al. [ 36]. It has
temperatures. However, it possesses lesser resis-
been suggested that the presence of transition
tance to deactivation than zeolites. In this context,
metals may attract olen molecules which form a
S-ZrO
2
catalysts modied with various transition
butene pool that enhances the local concentration
metals such as Pt, Pd, Ir, Fe, Mn, etc. have been
of the olens near the acid sites. Under such a
found to exhibit better catalytic activity. Amongst
condition, the rate-limiting oligomerization step
these modifying agents, Pt, Fe and Mn tend to
would be greatly accelerated by the higher surface
exhibit better activity.
concentration of the olens. These catalysts, how-
Hsu et al. [43] observed that the activity of
ever, suer from rapid deactivation [50]. Other
S-ZrO
2
for isomerization of n-butane could be
compounds used for modication of S-ZrO
2
are greatly enhanced by the addition of Fe and Mn.
NiO [5153], WO
3
[54,55], SbF
5
[56] and hetero- They postulated that this enhancement was due to
the generation of additional sites with higher acid poly acids [5761].
4.1. Eects of Pt modication CO was not adsorbed and neither hydrogenation
nor hydrolysis occurred. Temperature-pro-
grammed reduction ( TPR), XPS and EXAFS indi- It has been found that the Pt-promoted
S-ZrO
2
shows higher rates for alkane isomerization cated that the Pt on an S-ZrO
2
surface was mostly
in the cationic state, only a small fraction being than Pt-containing unpromoted zirconia and even
zeolitic and mesoporous aluminosilicates. metallic. A similar state of supported Pt was
observed by Ebitani et al. [71] with the use of Furthermore, the incorporation of Pt on the sur-
face and the presence of S-ZrO
2
has been found XANES/EXAFS and TPR for characterization.
Their TEM studies have further revealed that the to increase the stability of the catalyst towards
deactivation during the isomerization of alkanes. presence of sulfate ion causes an increase of Pt
particle size. The presence of the surface sulfates Higher conversions accompanied by improved
selectivities have been claimed for Pt-modied has been found to suppress strongly the reducibility
of Pt particles, as well as the chemisorptive capac- S-ZrO
2
in alkane isomerization [62,63].
PtS-ZrO
2
catalyst in the presence of H
2
catalyzes ity for CO [72]. This eect has been attributed to
the redox metalsupport interaction that is caused the isomerization and cracking of alkanes. The
carbenium ions formed in this reaction can subse- by the acidic properties of the S-ZrO
2
support.
These authors have also observed from XPS quently alkylate aromatic and naphthenic com-
pounds [64,65]. Another role that has been studies that the partial conversion of the S6 to
S2 species is a result of hydrogen spillover on suggested for the supported Pt is the cleansing of
sites by the hydrogenation of the coke that causes the catalyst.
Gao et al. [49] have reported that, in an deactivation [66].
Cui et al. [67] have studied the eect of support- hydrogen atmosphere, the activity of S-ZrO
2
is
signicantly decreased. Supporting Pt on to these ing Pt on the morphology and active sites of
S-ZrO
2
by FTIR, XPS, XRD and acidity measure- catalysts increases their activity and selectivity
towards isomerization. From IR studies they have ment. They found that the addition of Pt and its
addition method did not aect the catalytic prop- concluded that the sulfates on the surface of
ZrO
2
may be partially reduced by H
2
, resulting in erty, the crystal forms, and the structure and
strength of the superacidic sites. During calcination a decrease in the superacidic sites. Pt loading
inhibits this reduction of surface sulfates and thus in air, Sayari and Dicko [68] have proposed that
the SO
2
evolved as result of decomposition of the activity of the catalyst is retained. A similar
result has also been reported by Cui et al. [67]. surface sulfates reduces Pt. On the other hand, Pt
supported on zirconia is not promoted by sulfates Gao et al. [49] have also suggested the formation
of new strong Lewis and Bronsted sites with the and remains in the oxidized state.
Tanaka et al. [69] have characterized Pt addition of Pt in the presence of H
2
. Similar
ndings were previously reported by Sohn and S-ZrO
2
to investigate the state of Pt in the catalyst.
Their X-ray absorption near edge structure Jang [73]. In fact, Hao et al. [ 62] have used the
term ultra strong acid system to describe their ( XANES) studies show that Pt is electron decient
after activation by hydrogen treatment and the catalyst modied by Pt, Pd or a mixture of these
noble metals. The results of Yori et al. [74] on the extended X-ray absorption ne structure
( EXAFS) studies indicate the presence of PtMO addition of Pt as a promoter to S-ZrO
2
are shown
in Table 7 for the isomerization of n-butane and PtMPt pairs as in PtO
2
and Pt metal respec-
tively. They have explained the contradictory result wherein the cracking products are suppressed in
presence of Pt. showing Pt metallic (by XRD) and Pt in an
oxidized state by ( XPS) by postulating that an
oxidized Pt particle with a metallic Pt core is 4.2. Eect of carbon coating
present in the activated catalyst. Hattori [70] has
found that the state of Pt supported on S-ZrO
2
Foley [75] had prepared shape-selective catalyst
by combining metal oxide with carbon molecular was dierent from the usual supported Pt catalysts;
Table 7
Conversion of n-butane and product selectivities at 5 min time-on-streama [ 74]
Catalyst WHSV H
2
/n-C
4
Conv. S
C
1
S
C
2
S
C
3
S
i-C
4
S
C
5
Pt/SO2
4
ZrO
2
4 0 39.6 0.25 1.26 13.13 76.01 9.34
Pt/SO2
4
ZrO
2
4 2 29.3 1.02 8.87 82.6 7.5
Pt/SO2
4
ZrO
2
4 4 17.4 1.15 5.74 87.35 5.75
Pt/SO2
4
ZrO
2
4 6 6.0 1.66 5 95
Pt/Al
2
O
3
0.36 6 3.0 3.33 20 13.33 53.3 10
Pt/Al
2
O
3
+SO2
4
ZrO
2
(Catalyst G-1) 0.36 6 39.8 0.75 4.27 13.82 73.6 7.28
a S is the selectivity for C
i
hydrocarbon.
WHSV=weight hourly space velocity (h1).
sieve (CMS). In this method the metal oxide was in dierent weight ratios. These mixtures are then
calcined in a furnace at the desired temperature in immersed or dispersed in the desired polymer and
the excess polymer drained o. The metal oxide an inert atmosphere to obtain the catalyst.
These kinds of material have been prepared by with the adsorbed polymer was then calcined in a
furnace under inert atmosphere. These steps were Foley [75] and are conceptualized as a dispersion
of very ne inorganic oxide particles, distributed repeated until a sucient amount of carbon had
been added to produce the desired molecular siev- through the carbon matrix (Fig. 11). This is in
contrast to the idealized form of the material ing properties.
These types of material ideally comprise of a prepared as per method I in which the inorganic
oxide particle is large and in eect supports the particle of inorganic oxide surrounded by a shell-
coating of the CMS. In this way the inner non- CMS.
Similarly, recently Yadav and co-workers sieving particle is surrounded by a molecular siev-
ing gate of carbon (Fig. 10). Molecular communi- [ 76,77] have shown that S-ZrO
2
can also be modi-
ed and can be made a more shape-selective cata- cation to the inorganic oxide is regulated by the
pore restrictions of the carbon; however, once lyst by coating it with dierent polymers in this
case polyvinyl alcohol followed by carboniza- through the gate the reactants experience the same
catalytic environment present in the untreated tion at dierent temperatures. The carbonization
step helps to create a barrier of CMS for bulkier inorganic oxide.
In another method the metal oxide precursor, molecules, having a well dened pore size distribu-
such as a metal alkoxide, is mixed with the polymer
Fig. 11. Schematic of type II structure [ 75]. Fig. 10. Schematic of type I structure [75].
tion. The catalyst, thus obtained, confers with the tion proceeds via chain transfer pathways on
Pt-modied S-ZrO
2
, in which carbenium ions structure shown in Fig. 10.
propagate after a chain initiation step involving
loss of hydrogen from the alkane, by hydride 4.3. Mechanism for acidity generation
transfer from neutral species to carbocations.
Adamantane increases hydride transfer and carbe- Hattori [70] has proposed a possible mechanism
of protonic acid site generation on Pt-modied nium ion termination rates, thus reducing the
surface residence time required for a catalyst turn- S-ZrO
2
in the presence of H
2
. An IR study of
adsorbed pyridine has revealed that protonic acid over. This results in desorption of the isomerized
carbenium ions before they undergo secondary sites are generated on the catalyst surface in com-
pensation for elimination of Lewis acid sites when cracking. This type of chemistry is bifunctional in
that it requires both the presence of acid sites and exposed to H
2
. He has proposed a dissociative
adsorption of H
2
on the Pt particles to form H platinum metal. When compared with conven-
tional bifunctional catalysis, however, it diers in atoms, which subsequently undergo spillover on
to the support (Fig. 12). The H atom migrates on that it does not form or require gas-phase alkene
intermediates. the surface of S-ZrO
2
to Lewis acid sites where it
loses an electron to form a proton stabilized on
the surface O atoms near the Lewis acid site. 4.4. Eect of water of hydration
Similar results have been forwarded by Ebitani
and co-workers [7881]. The eect of water of hydration in acid catalysis
has long been known to catalytic scientists. With Another eect observed with the presence of
H
2
is the improvement of the selectivity towards the use of conventional acid catalysts, like anhy-
drous AlCl
3
, water has many times been found to isomerization. This eect has been attributed to
the dissociative formation of hydridic and protonic increase the rate of reactions like dehydration,
etherication, isomerization, cracking, etc. hydrogen species at the metal crystallite [82]. The
mechanism proposed for this phenomenon is sim- Although the role of water with these conventional
catalysts is clearly known, its eect on S-ZrO
2
is ilar to that described below for the increase in
selectivity in the presence of adamantane. controversial. Some authors have reported an
enhancement in the activity of these catalysts in Iglesia et al. [82] have studied the eect of
hydride donor species during the isomerization of the presence of minute amounts of water adsorbed
on their surface [83]. On the other hand, some of alkanes. The presence of hydride transfer species,
like adamantane, greatly increases the isomeriza- the researchers have found water, even at very low
concentrations, to be detrimental for the catalytic tion rates and selectivity to branched isomers even
with higher alkanes. Their results depict that the activity [10,84]. There are still other reports that
describe no eect of small amounts of water on isomerization of heptane shows positive orders
with respect to hydrogen, suggesting that the reac- the catalytic activity [12]. The eect of water on
the catalytic activity for hexadecane conversion is
shown in Table 8.
The nature of adsorbed water has been investi-
gated by Keogh et al. [10], and Morterra et al.
[ 20]. These authors have employed a combined
thermal gravimetric analysis/dierential scanning
calorimetry/mass spectroscopy technique for the
characterization of the catalysts and proposed that
water adsorbed on the catalyst converts some of
the strong Lewis acid sites into Bronsted sites. It
has further been proposed that these sites formed
Fig. 12. Mechanism of hydrogen spillover [70]. are not the catalytically active ones. Morterra et al.
Table 8
The eect of moisture-free atmospheres on activity on n-hexadecane isomerization [10]
Atmosphere Exposure time (h) Catalyst weight gain (wt%) n-Hexadecane conversion (wt%)
100% H
2
SO
4
22 0.160.9 0.530.04
Desiccator 22 0.080.9 0.520.1
Vacuum oven (21C) 22 1.78 0.5
Normal experimental procedure 76.25
[23] have studied the eect of partial rehydration rium with adsorbed water. The scheme proposed
by them is as follows: on the catalytic activity of S-ZrO
2
. According to
them, the sulfates detected on the surface of
(SO
3
)
ads
+(H
2
O)
ads
P(H
2
SO
4
)
ads S-ZrO
2
exhibit a strongly covalent character at
medium to high degrees of dehydration. Partial ( H
2
SO
4
)
ads
+(H
2
O)
ads
P(H
3
O+)
ads
+(HSO
4
)
ads
rehydration, however, tends initially to impart a
( HSO
4
)
ads
+(H
2
O)
ads
P( H
3
O+)
ads
+(SO2
4
)
ads less covalent character to the surface sulfates.
Higher doses of water convert these sulfates to the
The superacidity generated on the surface of ionic form. Thus, water dosing results in the
transformation of Bronsted sites, not catalytically S-ZrO
2
has been a matter of debate. Small amounts
of water tend to balance the Bronsted and Lewis active, at the expense of the strongest Lewis cen-
ters. Thus, this explains the loss of activity on the acid sites in specic reactions, leading to much
higher activities. rehydration of these catalysts. The initial activity
can be recovered by repeating the activation step.
This reversible transformation of Lewis and 4.5. Eect of calcination temperature
Bronsted sites, on adsorption and desorption of
water, has also been reported by Zecchina et al. The catalytic activity of S-ZrO
2
is found to
depend on the calcination temperature as well as [85].
It has been conrmed from IR spectra of the pre-calcination temperature of ZrO
2
. Table 9
suggests that the superacidic S-ZrO
2
is produced adsorbed pyridine that the sulfates adsorbed on
(some of the) regular top terminations of the when the pre-calcination temperature is between
110 and 400C and the calcination temperature ZrO
2
crystallites, when hydrated, are responsible
for protonic Bronsted acidity [17]. It has further upon sulfation with sulfuric acid is 650C. Pre-
calcination temperatures beyond 400C, lead to a been put forward that the polynuclear sulfates are
more active in yielding protonic acidity. Iglesia
et al. [82] have proposed that the presence of small
Table 9
Eect of calcination temperature before and after sulfation on
amounts of water in the hydrocarbon feed can
acid strength [14]
lead to the formation of surface hydroxyl groups
with highly polarized OMH bonds. These sites can
Pre-calcination Calcination temp. Acid strength H
o
function as the strong Bronsted site for the reac-
temp. of ZrO
2
(C) of S-ZrO
2
(C)
tion. Thus, the ndings of these authors contradict
200 650 16.12
each other in describing the catalytic activity of
400 650 16.12
the Bronsted acid site formed as a result of the
500 650 13.75
adsorption of water.
600 650 12.70
With the use of IR spectroscopy, Babou et al.
800 650 >12.70
110 200 >12.70
[35] have pointed out that there is a reversible
110 400 12.70
eect of water on the sulfate species on the surface
110 650 16.12
of S-ZrO
2
. They have detected four sulfate species
110 800 12.70
on the surface, which are assumed to be in equilib-
Table 10
Physico-chemical characteristics of S-ZrO
2
catalysts and conversions in n-butane isomerization at 150C, WHSV=2 h1 [ 18]
Temp. (C) H
2
SO
4
concentration (N) Sulfur contents (wt%) Surface area (m2 g1) k (mol h1 m2106)
500 1.0 5.36 147 n.d.
0.1 1.14 117 0.45
0.2 1.95 128 40
550 0.3 2.41 126 44
0.5 3.90 156 15.5
1.0 5.70 136 3.8
0.1 1.09 95 0.8
600 0.2 1.55 114 7
0.3 1.99 115 46.5
0.5 2.95 133 33
0.2 1.22 83 10
650 0.3 1.17 93 20.3
0.5 1.33 116 43.5
1.0 1.50 112 36.5
700 1.0 1.14 90 26.5
reduction in superacidity. In fact, the test reaction
of isomerization of n-butane to isobutane [18] has
shown that there is a combination of calcination
temperature and concentration of sulfuric acid to
give a better catalyst; for example, 600C and
0.3 N H
2
SO
4
or 650C and 0.5 N H
2
SO
4
, produce
almost identical activities ( Table 10).
4.6. Modication of zirconia with other mineral
acids
Zirconia can be modied with other mineral
acids to obtain various acid-treated zirconia to
verify if superacidity could be incorporated into
it. Yadav and co-workers [6] had extensively
studied the inuence of treatment of zirconia with
sulfuric acid to give S-ZrO
2
, phosphoric acid to
give phosphated zirconia (P-ZrO
2
) and boric acid
to give borated zirconia (B-ZrO
2
). The results
showed that the addition of sulfate, borate and
phosphate ions signicantly altered the properties.
The XRD results (Fig. 13 and Table 11) show that
there is a phase dierence between pure and acid-
treated zirconia and also a change in the
particle/crystallite size. Pure zirconia transforms
Fig. 13. XRD patterns for (1) ZrO
2
, (2) S-ZrO
2
, (3) P-ZrO
2
and (4) B-ZrO
2
. into a monoclinic phase from a tetragonal phase
Table 11
exhibit peaks in the region of 1200 cm1, where
Crystallographic phases in various ZrO
2
[6]
pure ZrO
2
does not show any bands. For S-ZrO
2
the spectrum shows a broad peak having shoulder
Catalyst Nature of phasesa Crystallite size (A
)
peaks at 1218, 1152, 1066 and 1058 cm1, which
Pure ZrO
2
Mb 204.8
are typical of a chelating bidentate sulfate ion
S-ZrO
2
T 164.67
coordinated to metal cation. This structure is
P-ZrO
2
M+T 137.2
stronger than that of the usual metal sulfates and,
B-ZrO
2
M+T 136.5
owing to an inductive eect of sulfuroxygen
a M: monoclinic; T: tetragonal.
bonds, there is an increase in the Lewis acidity of
b A small amount of tetragonal phase is also present.
the Zr4+ metal cation. Also, it is quite probable
that the hydroxyl groups formed on the surface
above a calcination temperature of 600C.
act as Bronsted acid sites. Further evacuation of
However, due to doping of SO2
4
ions this trans-
the catalyst at 300C leads to the removal of OH
formation is prevented in the case of S-ZrO
2
. The
group and only Lewis sites are present. The authors
PO3
4
and BO3
3
ions were found to be less eective
have proposed a mechanism for the generation of
in introducing this type of eect in the P-ZrO
2
acidity on the basis of FTIR studies (Fig. 15).
and B-ZrO
2
. The FTIR spectra of pure ZrO
2
,
For P-ZrO
2
and B-ZrO
2
, the IR spectra show a
S-ZrO
2
, P-ZrO
2
and B-ZrO
2
are shown in Fig. 14
broad band with peak maxima at 1056.8 and
respectively. The spectra of acid-treated zirconia
1072 cm1 and characteristic phosphorusoxygen
and boronoxygen stretching modes in the phos-
phate and borate anions respectively. But it is not
possible to determine the exact structure of active
species from this data. However, by analogy with
the earlier structure determined for S-ZrO
2
, the
formation of similar structures for P-ZrO
2
and
B-ZrO
2
, is expected (Fig. 15). A similar structure
has been proposed for phosphate-modied TiO
2
by Davydov et al. [86].
Pore size distribution plots of the acid-treated
catalysts are shown in Fig. 16. The results of
surface area and pore size distribution are summa-
rized in Table 12. For pure ZrO
2
it was observed
by Tanabe et al. [87] that the BET surface area
decreases rapidly from 175.5 to 21.4 m2 g1 as the
calcination temperature increases from 300 to
700C. From Table 12 it can be seen that the
surface area of S-ZrO
2
is very much greater than
that of pure ZrO
2
at the same calcination temper-
Fig. 14. FTIR Spectra of (1) ZrO
2
, (2) S-ZrO
2
, (3) P-ZrO
2
and
Fig. 15. Model proposed by Yadav and co-workers [6]. (4) B-ZrO
2
.
Fig. 16. Pore size distribution plots of ZrO
2
(6), S-ZrO
2
(%),
P-ZrO
2
(#), B-ZrO
2
($).
ature, which means that the doping of sulfate ions
has suppressed the decrease in the surface area
with respect to calcination temperature. Phosphate
and borate ion modied ZrO
2
and pure ZrO
2
show
Fig. 17. NH
3
TPD proles for ZrO
2
( ), S-ZrO
2
( ),
negligible dierences in the surface area. Fig. 16 P-ZrO
2
( ) and B-ZrO
2
().
shows that the peak of the pore size distribution
curve is shifted towards a smaller value of pore
and strong acid sites. For S-ZrO
2
the spectrum
diameter for acid-treated zirconia, which indicates
reveals that there is generation of intermediate
that there is an increase in the microporosity. For
(160C) and very strong acid sites (415C), in
P-ZrO
2
, and B-ZrO
2
the pore size distribution
addition to strong acid sites (210C), but it does
curves are almost identical. There is an increase
not have weak acid sites. For P-ZrO
2
there is
in the pore volume in the order S-Zr
generation of medium-strong acid sites, but loss
O
2
&P-ZrO
2
>B-ZrO
2
.
of strong acid sites. B-ZrO
2
exhibits the presence
Fig. 17 shows the ammonia temperature-pro-
of weak (100C) intermediate (198C) and strong
grammed desorption (TPD) proles of pure
acid sites (270C). Yori et al. [88] have reported
ZrO
2
, S-ZrO
2
, P-ZrO
2
and B-ZrO
2
. The most
that a linear correlation exists between acid
striking feature of Fig. 17 is the large increase in
strength H
o
determined by indicators and the
the intensity of peaks for acid-treated zirconia
reciprocal of the ammonia desorption temperature
compared with pure zirconia. Pure ZrO
2
exhibits
for alumina and silica-alumina. A similar relation-
two maxima (77 and 230C) representing weak
ship is expected to hold for pure ZrO
2
and acid-
treated ZrO
2
. It is already known that S-ZrO
2
Table 12
possesses superacidic sites having H
o
<16. The
Surface area and pore size distribution studies of various acid-
treated ZrO
2
(by mercury porosimetry) [6]
very strong acid sites observed in the TPD of
S-ZrO
2
probably represent superacidic sites.
Catalyst Surface area Total intrusion
However, neither P-ZrO
2
nor B-ZrO
2
posses
(m2 g1) volume (ml g1)
superacidic sites.
Pure ZrO
2
16.2 0.5256
The results in Table 13 show that the increase
S-ZrO
2
91.14 0.9298
in the acidity of S-ZrO
2
is larger than the other
P-ZrO
2
21.08 0.7904
two, which have almost identical acidities. The
B-ZrO
2
25.82 0.6933
order of the acidities is S-ZrO
2
&B-ZrO
2
~
Table 13
Acidity distribution of various zirconias determined by NH
3
TPD [6]
Catalyst Acidity (mmol g1)
weak (<100C) intermediate (100200C) strong (200400C) very strong (>400C) total
Pure ZrO
2
0.0735 0.608 0.1343
S-ZrO
2
0.2858 0.2529 0.0653 0.6040
P-ZrO
2
0.1290 0.1493 0.2783
B-ZrO
2
0.1482 0.0822 0.0784 0.3030
P-ZrO
2
>pure ZrO
2
. This result is quite similar to rizes the results of these studies. The main product
of the reaction is diphenylmethane (DPM). There that obtained in the case of sulfate-modied, phos-
phate-modied and pure alumina [89]. is formation of polymeric by-products. The initial
rates and conversion of benzyl chloride (after 4 h
of reaction) for S-ZrO
2
are very much higher than
those of P-ZrO
2
, B-ZrO
2
and ZrO
2
. The order of 5. Applications of S-ZrO
2
catalysts
the activity is S-ZrO
2
&B-ZrO
2
~P-ZrO
2
>
pure ZrO
2
. S-ZrO
2
shows high selectivity for DPM Many industrially important reactions have
been studied over S-ZrO
2
because of its strong or at a conversion of 27.6%. For acid-catalyzed reac-
tions, it is generally observed that the activity is superacidic character. Some of these reactions are
FriedelCrafts alkylation, acylation, condensation, proportional to the number of acid sites available
for the reactants. For the present reaction the esterication, etherication, isomerization, nitra-
tion, cracking, dehydration, oligomerization, etc. activity, dened as the initial rate of reaction
(gram-moles per second per gram), was found to The application of S-ZrO
2
catalyst to these reac-
tions is not only industrially important, but also vary linearly with the total acidity, as is evident
from Table 14. The structural model of S-ZrO
2
there is an academic merit because very little is
known about the exact functioning of these cata- pertaining to this reaction, proposed by Kumbhar
et al. [6], is shown in Fig. 2. lysts. Comparison is also provided with other acid
catalysts.
5.1.2. Inversion in rates and selectivities in
benzylations 5.1. Alkylations
Benzylation could also be performed with
benzyl alcohol and benzyl chloride [90]. The appli- Alkylation forms an important class of reactions
in the chemical industry. A variety of acid catalysts cation of solid acid catalysts to alkylations with
and alkylating species, usually alcohols, alkyl chlo-
rides, ethers and olens, are used to aect these
Table 14
reactions. Olens are the most common alkylating
Catalytic properties of the modied zirconia in benzylation of
agents used to obtain high octane number fuels.
benzene with benzyl chloride [6]
Catalyst Initial rate/activity Conversiona Selectivityb
5.1.1. Benzylation of substituted benzene
106(gmol s1 g1) (%) (%)
S-ZrO
2
is a good catalyst for a number of
alkylation reactions, for instance benzylation of
Pure ZrO
2
1.46 27.6 86.2
S-ZrO
2
3.24 99.53 97.47
benzene and toluene with benzyl chloride [6].
P-ZrO
2
2.09 34.86 94.6
The alkylation reaction of benzene with benzyl
B-ZrO
2
2.35 39.40 90.16
chloride was found to be a very good test reaction
to compare the eciency of sulfated, phosphated
a After 4 h of reaction.
b At a conversion of 27.6%. and borated zirconia catalysts. Table 14 summa-
Table 15
Reaction between toluene and benzyl chloride (BnCl )/benzyl alcohol (BnOH) and their mixtures over various catalysts [92]
Catalyst Temp. (C) Time (min) Conversion (%) Product distributiona (%)
BnCl BnOH BT BE
90 90 39.36 100
S-ZrO
2
90 90 21.76 39.07 60.93
90 90 0.0 55.44 52.84 47.16
80 90 52.00 100
Filtrol-24 80 90 19.26 51.56 48.43
80 90 0.0 100 84.76 15.23
80 90 36.90 100
DTP/SiO
2
80 90 12.30 50.13 49.86
80 90 0.0 36.48 63.20 36.79
100 60 68.92 100
S-ZrO
2
100 60 43.56 37.67 62.33
100 60 12.20 100 71.78 28.92
Filtrol-24 100 30 9.84 100 97.03 2.97
a BT: benzyl toluene; BE: benzyl ether; DTP: dodecatungstophosphoric acid.
alkyl alcohols and alkyl chlorides led to the discov- lone pair of electrons associated with the chlorine
in benzyl chloride then forms a polar complex ery of the phenomenon of inversion in reactivities
of the alkylating species [91,92]. It is found that with this species leading to the formation a super-
electrophile. This species then aects the alkylation when benzyl alcohol and benzyl chloride, as a
mixture, are used to alkylate toluene, reaction of of toluene at a much faster rate than that when
benzyl alcohol is present alone. benzyl alcohol with toluene proceeds at a much
faster rate in the presence of benzyl chloride than The eect of substituents in the alkylating
agents has also been studied with a view to obtain- when present alone as the alkylating species. This
enhancement comes at the expense of no reaction ing further insight into this phenomenon. Thus, a
substituent, preferably a halogen for its ortho of benzyl chloride, which, when present alone,
reacts at a much faster rate than benzyl alcohol para directing and deactivating eect, in the para
position of the benzene ring has been used. The ( Table 15).
Yadav and co-workers [90,92] have investigated results of this analysis also lead to the occurrence
of similar inversion phenomena in this case, thus the application of S-ZrO
2
catalyst to the Friedel
Crafts alkylation of toluene with benzyl chloride, supporting the above discussion.
benzyl alcohol and benzyl ether. From a series of
adsorption experiments, it is proved that benzyl 5.1.3. Alkylation of cresols with isobutylene and
methyl tertiary butyl ether (MTBE) alcohol, in the presence of benzyl chloride, is
preferentially adsorbed on to the catalyst site. On S-ZrO
2
has also been used as a catalyst for the
alkylation of cresols with MTBE ( Table 16) [60]. the basis of these ndings a mechanism has been
formulated to account for the inversion phenome- This is an interesting reaction because MTBE is a
cheap and readily available liquid, easy to trans- non observed in the single-pot alkylation of toluene
with benzyl chloride and benzyl alcohol. It is port. Yadav and Kirthivasan [60] have compared
the performance of S-ZrO
2
with other solid acid proposed that benzyl alcohol gets preferentially
adsorbed on the acid site of the catalyst and forms catalysts for the alkylation of p-cresol with MTBE
( Table 16). The results show lower activity and a benzyloxonium species. The interaction of the
Table 16 Table 18
Alkylation of hydroquinone with MTBEa [93] p-Cresol alkylation with MTBE [ 60]
Catalyst Hydroquinone Product distribution Catalyst Conversion (%) Selectivity (%)
conversion (%)
Indian-130 39 92
2-TBHQ 2,5-DTBHQ
Filtrol-24 19 96
S-ZrO
2
15 91
DTP 80 100
K-10 12 96
5% DTP/K-10 33 40 60
DTP/K-10 30 96
10% DTP/K-10 37 66 34
20% DTP/K-10 46 72 28
40% DTP/K-10 66 45 55
selectivity for alkylation. This could be attributed
K-10 29 100
20% ZnCl
2
/K-10 15 100
to higher rates of isobutylene oligomerization,
20% DTS/K-10 36 42 58
formed in situ, during the reaction.
S-ZrO
2
26 100
5.1.4. Alkylation of phenol and hydroquinone with
a Phenol:MTBE=1:3; temperature: 150C; catalyst loading:
20% w/w of hydroquinone; 1,4 dioxane: 30 ml; speed of agita- MTBE
tion: 800 rpm; reaction time: 4 h; DTP: dodecatungstophos-
Alkylation of phenol with olens gives very
phoric acid; DTS: dodecatungstosilicic acid.
important intermediates for applications in a vari-
ety of industries. The use of MTBE as an alkylating
agent has been made by Yadav and Doshi [93]
shows only 72% formation of 2-tert-butyl
over a variety of catalysts to produce tert-butylated
hydroquinone.
phenols ( TBPs) (Table 17) especially 4-tert-butyl
Both the alkylation reactions are Bronsted-acid-
phenol, which is widely used as an antioxidant in
catalyzed reactions, as is evident from the superior
industry. S-ZrO
2
is found to give the best yields
activity of 20%DTP/K-10, which is a Bronsted
of 4-tert-butyl phenol, though its activity is very
acid type of catalyst with Lewis acid sites. Hence,
low compared with 20%DTP/K-10.
S-ZrO
2
, which is a Lewis acid catalyst, was found
2-tert-Butyl hydroquinone is a very important
to be less active compared with 20%DTP/K-10.
derivative for its use in pharmaceuticals and in
developing photographic plates. Yadav and Doshi
5.1.5. Alkylation of o-xylene with styrene
[93] have also studied the alkylation of hydroqui-
The alkylation of aromatic hydrocarbons with
none with MTBE, where S-ZrO
2
gives 100% yield
styrene to give 1-phenyl-1-arylethane in the pres-
of 2-tert-butyl hydroquinone ( Table 18). However,
ence of Bronsted or Lewis acid catalysts is a well-
here again the activity of S-ZrO
2
was found to be
known process [94]. But the process is beset with
inferior to that of 20%DTP/K-10, but the latter
the problem of dissolution of the catalyst in the
reaction mixture and hence is not very economical.
Table 17
Also, there is another drawback of formation of
Alkylation of phenol with MTBEa [ 93]
styrene oligomers. Rajadhyaksha and Chaudhari
[ 95] have reported the use of S-ZrO
2
in the alkyla- Catalyst Phenol Product distribution
conversion (%)
tion of o-xylene with styrene to produce phenylxy-
2-TBP 4-TBP 2,6-DTBP
lylethane (PXE) with 65% conversion and 100%
selectivity. PXE is a vital ingredient of corrosion
DTP 95 2 7 91
protective coatings of chlorinated rubber and chlo-
K-10 52 33 39 28
rine-containing synthetic resins [96]. It has also
20% DTP/K-10 68 38 38 24
S-ZrO
2
30 40 48 12
found applications in high energy fuel for jets,
20% ZnCl
2
/K-10 30
turbojets, rockets, missile engines, and high sta-
bility lubricants [97]. The activity of S-ZrO
2
was
a Phenol:MTBE=1:2; temperature: 150C; catalyst loading:
found to be comparable to that of Naon-H and
20% w/w of phenol; 1,4 dioxane: 15 ml; pressure: 100 psi; speed
of agitation: 800 rpm; reaction time: 4 h. cation-exchange resin catalyst. Para-substituted
product was obtained selectively and no formation active and selective towards the formation of
2,2,4-trimethyl pentane. However, it was observed of styrene dimer could be detected and the result
demonstrated potential of S-ZrO
2
catalyst for that the catalyst deactivation was rapid, but the
catalyst could be regenerated easily by heating in industrial use, particularly in view of its lower cost
and high thermal stability. Yadav and Dixit [98] owing air. It was found that catalyst containing
a high amount of sulfur gives more cracked have compared the activity of S-ZrO
2
with ion-
exchange resins for the same reaction. products.
Oligomerization of butene and cracking of alkyl-
ate products have also been found to accompany 5.1.6. Manufacture of gasoline alkylates
Alkylation of alkanes with olens is an impor- this reaction [28,42,100]. The cracking of the alkyl-
ated products can be suppressed by lowering the tant industrial process for the manufacture of high
octane number gasoline from petroleum fractions. reaction temperature. Guo et al. [14] have specu-
lated the sites of low acid strength to be the active Catalysis of these reactions under mild conditions
demands a highly acidic nature of the acidic sites. site for the oligomerization of butene.
Guo et al. [14] have alkylated isobutane with
butene using S-ZrO
2
as catalyst. The catalyst prep- 5.1.7. Preparation of alkyl phenols
Phenols and substituted phenols have also been aration parameters have been found to inuence
greatly the reaction conversions, as well as the alkylated in a similar manner with olens to obtain
their alkyl-substituted derivatives. Alkyl phenols selectivity. The eect of calcination temperature is
shown in Table 9. The activity of the catalyst are very important commercially because of the
variety of their applications such as antioxidants, correlates well with the acid strength of the cata-
lyst, as is depicted in Fig. 18. Higher conversion perfumes and disinfectants. These alkylations are
comprise of series and parallel reactions leading and selectivity to trimethyl propane makes this
catalyst superior to zeolite catalysts. These cata- to a number of products, such as monoalkylated
and dialkylated aromatics, and oligomers of the lysts, however, show a rapid deactivation with
time on-stream. Fig. 18 shows the deactivation of alkene. Ion-exchange resin catalysts have widely
been tested for the alkylation of p-cresol with catalyst calcined at dierent temperatures.
Das and Chakrabarty [99] have studied the isobutylene [101103]. p-Cresol has been alkylated
with isobutylene at atmospheric pressure in the alkylation of isobutane with 1-butene over
S-ZrO
2
as catalyst. S-ZrO
2
was found to be highly presence of S-ZrO
2
as the catalyst [104] ( Fig. 19).
Yadav and Thorat [104] have investigated the
mechanism of this complex reaction. In a situation
like this, where both the reactants can be proton-
ated in the presence of solid acids and superacids,
it is proposed that the formation of carbenium ion
as a result of adsorption of isobutylene onto the
catalyst surface will dominate due to its higher
basicity, as is evident from the pK
a
values, as
compared with p-cresol. The oligomerization of
olens observed during this reaction also suggests
that adsorption of the olen on the catalyst surface
plays a dominant role in the reaction. The validity
of the LangmuirHinshelwood and the Eley
Rideal mechanisms has also been tested with the
experimental data. It is observed that the experi-
mental data are better tted for the EleyRideal
Fig. 18. Activity change of S-ZrO
2
calcined at dierent temper-
mechanism. The eect of various diusional resist-
atures as a function of time at calcination temperature: 650C
(#); 400C ($); 200C (6); 800C (&). ances has also been evaluated. In light of these
5.1.9. Trans-alkylation of di-isopropylbenzene
(DIPB)
Suresh et al. [106] have reported the use of
S-ZrO
2
in the trans-alkylation of DIPB with ben-
zene and substituted benzenes. The reaction with
benzene produces cumene, an intermediate in the
production of phenol [107]. The reactions were
carried out in a 100 ml Parr autoclave at 200C.
The results of the reaction of DIPB with other
substituted benzenes, like toluene, phenol and
benzonitrile, are given in Table 19. However, it
was found that S-ZrO
2
would deactivate because
of the heavy compounds in the starting reaction
mixture and coke formation.
5.1.10. Alkylation of aromatics with olens
The alkylation of benzene with decene and
dodecene is commercially important for precursors
for linear alkyl benzenes (LAB).
S-ZrO
2
catalyst has been evaluated in compari-
son with other catalysts by Yadav and Doshi [93]
( Table 20).
Other alkylations reported with S-ZrO
2
cata-
lysts are alkylation of aromatics with olens
[ 65,108], alkylation of ethyl benzene with styrene
[ 64], etc.
5.1.11. Alkylation of diphenyl oxide with 1-decene
Yadav and Kundu [109] have used S-ZrO
2
and
modied S-ZrO
2
for the alkylation of diphenyl
Fig. 19. Reaction scheme for alkylation of p-cresol with isobu-
tylene [104]. oxide (DPO) with 1-decene at 150C, under auto-
geneous pressure with a mole ratio of DPO to
olen of 5:1( Fig. 20).
88% conversion of 1-decene is obtained in 2 h.
ndings, a possible mechanism has been proposed
The modication with ZnCl
2
, AlCl
3
and ZnCl
2
+
for the reaction. It has been found that the mono-
AlCl
3
was studied. There are eight isomers of
and di-alkylation steps are kinetically controlled,
decyldiphenyl oxide, with the major being
whereas the oligomerizations are internal diusion
2-diphenyl oxide decane.
controlled. This explains the higher selectivity for
alkylation obtained with this catalyst. The activity
Table 19
of S-ZrO
2
compared with Amberlyst-15 is also
Reaction of substituted benzenes with DIPB [106]
signicantly higher.
Reactant Reactant:DIPB Reaction DIPB conversion
mole ratio time (h) (%)
5.1.8. Propylation of naphthalene
Benzene 10:1 2 60.0
Naphthalene has been propylated by using
Toluene 6:1 2 21.5
S-ZrO
2
catalysts and high selectivity for monoalky-
Phenol 10:1 2 5.0
lation at high conversions has been claimed (see
Benzonitrile 10:1 2 0
Ref. [105]).
Fig. 20. Reaction scheme of DPO with alkene [109].
5.2. Isomerizations results into a number of products, such as
1-octanal, furan, 2-octene-1-ol, 3-octene-1-ol (cis),
3-octene-1-ol (trans) and the products of aldol S-ZrO
2
has been found to catalyze a number of
isomerization reactions of industrial importance, condensation of these. 1-Octanal and the allylic
alcohols formed exhibit perfumery properties and such as isomerization of 1,2-epoxides, citronellal
and unsaturated hydrocarbons. thus an increase in the selectivity for these products
is of considerable academic as well as industrial
importance. The overall reaction follows a complex 5.2.1. Isomerization of epoxides to aldehydes
The isomerization of epoxides to corresponding pathway consisting of several series and parallel
reactions. aldehydes by using acidic or basic catalysts is of
great commercial importance in the manufacture It is seen from Table 21 that S-ZrO
2
shows
lower conversion of the epoxide, although the of perfumery aldehydes and their acetals (Fig. 21).
The rearrangement of epoxides leads to several formation of the aldol product is suppressed to a
large extent. This can be attributed to the fact that products and the selectivity to a particular product
is largely dependent upon the nature of the cata- selectivity for the aldehyde that undergoes aldol
condensation is also low. On the other hand, the lysts. Yadav and Satoskar [61] have conducted a
detailed investigation of the rearrangement of selectivity for the allylic alcohols, also commer-
cially important, is higher. As is obvious from the 1,2-epoxyoctane with a variety of solid acid cata-
lysts. The comparative performance of these cata- data, other Lewis acid catalysts also show lower
selectivity for the aldehyde, but in these cases the lysts is shown in Table 21. The isomerization
formation of the aldol is much higher than that
with S-ZrO
2
. This suggests that the formation of
Table 20
Alkylation of benzene with 1-dodecenea [ 93] aldehyde in these cases is high, but it is subse-
quently accompanied by rapid aldol condensation.
Catalyst 1-Dodecene Selectivity of
In addition, the formation of furan is also sup-
conversion (%) 3-phenyl-dodecane (%)
pressed with the use of S-ZrO
2
. These results
DTP 22 20 suggest a strong inuence of the strength and
K-10 95 47
nature of acidic sites in the formation of various
20% DTP/K-10 100 62
products.
Filtrol-24 90 47
Al-pillared/K-10 75 50
S-ZrO
2
12 32
5.2.2. Hydroisomerization-cracking of n-octane
Na-montmorillonite 24 40
S-ZrO
2
and H-mordenite catalysts were studied
20% DTP/C 0 0
by Grau and Parera [110] for hydroisomerization-
20% DTS/K-10 95 50
cracking of n-octane at 573 K and 1.5 MPa, in
20% DPM/K-10 95 52
order to produce light isoparans. Since the deac-
20% DTP/SiO
2
57 42
tivation by pore blockage was decreased, the com-
a 1-Dodecene:benzene=1:10; temperature: 150C; catalyst
posite catalysts with H-mordenite led to an
loading: 0.05 g cm3; pressure: 100 psi; speed of agitation:
improved stability. The composite catalysts with
800 rpm; reaction time: 4 h; DTP: dodecatungstophosphoric
S-ZrO
2
did not result in improvement because of
acid; DTS: dodecatungstosilicic acid; DPM: dodecaphospho-
molybdic acid. their wide pore size distribution.
content of around 3%. According to their observa-
tions it appears that the optimum catalyst should
contain the maximum amount of sulfate near the
surface, but not necessarily on the surface, and it
should crystallize in the tetragonal form. The study
has also indicated that, for the same calcination
temperature, activity is a function of the sulfate
present on the surface, but an examination of the
XPS data indicates that the relationship is not a
simple one, because the activity still increases after
some sulfate has already migrated into the bulk.
It appears likely that some of the sulfate groups
present in the underlying layer might also contrib-
ute to the initiation of the carbocationic reaction
by one-electron oxidation, characteristic to bifunc-
tional types of catalyst. Considering that incorpo-
ration of promoters with redox properties into
S-ZrO
2
greatly increases the catalytic activity with-
out changing the acidity measured by the standard
techniques, it is most likely that oxidizing ability
is the activity-controlling property of this and
similar catalysts. Once the reactive carbocation
precursors have been generated by oxidation, the
acid-catalyzed reactions proceed smoothly. At the
same time, considering that the special oxidizing
character of these materials is generated by the
interaction of sulfate groups with the metal oxide,
full coverage of the surface by sulfate, that is
conversion of the surface to zirconium sulfate,
should destroy the activity. The activity is also
tied to the crystal structure of the zirconia support,
but the latter is, in turn, tied to the quantity of
sulfur present as sulfate on the surface. Hence,
Farcasiu et al. [111] have suggested that a zirconia
support crystallized in the tetragonal form seems
to be essential for high catalytic activity.
5.2.4. Isomerization of d-citronellal to isopulegol
The absence of shape selectivity and micropo-
rosity in S-ZrO
2
is reected in the isomerization
Fig. 21. Consecutive and parallel reactions in isomerization of
1,2-epoxyalkanes [61]. of d-citronellal to isopulegol, an important perfum-
ery chemical [112].
Recently, Yadav and Nair [113] have reported 5.2.3. Isomerization of methyl cyclopentane to
cyclohexane the use of modied S-ZrO
2
in the manufacture of
isopulegol from citronellal. It is well established Farcasiu et al. [111] have studied the activity
of S-ZrO
2
for the isomerization of methyl cyclo- that the formation of isopulegol ether takes place
if citronellal is easily accessible to the Bronsted sites pentane to cyclohexane at 65C. S-ZrO
2
was found
to give the best results with a maximum sulfur of the catalyst. Hence, in the case of S-ZrO
2
[650]
Table 21
Isomerization of epoxyoctane over dierent acid catalysts [61]
Catalysta Epoxide conversion (%) 1-Octanal Furan 2-Octene-1-ol 3-Octene-1-ol (cis) 3-Octene-1-ol (trans) Aldol
H
3
PO
4
/SiO
2
100 19 20 9 12 11 29
H
3
PO
4
/Carbon 76 8 11 14 16 13 38
Aq. H
3
PO
4
31 2 10 2 3 4 9
H
3
PO
4
/Clay 100 16 21 3 8 6 46
H
3
PO
4
/SiO
2
b 100 38 c c c c c
HPA/Clay 74 14 19 8 12 8 39
HPA 100 12 12 c c c 21
HPA/SiO
2
66 9 22 6 7 5 51
HPA/carbon 32 6 20 16 18 10 30
ZnCl
2
/carbon 12 2 15 20 21 18 24
ZnCl
2
/clay 29 2 18 12 22 12 34
ZnCl
2
/Filtrol 87 12 16 11 12 13 14
ZnCl
2
/SiO
2
25 7 15 14 10 16 45
S-ZrO
2
24 3 11 23 16 29 18
Filtrol-24 55 8 22 10 13 16 31
ZSM-5 12 0.4 12 21 16 23 31
ZSM-5b 80 7 24 12 14 22 19
a HPA: dodecatungstophosphoric acid.
b Reaction time: 2 h.
c Very low values were detected.
Table 22
Activities of catalysts for cyclization of d-citronellal over S-ZrO
2
and composite S-ZrO
2
CMS catalysts ( UDCaT-2)a [112,113]
Catalystb Time (min) d-Citronellal conversion (%) Selectivity for l-isopulegol (%)
ZrO
2
[230350] 90 0
S-ZrO
2
[ 230350] 10 96 46
S-ZrO
2
[ 230350]/C 30 91 65
S-ZrO
2
[ 230350]/benzene/C 20 95 52
S-ZrO
2
[ 230350]/cyclohexane/C 20 96 61
S-ZrO
2
[ 230350]/CCl
4
/C 30 88 53
S-ZrO
2
[ 230350]/hexane/C 20 95 58
S-ZrO
2
[ 230350]/C[ 120] 90 91 71
S-ZrO
2
[ 230350]/C[ 230] 30 95 65
DTS/coal (not activated) 30 27 69
30% ZnCl
2
/CMS(coal ), calcined 30 49 53
30% ZnCl
2
/CMS(coal ), uncalcined 30 54 91
S-ZrO
2
10 100 9
K-10 10 100 38
DTS 05 100 0.3
30% DTS/coal/CMS 30 34 31
30% DTS/CMS(coal )/polymer coated 30 12 19
K-10/CMS 30 85 61
a Solvent: toluene, 15 g; reactant: citronellal, 5 g; temperature: 95C; catalyst loading: 10% w/w of citronellal; speed of agitation:
2400 rpm.
b DTS: dodecatungstosilicic acid. Values in square brackets indicate the calcination temperature.
Table 23
of isopulegol. The same reason is true for the
Catalytic activity of sulfate-promoted oxides in butane isomer-
decrease in the rate of the reaction. Further, when
ization [ 2]
S-ZrO
2
[230350] is coated with CMS a uniform
barrier of pore size 17 A
is obtained. This marginal

Catalyst Reaction temp. (C) Time (h) Yield (%)
drop in pore size provides further resistance to the
ZrO
2
25 24 30.5
formation of isopulegol ether and hence favors the
Fe
2
O
3
25 24 18
formation of isopulegol. Also, the external surface
TiO
2
50 20 30.4
of the catalyst, which may consist of Bronsted acid
SiO
2
Al
2
O
3
100 24 1.5
sites, becomes inaccessible to citronellal, which fur-
ther decreases the formation of isopulegol ether.
S-ZrO
2
-modified CMS can be prepared using as catalyst (number in brackets indicates calcination
temperature), where the calcination temperature is dierent polymers as precursors and hence the
catalysts can be tailor-made by ne-tuning the high the average pore size of the same was found
to be 41 A
by nitrogen adsorption isotherm using pore size according to the requirements. Thus
eclectically engineered S-ZrO
2
CMS catalysts lead a Micromeritics surface area analyzer (ASAP 2010
Model ). When S-ZrO
2
[650] was compared with to much greater selectivity to isopulegol in the
cyclization of citronellal. Table 22 shows the com- S-ZrO
2
[230350] the selectivity towards the forma-
tion of isopulegol was found to increase with the parison between S-ZrO
2
and CMS-modied
S-ZrO
2
. The results show that the selectivity of latter. The pore size of S-ZrO
2
[230350] was found
to be 28 A
. Hence, even though the Bronsted acidity isopulegol can be varied drastically by simply
modifying the calcination temperature of S-ZrO
2
is expected to be more in the case of
S-ZrO
2
[230350] compared with S-ZrO
2
[650], or with CMS.
which is a Lewis acid catalyst, the pore size is
smaller than the latter. This leads to the diusion- 5.2.5. Isomerization of straight-chain alkanes to
branched isomers controlled formation of isopulegol ether, which is
kinetically much bulkier than isopulegol, and hence Another isomerization of industrial importance
is the selective transformation of hydrocarbons to leads to the subsequent increase in the formation
Table 24
Catalytic activity of sulfur-promoted metal oxides in isomerization of cyclopropane [2]
Catalyst X
i
CN HSAB Promotera Amount of S Reaction rate
(wt% as SO
3
) (mmol min1 g1)
Fe
2
O
3
12.6 6 hard AS 2 680
Fe
2
O
3
12.6 6 hard SO
3
2 400
Fe
2
O
3
12.6 6 hard SO
2
2 0 (350)b
Fe
2
O
3
12.6 6 hard H
2
S 2 0 (280)b
Fe
2
O
3
12.6 6 hard none trace
ZrO
2
12.6 7 hard AS 8 243c
TiO
2
13.5 6 hard AS 2 226c
Fe
2
O
3
12.6 6 hard AS 2 202c
Al
2
O
3
10.5 6 hard AS 4 69c
SnO
2
9.0 6 hard AS 2 49c
SiO
2
16.2 4 hard AS 2 0c
Bi
2
O
3
13.3 5, 6 medium AS 5 0c
a AS: ammonium sulfate.
b Reaction at 150C. Values in parentheses obtained after oxidation.
c Reaction at 100C.
X
i
: electronegativity.
HSAB: hard soft acid base.
corresponding high octane number branched iso- 5.2.6. Isomerization of terpinolene
Tanabe et al. [83] have reported the isomeriza- mers for blending with gasoline.
n-Alkane (C
4
C
7
) isomerization reactions are tion of terpinolene with 65% conversion and 78%
selectivity over S-ZrO
2
as catalyst. known to require superacidic catalysts to drive the
reactants towards the formation of branched pro-
ducts under milder conditions. Since the chemistry
of this reaction is known, it has been used as a 5.3. Condensation reactions
model reaction to characterize the catalytic beha-
vior of S-ZrO
2
catalysts. The activity of S-ZrO
2
5.3.1. Condensation of hydroquinone with aniline
and substituted anilines was studied vis-a`-vis other sulfate-promoted oxides
by Yamaguchi [ 2] for isomerization of n-butane S-ZrO
2
has also been employed for several
condensation reactions. The use of S-ZrO
2
to ( Table 23) and cyclopropane ( Table 24). In the
case of n-butane isomerization S-ZrO
2
is found to catalyze the condensation of hydroquinone with
aniline and substituted anilines has been investi- give the highest yield at ambient temperature,
which is indicative of the superacid nature of the gated by Kumbhar and Yadav [119]. Conventional
methods to carry out these reactions involve high catalyst. In cyclopropane isomerization the cata-
lytic activity of S-ZrO
2
is attributed to the highly temperature of reaction, sometimes accompanied
by super-atmospheric pressures with the use of electronegative cation, Zr4+. However, even
though cyclopropane isomerization is certainly a catalysts such as ZnCl
2
, FeCl
3
, HCl and p-tolu-
enesulfonic acid. The condensation of aniline and good test reaction to see the acidic property, it
does not need superacidity. hydroquinone lead to the formation of N,N-diphe-
nylenediamine and N,N-di-o-toluyl-p-phenylene- Isomerization of n-alkanes catalyzed by
S-ZrO
2
and modied S-ZrO
2
has been studied by diamine. These reactions proceed via a
combination of series and parallel reactions. The many researchers [114118]. S-ZrO
2
catalyzes the
isomerization of n-alkanes at very low temper- reaction scheme for the condensation of hydroqui-
none with aniline is shown in Fig. 22. atures. With the use of unmodied S-ZrO
2
, how-
ever, low selectivity accompanied by rapid Comparison of activities of various catalysts
vis-a`-vis S-ZrO
2
is presented in Table 25. It is deactivation of the catalyst has been reported. The
deactivation of the catalyst is attributed to coking evident that S-ZrO
2
is capable of catalyzing these
reactions under milder conditions compared with of the catalytic sites. Higher stability of the inter-
mediate carbenium ions formed during these reac- the conventional catalysts. The increased conver-
sion for superacidic zirconia (H
o
16) in com- tions and lower rates of hydride transfer from the
n-alkane molecule to carbenium ions has been parison with pure zirconia (H
o
=3) is due to the
large increase in the acidity due to sulfuric acid found to be responsible for the lower selectivity.
Use of dihydrogen in such cases to transfer hydride treatment; the higher conversions for p-toluene-
sulfonic acid (PTSA) (H
o
=1.34), with a much quickly to the carbenium ion causes deactivation
through the removal of sulfates in the form of lower acidity than S-ZrO
2
, is intriguing, but is in
agreement with the earlier results obtained by reduced species. Addition of Pt quantitatively
increases the stability of the catalyst towards deac- Rajadhyaksha and Chaudhari [95]. This might be
due to the fact that S-ZrO
2
, which is a hetero- tivation, as well as increasing the selectivity
towards branched products through such eects geneous catalyst, has a very wide acid site distribu-
tion and the number of acid sites available for the as hydrogenation of coke and hydride transfer via
such phenomena as hydrogen spillover to the reactants is limited. For PTSA the strength is
directly related to the number of H+ available due surface sulfates ( Table 7).
The isomerization of n-parans (C>10) has to its homogeneous nature. However, although
PTSA shows activity comparable to S-ZrO
2
, the also been studied by Wen et al. [84], and yields
conversions of 6080% with a selectivity of 60% latter is a better catalyst because of its reusability.
S-ZrO
2
has been found to be reusable after treat- to the iso-parans.
Fig. 22. Condensation of hydroquinone with aniline [119].
ment with methanol to clear the pore blockage. Hence, even though the cost of S-ZrO
2
is much
more than that of PTSA, because of its reusability, The blockage of pores accompanied by reduction
in surface area of the catalyst has indeed been non-corrosiveness and easy separability, it might
prove advantageous and be promising for indu- found from the pore size distribution and surface
area measurements before and after the reaction. strial exploitation.
Table 25
Condensation reactions of hydroquinone (HQ) with aniline (B) and o-toluidine (C)a [119]
Reactant Mole ratio Temperature Pressure Catalyst Catalyst Time Yield Ref.
HQ:B/C (C) (kg cm2) loading (h)
B 1:3 350 10 Cu
3
(PO
4
)
2
3H
2
O 6 78.4% DPPA [26]
B 1:3 300 10 P(OEt)
3
2% (w/w) 75% DPPA [120]
B 180250 AlCl
3
1:1 with respect 90% p-OH DPA [121]
to HQ
B 1:2 260 ZnCl
2
1:2 with respect DPPA [122]
to B
Bb 1:2.1 180240 AlCl
3
ZnCl
2
0.19 mol 10 92% of N,N-DPPA [123]
B+C+ 3:2.5 Mixture of diarylamines [124]
xylidenes
B+NH
3
270350 20350 c-Al
2
O
3
78.6% p-NH
2
DPA [125]
B 1:1.1 260 34 I
2
0.052% (w/w) 94.4% of p-OH DPA [126,127]
B 1:2 214 S-ZrO
2
12% (w/w) 6 60% of p-OH DPA [118]
C 1:2 188 S-ZrO
2
12% (w/w) 6 38% of 4-OH MDPA [118]
a DPPA: N,N-diphenyl-p-phenylenediamine; p-OH DPA: p-hydroxydiphenylamine; p-NH
2
DPA: p-aminodiphenylamine; 4-OH
MDPA: 4-hydroxy-2-methyl diphenylamine.
b C
6
H
4
Cl
2
used as an entrainer.
Fig. 23. Condensation of aniline with acetone [130].
5.3.2. Cyclocondensation of aniline with acetone out under atmospheric pressure and semibatch
addition of acetone, with a selectivity towards 2,2,4-Trimethyl-1,2-dihydroquinoline ( TDQ) is
a very important antioxidant, especially used TDQ formation of more than 96% being obtained.
The detailed reaction scheme is given in Fig. 23. with insulating polymers in the cable industry.
2,2,4-Trimethyl-decahydroquinoline, an important The formation of TDQ proceeds via diacetone
alcohol, which is generated in situ by condensation UV stabiliser, is generally prepared by the hydro-
genation of TDQ by using a Raney Ni catalyst of two molecules of acetone in the presence of
either an acid or base catalyst. [128,129]. Generally homogeneous acid catalysts
such as PTSA are employed in industry for acid-
catalyzed reactions. However, in this process, 5.4. Etherication and dehydration of alcohols
appreciable amounts of oligomers are formed with
PTSA along with TDQ. Yadav and Dixit [130] 5.4.1. Etherication of tert-butanol with methanol
S-ZrO
2
has also been applied for etherication have prepared TDQ by cyclocondensation of ace-
tone and aniline using various solid acid catalysts reaction and dehydration reactions. The high activ-
ity of this catalyst for such etherication reactions ( Table 26). The reactions were carried out in batch
mode. Filtrol-24 and Amberlyst-15 were found to is evident from the fact that they lead to the
formation of dibenzyl ether during the alkylation give almost identical highest fractional selectivity
for TDQ followed by S-ZrO
2
and DTP/SiO
2
. of toluene with benzyl alcohol [90]. The etherica-
tion of tert-butyl alcohol and methanol to form However, the cyclocondensation was found to be
even more eective with Filtrol-24 when carried MTBE, the fastest growing gasoline oxygenate
Table 26
Comparison of the fractional selectivity (weight of monomer/weight of oligomers) of TDQ monomer for various solid acid catalysts
(batch reaction)a [ 130]
Time (min) Filtrol-14 Amberlyst-15 S-ZrO
2
DTP/SiO
2
(33% w/w)
30 0.93 0.96 0.93 0.83
60 0.88 0.92 0.88 0.75
120 0.83 0.88 0.82 0.69
180 0.78 0.84 0.71 0.66
240 0.75 0.77 0.62 0.61
a Aniline: 0.1612 gmol; acetone: 0.8064 gmol; catalyst loading: 10% w/w of aniline; temperature: 120C; autogeneous pressure:
5.85 atm.
Srinivasan and Davis [133] to get very high selec-
tivity to 1-octene. Methanol has also been dehy-
drated to dimethyl ether using S-ZrO
2
catalyst
[ 134]. The possible interaction of methanol and
water formed with the catalyst has, however, been
proposed to decrease the stability of the catalyst
by increasing the ionic character of the surface
sulfates that are otherwise responsible for the high
activity of these catalysts.
5.4.2. Etherication of isobutylene with methanol
Recently, Quiroga et al. [135] have carried out
the synthesis of MTBE from methanol and isobu-
tylene in a gassolid heterogeneous system over
Fig. 24. Reaction scheme for etherication of tert-butyl alcohol
S-ZrO
2
. The reaction temperature was varied in
with methanol.
the range of 90110C and methanol to isobutylene
molar ratio was changed from 1.0 to 1.3. The
[131] is a combination of several series and parallel
catalyst acidity was found to be a direct function
reactions leading to a number of products. The
of the sulfur loading, which, in turn, is a conse-
reaction scheme is given in Fig. 24.
quence of the calcination temperature. It was
It is found that the acid-catalyzed in situ dehy-
observed from TPR experiments that the sulfur
dration of tert-butyl alcohol to isobutylene fol-
reduction process was dierent according to the
lowed by the oligomerization of the alkene and
calcination temperature. The highest activity was
the formation of dimethyl ether reduces the selec-
observed at the calcination temperature of 600C,
tivity of the catalyst for MTBE [60] ( Table 27).
which was comparable to that of the reference
Dehydration of mixtures of isobutanol, showing
catalyst Amberlyst-15 under the same conditions.
lesser tendency to get dehydrated than tert-buta-
The injection of water was found to poison the
nol, and methanol have indeed been dehydrated
catalyst activity in a reversible manner.
with S-ZrO
2
catalyst to yield isobutene [132].
Dehydration of 2-octanol has also been studied by
5.4.3. Etherication of b-naphthol with methanol
The etherication of b-naphthol with methanol
Table 27
to produce b-naphthyl methyl ether is industrially
Activities of catalyst of MTBE synthesis from tert-butanol and
very relevant because this happens to be a precur-
methanol [60]
sor of the acylated ether that is used in the
manufacture of the drug naproxene. Yadav and Catalyst tert-BuOH Selectivity to
conversion (%) MTBE (%)
Krishnan [136] have studied this reaction with a
variety of catalysts ( Table 28). S-ZrO
2
is not as
Na+ 21 33
eective as heteropolyacids supported on K-10
A3+ ILC (25 meq Al3+/g) 34 73
clay.
Zr2+ ILC 52 94
Cr2+ ILC 44 95
S-ZrO
2
66 93
5.5. Acylation
K-10 56 70
30% DTP/silica 55 76
5.5.1. Acylation of benzene and chlorobenzene with
20% DTP/K-10 71 99
p-chlorobenzoyl chloride
Amberlyst-15 74 86
20% DTP/carbon 0 0
The usefulness of S-ZrO
2
has also been tested
HZSM-5 77 52
in the acylation of p-chlorobenzoyl chloride and
20% DTS/K-10 74 91
chlorobenzene [137]. In spite of the fact that
20% DMP/K-10 76 86
chlorobenzene is a highly deactivated compound
Table 28
54%, under otherwise similar conditions, and the
Etherication of b-naphthol with methanola [136]
catalyst is reusable. Commercially available clays,
such as K-10 and Filtrol-24, and ion-exchange
Catalyst Conversion (%)
resins, such as Amberlyst-15, IR-120 and
DTP 93
Indion-130, did not catalyze the reaction at all
20% DTP/K-10 74
under otherwise similar conditions. All these cata-
Amberlyst-15 92
lysts are Bronsted acids and seem to be ineective.
Filtrol-24 29
This is further supported by the fact that even
K-10 03
S-ZrO
2
18 heteropoly acids did not catalyze the reaction as
they do not have enough strength to form carbe-
a Temperature: 150C; catalyst loading: 2% w/w; speed of agi-
nium (carbo-cation) ions of the acylating species.
tation: 600 rpm; b-naphthol: 5 g; methanol: 30 g; total volume
The acylation requires very strong acids, especi-
42 ml.
ally Lewis acidity, and except for S-ZrO
2
and
DTP: dodecatungstophosphoric acid.
AlCl
3
, which possess very strong Lewis acid sites,
the other acids were found to be ineective. A
for such a substitution, substantial yields of 4,4-
possible reaction mechanism as to the ecacy of
dichlorobenzophenone under milder conditions
S-ZrO
2
is shown in Fig. 25.
have been claimed. This can be attributed to the
superacidic nature of the active sites of S-ZrO
2
.
Similar acylation of chlorobenzene with o-chlo- 5.5.2. Acylation reactions with carboxylic acids
S-ZrO
2
has also been found to be an active robenzoyl chloride has been investigated by
Tanabe et al. [138] and Yamaguchi [2], wherein catalyst for the vapor-phase acylation of toluene
with acetic acid [140] to give methyl benzophe- the S-ZrO
2
has been found to be highly active in
such an acylation ( Tables 29 and 30). none. S-ZrO
2
was found to give the highest selec-
tivity of 89%towards the ketone at 51%conversion S-ZrO
2
is also found to be a highly active
catalyst for the acylation of benzene with p-chlo- along with the formation of isomers, o-, m- and p-
methylbenzophenone as by-products. Hino and robenzoyl chloride [139]. With homogeneous
AlCl
3
catalyst, a conversion of 90% and a yield of Arata [140] have also reported acylation of ben-
zene with acetic acid using S-ZrO
2
as catalyst. 70% of the acetylated product was obtained.
S-ZrO
2
gives a conversion of 60% and a yield of However, the catalyst was not found to be very
Table 29
Catalytic acylation of o-chlorobenzoylchloride with chlorobenzene by solid superacid and H
2
SO
4
[2]
Catalysta (3 g) Reaction temp.(C) Reaction time (h) Product
yield (%) 2,4- 2,2- 4,4-
AS/ZrO
2
133 1 26.2 88.1 11.6 0.3
AS/ZrO
2
133 10 100b
AS/TiO
2
133 1 6.3 87.6 12.4 0
AS/ZrO
2
SnO
2
133 3 0.6
NH
4
F/ZrO
2
133 3 0
NH
4
F/SiO
2
Al
2
O
3
133 3 0
SiO
2
Al
2
O
3
135 1 0.17 90.4 9.6 0
ZrO
2
135 3 0
ZSM-5 135 3 0
Mg-Y 135 3 0
H
2
SO
4
135 3 0.17 91.0 6.6 2.4
a AS: activated by (NH
4
)
2
SO
4
.
b Amount of catalyst: 6 g.
Table 30
Synthesis of benzophenone derivatives by S-ZrO
2
from benzoyl chloride and chlorobenzene [2]
Substituent Reaction Temp. (C) Product
X Y yield (%) 2,4- 2,2- 4,4-
Cl Cl 133 25.1 89.0 11.0 0.0
H Cl 133 4.5 76.5 23.5 0.0
Cl CH
3
110 93.0 84.4 14.2 1.4
H CH
3
110 13.8 69.1 27.3 3.6
eective for this reaction, as only 25% conversion catalyst to strong Lewis acid of Zr4+ created by
the inductive eect of SNO or a Bronsted acid was obtained with obviously 100% selectivity
towards the ketone. This can be attributed to the formed by the adsorption of water on Zr4+. Kurek
[ 141] has carried out the acylation of aromatic, lower reactivity of benzene over toluene. The
authors [140] have attributed the activity of the hydroxy-substituted hydrocarbons, alkoxy-substi-
Fig. 25. Reaction mechanism over S-ZrO
2
: acylation of benzene with p-chlorobenzoyl chloride.
Table 31
tuted aromatic hydrocarbons where the alkoxy
Esterication of phenethyl alcohol and cyclohexanol with acetic
group contains 110 C atoms and halogen-substi-
acid [ 143]
tuted aromatic hydrocarbons with a carboxylic
acid anhydride using S-ZrO
2
as catalyst. S-ZrO
2
Catalyst Conversion after 5 h (%)
showed very high activity in FriedelCrafts benzo-
Phenethyl alcohola Cyclohexanolb
ylation of benzene and substituted benzenes, such
as chlorobenzene, toluene and 1,3,5-trimethyl ben-
Amberlyst-15 97 78
zene, to give benzophenones in 90100% yield as
Filtrol-24 76 49
S-ZrO
2
70 40
reported by Jia et al. [142]. The calcination temper-
DTP/SiO
2
63 30
ature was found to greatly inuence the acid
DTP/C 39 26
strength and activity of S-ZrO
2
in this reaction.
DTPc 100 94
Also, the reversibility of FriedelCrafts benzoyla-
tion and trans-acylation were observed with the a Phenethyl alcohol:acetic acid=1:4; temperature: 100c; cat-
alyst loading: 5% w/w on alcohol; speed of agitation: 1200 rpm;
superacidic S-ZrO
2
.
reaction time: 300 min.
b Cyclohexanol:acetic acid=1:3; temperature: 100c; catalyst
loading: 5%w/w on alcohol; speed of agitation: 1200 rpm; reac-
5.6. Esterication
tion time: 300 min.
c Reaction time: 180 min.
S-ZrO
2
has been tested for a number of esteri-
cations, such as phenethyl alcohol and cyclohexa- 5.6.2. Esterication of phthalic anhydride with
alkanol nol with acetic acid [143], phthalic anhydride and
alkanols such as 2-ethyl hexanol [144], methanol Thorat et al. [144] have used this catalyst for
the reaction of phthalic anhydride with 2-ethyl and ethanol [145].
hexanol leading to dioctyl phthalate, an indu-
strially important plasticizer. This is a two-step
reaction involving the monoester formation in the 5.6.1. Esterication of phenethyl alcohol and
cyclohexanol rst step followed by the diesterication, as shown
in Fig. 26. Phenethyl acetate and cyclohexyl acetate are
two of the basic esters having wide-spread applica- The monoester formation is a suciently fast
reaction and requires no catalyst. The second step, tions in the perfumery and avor industries [146].
Phenethyl acetate is widely employed in perfume however, is slow and requires the use of acidic
catalysts. Accordingly, the performance of compositions, from everyday soap and detergent
perfumes to ne cosmetics fragrances, room S-ZrO
2
has been compared with that of the conven-
tional catalysts like p-toluene sulfonic acid. A sprays, deodorants, etc. Cyclohexyl acetate is used
in masking odors for industrial purposes. It also detailed investigation of the reaction has been done
regarding the activity and reusability for the reac- has applications in avor compositions, mainly for
imitation apple, blackberry, banana, raspberry and tion. With S-ZrO
2
catalyst, the reaction is found
to follow an overall second-order kinetics. A com- in tutti-fruity avors [146].
Yadav and Mehta [143] have studied the esteri- parison of the activity of various catalysts for this
reaction indicates that S-ZrO
2
is the most active cation of phenethyl alcohol and cyclohexanol
( Table 31) using various solid acid catalysts. Of ( Table 32).
all the solid superacids, Amberlyst-15 gave the
highest conversion for the esterication of phe- 5.6.3. Esterication of phthalic anhydride with n-
butanol and iso-amyl alcohol nethyl alcohol with acetic acid. S-ZrO
2
was found
to give only 70% conversion. Amberlyst-15 was Yadav and Mujeebur Rahuman [145] have car-
ried out the esterication of phthalic anhydride again found to be a very eective solid acid catalyst
for the esterication of cyclohexanol with acetic with n-butanol using S-ZrO
2
as catalyst to give
dibutyl phthalate. The reaction was carried out at acid.
formation of diisoamyl phthalate was observed.
Here too, the reaction is found to proceed through
the formation of monoester of phthalic anhydride.
5.7. Nitration
Industrial aromatic nitrations are carried out in
a mixture of nitric acid and sulfuric acid predomi-
nantly giving ortho- and para-substituted products
for substituted benzene, etc. However, this process
has a major problem of the spent acid disposal.
The formation of water during the reaction causes
the dilution of the nitrating mixture, thus reducing
the rate of nitration as the reaction proceeds. At
about 68% w/w H
2
SO
4
, the nitration becomes
extremely slow. Moreover, it is desirable to
increase the para-selectivity, as the economic point
of view warrants it.
Recent advances in superacid catalysts have
brought considerable research importance to this
reaction. Attempts are being made to reduce the
spent acid generated during this reaction and
Fig. 26. Esterication of phthalic anhydride with 2-ethyl
increase the para-preference by properly substitut-
hexanol.
ing the type of catalyst with proper solvents.
Table 32
5.7.1. Nitration of chlorobenzene
Esterication of phthalic anhydride with 2-ethylhexanol a [144]
In this context, S-ZrO
2
has been used to nitrate
Catalyst Time (min) Monoester conversion (%) chlorobenzene with nitric acid and acetic anhy-
dride as the solvent [147]. They have claimed a
No catalyst 240 37
high para-selectivity of 77% at a conversion of
S-ZrO
2
240 93
100%. Also, Fe3+K-10 catalyst has been used to
P-ZrO
2
240 89
nitrate chlorobenzene with fuming nitric acid using B-ZrO
2
240 89
DTP/SiO
2
180 75
acetic anhydride as the solvent [148]; a high para-
ZrO
2
240 80
selectivity of 92% at a conversion of 90% was
S-Fe
2
O
3
180 35
observed. This seems consistent with the fact that
DTP/Al
2
O
3
120 65
acetic anhydride oers a reaction medium with a
a Monoester:2-ethylhexanol=1:1; temperature: 195C; cata- low dielectric constant. Laszlo and Pennetraeu
lyst loading: 1.2% w/w.
[ 149] have used cupric nitrate supported on K-10
(Claycop) to nitrate chlorobenzene at room tem-
perature, wherein they have obtained a o:p ratio 123126C for 6.5 h with 2.5% w/w of catalyst
loading, whereby 85% formation of dibutyl phtha- of 1:7.5 with 73%yield. Solid superacidic Naon-H
catalysts have also been used to aect nitration late was observed. The reaction proceeds through
the formation of monoester of phthalic anhydride. with the azeotropic distillation of water of reaction
[ 150]. Olah et al. [ 151] have investigated the state Esterication of phthalic anhydride with iso-
amyl alcohol using S-ZrO
2
as catalyst was also of nitric acid in acetic anhydride. Acids have been
found to increase the nitration rates in such reac- studied by Yadav and Mujeebur Rahuman [145].
The reaction was carried out at 138142C for 6 h tions. Several liquid superacids, such as uoro-
sulfonic acid anhydride, boron triuoride using 2.5% w/w of S-ZrO
2
as catalyst. A 90%
Table 33
Dierent catalysts used for the nitration of chlorobenzene
Nitrating medium/catalyst Temp. (C) Time (h) Yield (%) o:p ratio Ref.
S-ZrO
2
/nitric acid/acetic anhydride 30 1.5 100 1:3.6 [147]
Fe3+K-10/fuming HNO
3
/acetic anhydride 1.5 92 [148]
Cu(NO
3
)
2
/K-10/acetic anhydride/hexane 25 48 73 1:7.5 [149]
HNO
3
/BF
3
H
2
O 25 12 92 1:2.23 [152]
KNO
3
/BF
3
H
2
O 25 12 91 1:2.23 [152]
HNO
3
/(CF
3
SO
2
)
2
O/MeNO
2
or EtNO
2
0 0.5 86 1:3 [153]
HNO
3
/(CF
3
SO
2
)
2
O/CFCl
3
25 12 90 1:5.66 [153]
HNO
3
deposited on zeolite 1:1.13 [154]
HNO
3
/cryst. SiO
2
mol. sieves 90 2 14 17.4:0.4:82.2a [155]
HNO
3
/HZSM-5 90 2 45 19:1:80a [155]
HNO
3
/silicaalumina 90 2 8 40:60 [156]
98% HNO
3
60 3 70.5 1:1.88 [157]
98% HNO
3
/H
3
PO
4
80 0.5 99.5 1:3 [157]
70% HNO
3
/Nafion-Hb 1:0.02:1.61a [150]
70% HNO
3
/ Hg(NO
3
)
2
/Nafion-Hb 59 1:0.05:1.65a [150]
98% HNO
3
/98% H
2
SO
4
/MeSO
3
H 1:2.16 [158]
98% HNO
3
/95.5% H
2
SO
4
/CH
2
Cl
2
41 4.5 96.8 [159]
a o:m:p ratio.
b Azeotropic water removal; no NO
3
present.
monohydrate and methane sulfonic acid, have by-products was observed in this reaction.
Modication of S-ZrO
2
by coating it with CMS to been studied for this reaction with a variety of
solvents. The results of these investigations are yield S-ZrO
2
/CMS further enhanced the selectivity
towards the formation of the para-isomer, though summarized in Table 33.
As seen from Table 34 the use of S-ZrO
2
for the there was no considerable change in conversion.
This can be attributed to the fact that the CMS nitration of chlorobenzene gave high selectivity
towards the formation of p-chlorobenzene nitroben- around S-ZrO
2
acts as a barrier for the bulkier
ortho-isomer and hence favoring the formation of zene [160]. No formation of meta-isomer was
observed. Also, no formation of any dinitrated kinetically smaller para-isomer. This is further sup-
ported by the fact that the average pore size of
S-ZrO
2
was found to be 40 A
and that of
Table 34
S-ZrO
2
/CMS 17 A
as determined by nitrogen
Nitration of chlorobenzenea [160]
adsorption isotherm on a Micromeritics surface area
Catalyst HNO
3
conversionb (%) o:p ratio
analyzer (ASAP 2010). Also, the catalyst was found
to be reusable with initial washing of the used
No catalyst 0
catalyst with acetone. However, on increasing the
S-ZrO
2
47 110.6
S-ZrO
2
/CMS 45 1:13.2
acidity of S-ZrO
2
by supporting a heteropolyacid
DTP/S-ZrO
2
41 1:8.6
(dodecatungstophosphoric acid) on it the p:o ratio
CMS/DTP/S-ZrO
2
21 1:10.2
was found to decrease. When coated again with
CMS, this catalyst gave better selectivity towards
a Experimental conditions: chlorobenzene, 0.2 gmol; HNO
3
,
0.1 gmol; temperature, 30C; catalyst, 2.24 g; volume of organic the formation of para-product, further strengthening
phase, 78 ml; catalyst loading 0.028 g cm3 of the reaction mix-
the theory of CMS causing this change.
ture (organic phase, excluding the volume of nitric acid);
HNO
3
ow rate, 1.85105 gmol s1; acetic anhydride,
5.7.2. Nitration of toluene
0.5 gmol; time, 1.5 h.
Also, nitration of toluene has been carried out
b In a short while after the addition of nitric acid was
complete. using dierent solid superacid catalysts. Zeolite
H+ beta catalyst has been used to nitrate toluene water from the reaction mixture and providing a
reaction medium of low dielectric constant, also with fuming nitric acid using acetic anhydride as
solvent by Keith et al. [161], who have claimed a reacts with nitric acid to form a stable nitronium
salt, acetyl nitrate, which further nitrates the aro- high para selectivity of 78% at a yield of 99%.
Masci [162] used a mixture of triuoroacetic matic substrate [151,163,164]. Olah et al. [151]
have investigated the state of nitric acid in acetic anhydride (TFAA) and tetrabutylammonium
nitrate in CH
2
Cl
2
with dierent sizes of crown anhydride. It has been found from Raman and
infrared spectra that these solutions do not contain ether at 25C, whereupon he obtained an o:m:p
ratio of 1:0.08:5.54 to 1:0.03:0.70 with the 18C
6
nitronium ions. Further evidence is due to the fact
that nitronium salts react very vigorously with and 12C
4
ethers. In a similar way, benzoyl nitrate
ion in the presence of aluminum/proton-exchanged acetic anhydride to form acetyl nitrate. Acids have
been found to increase the nitration rates in such large-pore mordenite has shown a great preference
towards the para-isomer. Dierent metal nitrates reactions. Several liquid superacids, such as tetra-
triatoboric acid, triuoromethanesulfonic anhy- impregnated on the K-10 montmorillonite in the
presence of acetic anhydride show more para dride, uorosulfonic acid anhydride, boron
triuoride monohydrate and methane sulfonic anity. Nitration of toluene with nitric acid in
acetic anhydride as the solvent has been reported acid, have been studied for this reaction with a
variety of solvents. The results of these investiga- to yield higher amounts of the para-substituted
product. It is speculated that acetic anhydride, tions are highlighted in Table 35.
On the basis of excellent performance of besides acting as an eective means to absorb
Table 35
Dierent catalysts used for the nitration of toluene
Nitrating medium/catalyst Temp. (C) Time (h) Yield (%) o:m:p ratio Ref.
HNO
3
/H+ beta/acetic anhydride/toluene 020 0.5 >99 1:0.16:4.3 [161]
acetic anhydride/HNO
3
/H+ beta/toluene 020 0.5 >99 1:0.12:3.0 [161]
H+beta/acetic anhydride/HNO
3
/toluene 020 0.5 >99 1:0.12:2.88 [161]
HNO
3
/BF
3
H
2
O 25 2 93 1:0.03:0.81 (5% of dinitro [152]
products)
KNO
3
/BF
3
H
2
O 25 2 83 1:0.03:0.81 (14% of dinitro [152]
products)
HNO
3
/(CF
3
SO
2
)
2
O/MeNO
2
0 5 73 1:0.07:0.72 [153]
HNO
3
/(CF
3
SO
2
)
2
O/EtNO
2
0 5 70 1:0.05:0.58 [153]
HNO
3
/Claycop/Ac
2
O 25 2 97 1:0.06:1.2 [165]
HNO
3
/Ac
2
O 25 2 1:0.04:0.53 [165]
Benzoylnitrate/zeolite in tetrachloromethane 20+15 42 95 1:0.03:2.09 [166]
NO
2
/O
3
/dichloromethane 10 3 51 1:0.03:0.77 [167]
Mol. Sieves 4 A
(40 wt%)/NO
2
/O
3
AlCl
3
/NO
2
/O
3
BF
3
OEt
2
(3.5 mol%)/NO
2
/O
3
Claycop/acetic anhydride 25 2 7598 1:0.03:2.6 [168]
Nitric acid/acetic anhydride 25 2 1:0.02:0.33 [168]
Bu
4
NNO
3
TFAA/CH
2
Cl
2
25 5 min 1:0.03:0.71 [162]
Bu
4
NNO
3
TFAA/CH
2
Cl
2
/12C
4
25 5 min 1:0.03:0.70 [162]
Bu
4
NNO
3
TFAA/CH
2
Cl
2
/15C
5
25 5 min 1:0.03:0.73 [162]
Bu
4
NNO
3
TFAA/CH
2
Cl
2
/18C
6
25 5 min 1:0.04:1.08 [162]
Bu
4
NNO
3
TFAA/CH
2
Cl
2
/21C
7
25 5 min 1:0.08:5.54 [162]
Bu
4
NNO
3
TFAA/CH
2
Cl
2
/24C
8
25 5 min 1:0.09:2.92 [162]
Claycop/fuming nitric acid (0.75 ml mmol1) 25 4 86:13a [169]
a 2,4-dinitrotoluene:2,6-dinitrotoluene.
S-ZrO
2
/CMS as a shape-selective catalyst Yadav hydrogenation. Yadav et al. [170] have reviewed
this eld to note that a large number of patents and Nair [160] carried out the nitration of toluene
using the same catalyst. Here too, it was expected are issued, based on the use of several homogen-
eous catalysts such as AlCl
3
[171], free radical that the formation of para-product should
increase. In fact this behavior was observed, but initiator [172], ethyl aluminum sesquichloride/
titanium tetrachloride [173], BF
3
[174,175], the increase in selectivity of the para-product was
not that high. This is obvious because the nitration BF
3
alcohol [176], BF
3
H
2
O [177],
BF
3
carboxylic acid [178], BF
3
ethoxylated alco- of toluene is found to occur to a considerable
extent even in the absence of catalyst ( Table 36), hol [179], uorophosphoric acid supported on
montmorillonite [180,181], alkylaluminum in contrast with the case of chlorobenzene. Hence,
irrespective of the presence of the catalyst the chloridetert-butyl chloride [182] and reduced
chromium catalyst supported on SiO
2
[183]. nitration will take, place resulting in the formation
of both ortho- and para-products. Still, the small The oligomerization of 1-decene was studied
over dierent kinds of solid acidic catalyst by Akio increase in the formation of para-product can be
attributed to the CMS barrier around the catalyst; and Suzuka [184], in which boron phosphate
showed a higher oligomerization activity than this allows the selective formation of para-product,
which is kinetically smaller than the ortho-product. SiO
2
Al
2
O
3
and S-ZrO
2
. However, the yields of
the dimerized product are very high with S-ZrO
2
Here too, the catalyst was found to be reusable
after initial washing. and the dimer could be subsequently hydrogenated
to get the desired lubricant ( Table 37).
5.8. Oligomerization
5.8.1. Oligomerization of 1-decene 5.8.2. Oligomerization of butanebutene
High-silica TsVM zeolite and dealuminated The linear poly alpha olens are synthetic lubri-
cants, which are typically prepared by the oligo- mordenite-type zeolite catalysts are active in oligo-
merization of a butanebutene fraction at 250 merization of a-olens (C
10
, C
12
) followed by
550C [ 185]. Those authors also studied the oligo-
merization of low molecular weight olens using
Table 36
S-ZrO
2
as catalyst at 150180C, which predomi-
Nitration of toluenea [ 113]
nantly gave C
8
C
16
olens of normal structure,
Catalyst HNO
3
conversionb (%) o:p selectivityc
but their performance stability were found to be
low. Layered NiOSiO
2
catalysts with an antigor-
No catalyst 60 1:0.55
ite structure were found to be active at 180220C
S-ZrO
2
98 1:0.75
DTP/K-10 73 1:0.80
and yielded olen dimers with high selectivity.
S-ZrO
2
/CMS (250C) 98 1:0.77
S-ZrO
2
/CMS (350C) 98 1:0.86
DTP/S-ZrO
2
92 1:0.74
5.8.3. Oligomerization of trans-butene
CMS/DTP/S-ZrO
2
95 1:0.80
Soled and co-workers [186,187] have patented
Double-coated CMSd 94 1:0.85
the use of Ni supported on S-ZrO
2
catalyst used
a Experimental conditions: toluene, 0.2 gmol; HNO
3
,
for the dimerization of trans-butene. The reaction
0.1 gmol; temperature: 20C; catalyst, 0.92 g; volume of organic
was carried out in an autoclave along with decane
phase, 73 ml; catalyst loading, 0.012 g cm3 of the reaction mix-
and trans-butene feed that was maintained in the
ture (organic phase, excluding the volume of nitric acid);
HNO
3
ow rate, 1.85105 gmol s1; acetic anhydride, liquid state by cooling to 0C and under autogen-
0.5 gmol; time, 1.5 h.
eous nitrogen pressure. The autoclave was then
b In a short while after the addition of nitric acid was
heated to 95220C for 5 h. The liquid samples
complete.
analyzed after completion of the run indicated
c In all the experiments 11.5% of meta isomer was found.
that this catalyst was more active than
d S-ZrO
2
/CMS based catalyst was coated with PVA and
calcined at 300600C. It is named as UDCaT-2. NiO/SiO
2
Al
2
O
3
.
Table 37
Product distribution of dierent oligomers [170]
Catalyst Yield (%) Oligomers formed (%) Ref.
Dimer Trimer Tetramer Pentamer Hexamer
AlCl
3
80 20 40 30 [ 172]
BF
3
ROH 77 12 48 9 [ 178]
Al(C
2
H
5
)
3
TiCl
4
5 5 80 [ 172]
Di-tert-butyl peroxide 13 9 78 [ 174]
S-ZrO
2
23 95 5 [ 170]
5.8.4. Dimerization of fatty acids, unsaturated 5.9. FischerTropsch reaction
straight chain aliphatic acids and their esters
Branched alkanes are valuable fuels that meet Dimerization of unsaturated straight chain ali-
the reformulated gasoline specications and can phatic acids and their esters is an industrially
be used as premium motor fuels. FischerTropsch important reaction [188]. S-ZrO
2
has also been
synthesis ( FTS) is one of the promising approaches
used as a catalyst in the dimerization of fatty acids
for the production of hydrocarbons from resources
derived from saower oil and dehydrated castor
other than petroleum [190]. Song and Sayari [191]
oil. The ecacy of the catalyst was compared with
have reported the use of S-ZrO
2
in combination
that of triuoromethane sulfonic acid (triic acid).
with FTS catalyst (RuNaY) to produce branched
Triic acid was observed to be highly active;
alkanes from synthesis gas. According to their
however, the product obtained was deeply colored.
observations S-ZrO
2
did not contribute to carbon
S-ZrO
2
was found to give only 10% concurrent
monoxide conversion, but it did bring about sig-
trimer formation with 75%conversion of dimeriza-
nicant changes in hydrocarbon distribution. The
ble acid, which is comparable to that reported on
yield of C
3
was found to decrease with increase in
clay catalysts. However, most of the information
the amount of S-ZrO
2
, whereas the yields of C
1
,
on the clay catalysts, which are commonly used in
C
2
, C
5
and C
6
hydrocarbons were negligible. Also,
industry, is in the form of patents. Hence, a
the formation of isoalkanes was found to be sub-
detailed comparison of zirconia and these catalysts
stantially more than alkenes. All the above changes
cannot be presented. Also, with S-ZrO
2
as catalyst
were attributed to secondary reactions of primary
a very marginal color deepening was observed at
FTS products over the strongly acidic S-ZrO
2
.
the end of the reaction. The results demonstrate
These secondary reactions were found to involve
the promise of S-ZrO
2
as a potential industrial
oligomerization-cracking, skeletal isomerization,
catalyst in the dimerization of fatty acids.
hydrogen transfer and coking. The calcination
temperature of S-ZrO
2
had a strong eect on its
5.8.5. Preparation of synthetic lubricating base oils
activity for the secondary reactions. This eect
Sarin et al. [ 189] have employed S-ZrO
2
as
was attributed to the coke deposition on S-ZrO
2
,
catalyst for the preparation of poly (a-olen) syn-
which led to the catalyst deactivation. The very
thetic lubricating base oils. S-ZrO
2
showed high
strong Lewis acid sites were proposed to be respon-
activity for oligomerization, which increased with
sible for the rapid coking deactivation. The addi-
decreasing chain length. Isomerization accompa-
tion of small amounts of platinum on S-ZrO
2
or
nied oligomerization, which suggested a carboca-
mixing S-ZrO
2
with the FTS catalyst instead of
tion mechanism. These carbocations showed a high
using them in separate layers improved the overall
tendency for chain transfer by proton elimination, stability of the hybrid catalyst. Table 38 shows the
resulting in isomerization of monomeric olen and eect of amount of S-ZrO
2
on hydrocarbon
distribution. higher conversion to dimers.
Table 38
reached 88.7%at C
24
yield of 18 wt.%. The carbon
Hydrocarbon distribution in the presence of varying amounts
monoxide, carbon dioxide and methane concen-
of S-ZrO
2
[191]
trations in the product were found to be very low,
but the olen:paran ratio was high. Ammonium
Hydrocarbon (wt%) Amount of S-ZrO
2
(g)
hydroxide concentration had some eect on the
0 0.05 0.10 0.15 0.20 0.30
hydrocarbon distribution ( Table 39).
C
1
32.7 34.6 33.9 34.9 34.2 35.4
C
2
11.8 12.7 11.4 12.2 12.5 11.3
5.11. Cracking reactions
C
3
21.4 17.3 14.7 12.0 7.7 7.0
C2
3
a 17.7 12.7 8.7 6.6 0.8 0
C
3
b 3.7 4.6 6.0 5.4 6.9 7.0
As polystyrene is used in consumer product
C
4
18.9 20.6 24.1 27.1 32.5 33.9
packaging and to make disposable containers, it
C
5
10.7 10.3 10.9 9.8 9.3 8.9
comprises a signicant fraction of municipal plastic
C
6
4.5 4.5 5.0 4.0 3.8 3.5
waste. Recently, Lin and White [194] have studied
a Propene.
the cracking of polystyrene over various solid acid
b Propane.
catalysts. Silicaalumina, HZSM-5 and S-ZrO
2
were employed as cracking catalysts, whereby all
the catalysts were initially coated with polystyrene. 5.10. Methanol to lower olens
The polymer-coated catalysts were heated to
400C, when decomposition of the polymer took Zeng et al. [ 192] employed S-ZrO
2
as catalyst
for the conversion of methanol to lower olens. place. The most abundant volatile product gener-
ated by catalytic cracking was found to be benzene. The eect of calcination temperature of S-ZrO
2
was studied and detailed. It was found that at a HZSM-5 was found to give about 60% benzene,
whereas S-ZrO
2
gave 33% and silicaalumina 30%. calcination temperature of 773 K and reaction
temperature of 653 K the methanol conversion 12% ethyl benzene was the second most abundant
Table 39
Conversion of methanol into hydrocarbons over modied zirconias at a reaction temperature of 350Ca [ 193]
Catalyst ZrO
2
c S-ZrO
2
d S-ZrO
2
e HZSM-5
Product distribution (wt%)
CH
3
OH 30.7 6.1 4.5 0
CH
3
OCH
3
34.3 7.0 8.1 0
Hydrocarbons 0.8 33.2 30.5 39.6
CO+CO
2
11.3 1.9 1.0 2.8
Hydrocarbons (wt%)
CH
4
80.9 9.1 8.3 0.4
C
2
H
4
19.1 16.7 16.0 4.9
C
2
H
6
0 2.1 2.0 0.2
C
3
H
6
0 15.4 14.9 7.7
C
3
H
8
0 0.8 1.7 7.0
C
4
H
8
0 2.6 4.6 6.3
C
4
H
10
0 19.3 11.1 16.7
C
5+
b 0 9.1 9.1 26.0
Aromatics 0 24.8 32.4 30.9
a W/F=336 g h mol 1; CH
3
OH pressure, 5.33 kPa; conversion after 6 h on stream.
b C
5+
indicates hydrocarbons with more than ve carbon atoms, excluding aromatics.
c Calcined at 580C.
d Obtained from ZrCl
4
.
e Obtained from Zr(NO
3
)
4
.
substance obtained with S-ZrO
2
. Styrene, which is 5.12. Methane oxidative coupling
the principal radical depolymerization product
from polystyrene, was found to be a minor cata- Murata et al. [195] have studied the methane
oxidative coupling of methane to give ethene and lytic cracking product. Other alkylbenzenes and
indanes were also detected in signicant yields. ethane using Li-doped S-ZrO
2
catalyst. The reac-
tion was carried out at 1073 K, when methane Although acid-catalyzed polystyrene cracking
appears to involve many dierent parallel reactions conversion was found to be 43% and
C
2
-selectivity was found to be about 80%. and is quite complicated, the general reaction
scheme (Scheme 1) can be used to represent the However, the eectiveness of Li-doped S-ZrO
2
catalysts on the oxidative coupling of methane is primary reaction pathways. The initial step in
polystyrene cracking is protonation catalysts still not clear. Since the eect of Li doping on
MgO support has already been reported, it seems provide the protons of polymer aromatic rings,
which may result in chain shortening, yielding a likely that the preparation of the S-ZrO
2
surface
is a key step in the catalyst system. The authors chain end cation and a saturated chain end. Ortho
protonation can readily lead to benzene evolution [ 195] have shown that the catalyst performances
depend on the sulfate content and calcination and the formation of a secondary macro-cation,
which may subsequently cyclize to form an indane temperature: a maximum C
2
yield is attained over
catalysts those that contain 6 mass% sulfate and structure. Ortho ring protonation is found to be
the rate-limiting step for the evolution of benzene. which are calcined at 923973 K, being closely
related to the preparation conditions of S-ZrO
2
as Hydride abstraction appears to be an important
reaction pathway for chain-end cations, except solid superacids. If so, sulfated metal oxides other
than ZrO
2
might also be eective as supports. when the catalyst restricts the movement of poly-
mer chains (e.g. HZSM-5). Saturated chain ends Also, a ZrO
2
catalyst impregnated with an aqueous
solution containing both (NH
4
)
2
SO
4
and Li
2
CO
3
, are the likely source of alkyl benzenes, which can
be formed after protonation of chain end aro- followed by calcination in air at 873 K for 3 h,
showed much lower reactivity than that prepared matic rings.
Scheme 1
by the conventional method, whereby ZrO
2
is polyethylene (PE)], high density PE (HDPE), and
mixtures of Blind Canyon DECS-6 (high volatile added to (NH
4
)
2
SO
4
solution and calcined fol-
lowed by impregnation of aqueous solution of bituminous) coal with waste plastics in H
2
at
65 atm. Dierent catalysts evaluated for the con- Li
2
CO
3
. By investigating all these ndings, the
authors [ 195] have concluded that Li doping over version of waste plastics included solid superacids,
like sulfated Fe
2
O
3
, sulfated Al
2
O
3
, sulfated superacid surface is required for the generation of
high catalytic performances for the ZrO
2
-based Al
2
O
3
promoted by 0.5%Pt, and S-ZrO
2
(all added
at 10 wt%). Other conventional cracking catalysts, methane oxidative coupling reaction.
like SiO
2
Al
2
O
3
in a 4:1 ratio, a hydrocracking
catalyst, like NiMo/Al
2
O
3
mixed with 5.13. Thioacetalization of carbonyl compounds
SiO
2
Al
2
O
3
(both added at 50%), and HZSM-5
(added at 10%) were also used for this reaction. S-ZrO
2
was found to catalyze eectively the
reaction of carbonyl compounds with (CH
2
SH)
2
The cracking activity of the catalysts for waste
plastics was of the order: SiO
2
Al
2
O
3
, or PhSH to aord the corresponding dithioacetals
as useful organosulfur synthons [196]. HZSM-5>NiMo/Al
2
O
3
mixed with SiO
2
Al
2
O
3
>solid superacids. Of the solid superacids
studied, S-ZrO
2
was found to possess the highest 5.14. Adamantylation of substituted benzenes
cracking activity. The approximate order of
cracking activity for the superacids was Olah et al. [197] have investigated the ada-
mantylation of substituted benzenes with S-ZrO
2
>sulfated Al
2
O
3
>Pt supported on sul-
fated Al
2
O
3
>sulfated Fe
2
O
3
>no catalyst. The 1-bromoadamantane with various solid acids, like
acidic ion-exchange and ionomer resins, S-ZrO
2
, stronger the cracking catalyst, the lighter the ali-
phatic results were observed for HDPE with these HY zeolite and SiO
2
. The reaction was found to
take place in excellent yield, giving predominantly catalysts. For co-processing of coal with commin-
gled waste plastic HZSM-5 zeolite catalyst para products without formation of by-products.
The reactions did not require the usual work-up showed the most promising results by increasing
the rate of the decomposition reactions at 420C of FriedelCrafts reactions, as catalysts were
simply ltered o. Amberlyst was found to be nearly tenfold. Hydrocracking catalysts (e.g.
NiMo/Al
2
O
3
mixed with SiO
2
Al
2
O
3
) showed particularly suitable for this reaction.
potential promise for co-processing of coal with
commingled waste plastic due to their combined 5.15. Manufacture of hydrogen peroxide
hydrogenation and cracking ability. In contrast,
S-ZrO
2
and SiO
2
Al
2
O
3
appeared to have little Nagashima et al. [198] have developed a cata-
lytic process for the manufacture of high concen- eect on the decomposition rate of the mixture.
tration hydrogen peroxide from hydrogen and
oxygen. The process comprises of directly reacting 5.17. Carbonylation reaction
oxygen with hydrogen in a reaction medium con-
taining a promoter. The catalysts used for the Vapor-phase carbonylation of toluene to form
p-tolualdehyde over S-ZrO
2
is claimed by Hoechst process were a Pt-group catalyst supported on a
solid acid carrier S-ZrO
2
, Al
2
O
3
or TiO
2
or solid Celanese Corporation [200]. S-ZrO
2
is promoted
by copper, iron/manganese and chromium. The superacids like MoO
3
or WO
3
supported on
ZrO
2
. authors [200] mention testing a range of catalyst
compositions in a continuous vapor-phase reactor
and in a batch slurry reactor but provide only the 5.16. Decomposition of commingled waste plastics
sparest of experimental data. In one series of tests,
CO (0100 psig) is bubbled through a mixture of Liu and Meuzelaar [199] have investigated the
eects of dierent catalysts on decomposition reac- catalyst in toluene (0.040.06 g catalyst/g toluene)
at 50C. The highest reported yield is 1.7 g p- tions of commingled waste plastics [predominantly
tolualdehyde/100 g toluene (no mention of reaction structure of these catalysts and this paper is only
a step forward in this direction. time) by using a catalyst comprising 1.1 wt% sulfur
and 1.4 wt% chromium on zirconia. Toluene car- S-ZrO
2
and its modied forms have found their
utility in plethora of industrial reactions ranging bonylation chemistry is not new and has been
carried out with a variety of strong Lewis acids in from simple alkylations to complex decomposition
of commingled waste plastics. Though, they suer the liquid phase. Interest in this chemistry derives
from the fact that the p-tolualdehyde can be readily from deactivation in some of the reactions, still a
large number of reactions of industrial practice oxidized to terephthalic acid. Strong global
demand for polyethylene terephthalate and tereph- could be elegantly carried out using these catalysts.
The following processes may be converted to the thalic acid monomer (PTA) has promoted develop-
ment of technologies for increasing the availability heterogeneous process by utilizing S-ZrO
2
and its
modied forms as catalysts. of PTAs precursor material, p-xylene, above and
beyond the quantities available from conventional 1. Alkylation: o-xylene with styrene, manufacture
of gasoline alkylates, preparation of alkyl phe- sources, such as renery catalytic reformate or
pyrolysis gasoline from steam crackers. A notable nols, propylation of naphthalene.
2. Isomerization: citronellal to isopulegol. success has been the commercialization of the
so-called toluene disproportionation technologies, 3. Condensation: hydroquinone with aniline and
substituted anilines. which take toluene and convert it to xylenes and
benzene. 4. Etherication: isobutylene with methanol.
5. Acylation: benzene and chlorobenzene with p-
chlorobenzoyl chloride, benzoylation of
benzene, chlorobenzene, toluene and
1,3,5-trimethyl benzene 6. Conclusions
6. Esterication: phthalic anhydride with 3-ethyl
hexanol. S-ZrO
2
, as a solid acid, has come of age.
Whether the catalyst is superacidic, or not, depends 7. Nitration: production of para-substituted nitro
aromatic compounds. on the preparation conditions as well as source of
protons. The butane isomerization reaction under 8. Oligomerization: dimerization of fatty acids
derived from saower oil and dehydrated mild conditions has been taken as a proof of the
superacidic nature of S-ZrO
2
. However, the exact castor oil, preparation of poly(a-olen) syn-
thetic lubricating base oils. strength of acidic centers located in S-ZrO
2
has
been a matter of considerable debate, particularly 9. FischerTropsch reaction.
10. Cracking: polystyrene. to account for the superacidity of S-ZrO
2
. Hence,
various models have been proposed. The models 11. Methane oxidative coupling.
12. Decomposition of commingled waste plastics. described in this paper have been evaluated not
only on the basis of spectroscopic studies of We expect further modications in the surface
properties of S-ZrO
2
so that it could become a S-ZrO
2
, but also on the nature of the reactions.
However, the exact structure of S-ZrO
2
, and hence very attractive and reusable commercial catalyst
in a number of industrial reactions. its modied forms, is still a mystery. This is
probably because S-ZrO
2
and its modied forms,
as catalysts, are very sensitive to the kind of
atmosphere in which they are present; for example, Acknowledgements
these catalysts, except a few like S-ZrO
2
-modified
CMS, have a very strong tendency for absorbing Part of work was done under a research grant
by Department of Science and Technology (DST), moisture even when exposed to the atmosphere
for a small instance, which leads to a change in Government of India, and AICTE to GDY.
Financial assistance under Darbari Seth the morphology of the catalysts. Currently, several
attempts are being made to ascertain the exact Professorship Endowment is also acknowledged.
[ 25] M. Hino, K. Arata, J. Chem. Soc. Chem. Commun.
JJN would like to thank DST for a Senior
(1979) 1148.
Research Fellowship. Initial assistance from K.A.
[ 26] M. Bensitel, O. Saur, J.C. Lavalley, G. Mabilon, Mater.
Bhirud and V. Narendra is gratefully
Chem. Phys. 17 (1987) 249.
acknowledged.
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(1986) 4797.
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Catal. A: 116 (1994) 151.
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(1994) 219.
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Sulfated Zirconia and Its Modified Versions As Promising Catalysts For Industrial Processes

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Microporous and Mesoporous Materials 33 (1999) 148

which will be useful in certain types of reaction.

is obtained. This marginal

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