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REACTION
NETWORK
AND KINETICS
OF 0-XYLENE
V,CJ,/TiO2 (ANATASE)
CATALYSTS
Israel E. WACHS*
Intermediates
08801,
Technology
Division,
OXIDATION
Exxon Chemical
87
TO PHTHALIC
Company,
ANHYDRIDE
Annandale,
OVER
New Jersey
U.S.A.
*Department
of Chemical
Bethlehem,
(Received
PA 18015,
13 August
Engineering,
Whitaker
Laboratory
#5, Lehigh
University,
U.S.A.
1986, accepted
22 December
1986).
ABSTRACT
The reaction network of o-xylene oxidation to phthalic anhydride over V205/Ti02
(anatase) catalysts was determined in the present investigation.
The detailed oxvlene conversion/oroduct
selectivitv data obtained demonstrate that ohthalic
anhydride is not produced from the d4rect oxidation of o-xylene over V205/Ti02
(anatase) catalysts, but indirectly via a series of consecutive reaction steps
involving o-tolualdehyde
and phthaiide intermediates.
The maleic anhydride byproduct is produced from the over-oxidation
of phthalic anhydride. The influence
of the two reactive sites in V205/Ti02 (anatase) catalysts, surface vanadium oxide
monolayer and V705 crystallites,
upon the o-xylene oxidation reaction were obtained
for moderate am6unt.s of vanadium oxide by varying the crystalline V2O5 content of
the catalysts. The initial reaction step of the oartial oxidation of o-xvlene to
o-tolualdehyde
occurs almost exclusively over the surface vanadium oxide-monolayer.
The o-tolualdehyde
intermediate
is directly converted to phthalic anhydride
primarily over the surface vanadium oxide monolayer and to phthalide over both
the surface vanadium oxide monolayer and the V205 crystallites.
The partial
oxidation of phthalide to phthalic anhydride mostly occurs over the monolayer
of surface vanadium oxide. The over-oxidation
of phthalic anhydride to maleic
anhydride also occurs primarily over the monolayer of surface vanadium oxide.
The non-selective
formation of the combustion products, CO and CO2, primarily
occurs from the direct oxidation of o-xylene over the monolayer of surface
vanadium oxide. The turnover rate for o-xylene oxidation over V205/Ti02(anatase)
catalvsts is determined for the first time, and found to be ~1 x low3 molecules
site-1 s-1 for the experimental
conditions used in the present study. The apparent
activation energy for the conversion of o-xylene to all products is found to be
%32 kcal mole-l.
INTRODUCTION
The complex
V205/Ti02
reaction
(anatase)
network
catalysts
[l-7]. A generalized
reaction
the probable
pathways
by different
investigators
propose
scheme
is presented
of reaction
of o-xylene
for o-xylene
in Figure
oxidation
1. The various
1 [l-7].
product
and phthalide
and other
to phthalic
of several
in Figure
anhydride
0166-9834/87/$03.50
oxidation
anhydride
recent
which
includes
reaction
steps
all
proposed
Some investigators
intermediates
investigators
over
investigations
propose
by a series
(reaction
steps
that phthalic
88
0
Maleic Anhydride
0
Maleic
Reaction
Investigators
& Foster
FIGURE
Generalized
(anatase)
x
x
x
x
x
x
reaction
catalysts
Steps
10
11
x
x
x
X
x
x
x
x
for o-xylene
reaction
12
network
Anhydride
oxidation
steps proposed
over V205/Ti02
by different
investi-
gators.
anhydride
can be formed
step 6) [1,3,5,7].
of the maleic
direct
directly
Similar
anhydride
results
conditions.
containing
of these
(reaction
different
kinds of promoters
studies were
also performed
reactors
where
the observed
results.
In order
the oxidation
(anatase)
reaction
steps
catalysts,
difficulty
performed
transfer
catalysts
Several
in commercial
issues we decided
over unpromoted
isothermal
or
experimental
V205/Ti02
conditions
limitations
anhydride
and under
with
types of carriers.
some of these
to phthalic
a carrier,
1,2,3,4)
in comparing
were
under non-isothermal
to resolve
of o-xylene
without
(reaction
and different
(reaction
of o-xylene
size tubular
examine
paths
series
byproduct:
the above
reaction
reaction
to
V,O,/TiO2
conditions.
EXPERIMENTAL
The unsupported
V205/Ti02
described
possessed
a surface
contain
(anatase)
(anatase)
catalysts
was obtained
were
prepared
from Mobay
(anatase)
as previously
Corporation,
support
and
was found
0.15 wt% K, 0.10 wt% P, 0.10 wt% Al and 0.16 wt% Si as determined
absorption.
The V205/Ti02
in an aqueous
solution
excess water
was allowed
(anatase)
of oxalic
catalysts
to evaporate
were prepared
in oxygen
at %65"C.
for 2 h
by dissolving
the titania
The catalysts
at 450C.
to
by atomic
V205
support.
The
were subsequently
89
The performance
xylene
of the V205/Ti02
was examined
were examined
(anatase)
in the reactor
catalysts
unit previously
with
1.25 mole%
velocity
obtained
by varying
temperature.
passed
through
the reaction
an o-xylene
analyzed
concentration
immersed
in a molten
effluent
was analyzed
reaction
products.
tolualdehyde,
including
present
during
o.d.,
analyzed
maleic
anhydride
three
was always
anhydride,
and benzoic
startup
and overnight
the center.
throughout
catalyst
steel)
(corresponding
The remaining
inserted
volume
was filled
Blank
to o-xylene
oxidation
effluent
was
The
with N2
located
(0.5 in.
at
the temperature
the reactor
with 2 cm3 of
a particle
This catalyst
the length
with 3 mm glass
runs showed
they were
The reactor
monitored
(anatase)
along
products,
blanketed
in. thermowell
and the
feed analyses.
was usually
The reactor
to 1.96 g of V205/Ti02
to give an isothermal
reactor
the reactor
in the thermowell
the desired
anhydride,
because
phthalic
ignored
by several
The
of the reactor
Other
while
After
conversions
were
on-line
to the reactor
At each temperature
water
detector.
acid, were
the reactor
observed
A thermocouple
the catalyst
and entered
within
components.
for o-xylene
products
rate was
by a calibrated
balance
316 stainless
RESULTS
reaction
were
flow
controlled
Hi Tech)
typically
carbon
The main
in conversion
conductivity
(DuPont
in a temperature
phthalide,
Changes
with a thermal
of o-
in air, at a space
equipped
was established,
salt
citraconic
described
o-xylene
immersed
of the o-xylenelair
gas chromatograph
gas chromatograph
o-xylene
generator
diameter
dilution
of the catalyst
beads
walls
and beads to be
at the temperature
range
bed.
investigated.
AND DISCUSSION
The product
selectivity
7% V205/Ti02(anatase)
2. The conversion
(see Figure
the major
product.
was varied
6). At very
reaction
Tar formation
phthalide
and maleic
by changing
approaching
very rapidly
bed
zero % conversion,
over V205/Ti02
of o-xylene
to ~20%,
in Figure
of the catalyst
of o-xylene
is increased
decreases
of o-xylene,
for an unsupported
is presented
conversion
conditions
the temperature
are o-tolualdehyde,
anhydride
of o-xylene
of o-xylene
isothermal
at low conversions
vity approaches
under
low conversions
products
catalysts
conversion
as a function
catalyst
approaches
the selectivity
with o-xylene
(anatase)
region
anhydride
selecti-
zero. As the
to o-tolualdehyde
conversion,
and
90
90
7hV~0dTiO~ (Anatase)
90 -
O-Xylene Conversion, O?
FIGURE
The product
V20S/Pi02(anatase)
vity to phthalic
behavior
anhydride
of the o-xylene
tolualdehyde,
oxidation,
secondary
Further
which
in the phthalide
and decreases
selectivity
formation.
However,
anhydride
production
with
tolualdehyde.
consistent
with
in a parallel
of phthalide
increases
anhydride
anhydride
formation
probably
the behavior
[9,10].
reaction
results
partial
expected
The phthalide
reaction
varied).
The constant
conversion
where
stream.
oxidation
at very
products
for a series
anhydride
selectivity
towards
high conversions
COx as a function
anhydride.
conversion
is
consecutive
is probably
evidence
found
from o-tolualde-
can be produced
(additional
that
of o-
catalysts
to o-xylene
however,
is not present,
of phthalic
of first-order
intermediate,
for phthalic
oxidation
produced
that
anhydride
suggests
over V20S/Ti02
the over-oxidation
of o-xylene
suggests
phthalide
This
towards
The maximum
responsible
is only observed
at low conversions
phthalide.
intermediate
oxidation
are the
reactant.
the selectivity
towards
from
of o-xylene
anhydride
in the product
directly
products
The
that o-
o-xylene
of o-tolualdehyde
of the o-xylene
steps
increasing
can be produced
and most
The response
of o-xylene
the selectivity
is present
and phthalic
for 7%
conversion.
suggest
and maleic
Studies
that phthalide
directly
in the reaction
phthalide
anhydride
anhydride
phthalide
is an intermediate
phthalic
conversion
with o-xylene
with conversion
anhydride,
in the conversion
anhydride,
some phthalic
of o-xylene
increases
products
increase
phthalide
as a function
and phthalide
reaction
phthalic
reaction
selectivity
catalyst.
produced
independently
of the catalyst
of o-xylene
is
conversion
91
Tar +
CO,+H,O
Maleic
Anhydride
4
Phthalide
FIGURE 3
Reaction
V205/Ti02
(anatase)
suggests
that almost
little
network
by the significantly
tolualdehyde
over V205/Ti02
with supported
V205/Ti02
and by varying
conversion
The detailed
present
anhydride,
V205/Ti02
steps.
o-xylene
investigation
maleic
results
based on their
employed
experimental
by these authors,
of o-xylene
conditions
conditions.
and Ivanov
over V205/Ti02
minimized
[5], at Skrzypek
directly
integral
fixed
fluidized
catalyst
regime
phthalic
residence
An examination
microreactors
operating
anhydride
of o-xylene
that reaction
anhydride
over
over V205/Ti02
article
with the
of the experimental
apparatus
products
These
[6]
studies,
catalyst-basket
close
review
reaction
that phthalic
reactors
that these
and maleic
anhydride
at low conversions
oxidation
products
can be
however,
to the continuous
not surprising
reaction
network
[I], Calderbank
of o-xylene.
spinning
in the
as well as
suggests
[1,7],
anhydride,
in the literature,
and Froment
conditions,
in the reactor.
in their comprehensive
findings.
bed reactors
agree with
catalysts
were obtained
data obtained
study suggest
and Blanchard
of Herten
results
oxidation
by Vanhove
(anatase)
is subof o-
as described
This
non-isothermal
to phthalic
findings
and Foster
residence
The results
produced
reactor
proposed
of o-xylene
synthesis
kinetic
that phthalic
but indirectly
by Wainwright
networks
over
selectivity
demonstrates
The present
from o-xylene
of the present
(anatase)
reaction
anhydride
intermediates.
[2]. Similar
conversion/product
clearly
anhydride
directly
oxidized
under moderately
via residence
in Figure
proposed
to phthalic
selectivities
catalysts
catalysts,
catalysts,
The kinetic
network
higher
is not produced
(anatase)
on phthalic
oxidation
catalysts.
COx is produced
stantiated
for o-xylene
stirred
studies
of o-xylene.
in the spinning
used
[33 and
tank
observed
The long
catalyst-basket
92
g
2
60
55 I
CATALYST COMPOSITION
e 1.9% V,O,ITiO, (A)
q 3 % V,06/Ti0, (A)
l 7 % V,O,/TiO* (A)
0 21 % V,OJTiO, (A)
404
65
65
70
75
80
85
90
95
100
0-Xylene Conversion
FIGURE
Influence
G8-oxygenate
of V205 content
(o-tolualdehyde,
microreactor
intermediate
products
on the walls
of these reactors
presence
of external
conducted
in integral
be to further
diffusion
convert
gradients
(anatase)
Recent
anhydride
gradients
in highly
the partial
characterization
studies
in V205/Ti02
(anatase)
(350-575C)
[6,8,11-181.
These
the properties
crystallites
vanadium
(anatase)
catalysts
[IO]. Reaction
and reactant
The
concentrations
such as o-xylene
effect
The presence
integral
oxidation
oxidation,
would
of external
fixed
of phthalic
o-xylene
oxide
support.
Thus,
vanadium
bed reactors
anhydride
and/or
over V205/Ti02
corresponds
of surface
increases
vanadium
V205/Ti02
oxide
small
oxide
content
the amount
oxide
study,
and crystalline
a monolayer
on the Ti02
of the surface
vanadium
of V205/Ti02
(anatase)
oxide
of
are present
of vanadium
of
as small
crystallites
to the monolayer
modifies
a monolayer
as well
(anatase)
species
oxide
temperatures
(anatase)
by forming
coverage,
the vanadium
that Ti02
to %1.9%
in addition
showed
of vanadium
at moderate
vanadium
Above monolayer
above monolayer
amount
support
calcined
oxide phase
oxide content
(anatase)
increasing
have revealed
catalysts
coordinated
on the support
species.
species
the vanadium
layer coverage,
present
oxide
V205 depends,on
surface
during
investigations
of the supported
vanadium
support.
products.
employing
of these
catalysts.
are present
surface
anhydride
at low conversions
conversion
this situation.
reactions,
oxidation
responsible
exacerbate
upon the
selectivity.
in the further
in temperature
catalysts
anhydride)
and/or maleic
exothermic
in the investigations
likely
anhydride
result
could further
diffusion
(anatase)
and phthalic
[5] would
to phthalic
of V205/Ti02
phthalide
present
oxide
as VZ05
93
Tolualdehyde
Phthalide
0
A
.
.
Catalyst Composition
7% V2051Ti02 (A)
21% V105/Ti02 (A)
3% V205/Ti02 (A)
f
50
60
70
80
o-Xylene Conversion
FIGURE
Influence
o-tolualdehyde
crystallites.
of V205 content
and phthalide
The previous
a higher
of o-xylene
complete
because
of surface
the exposed
of the reaction
the catalytic
activity
during
of this phase.
o-xylene
oxidation
vities
at partial
dramatic
drop
monolayer
surface
conversion
coverage,
vanadium
greater
complete
coverage
catalytic
conversion
conditions.
sample,
of o-xylene
Significant
decrease
kinetically
underlying
significant
surface
(anatase)
is approached
amounts
anhydride
affect
selectivity)
catalysts
exhibit
Below monolayer
improvement
is shown
very
in Figure
similar
coverage
there
suggests
cover
is a
above
that the
titania
contents
are necessary
to assure
titania
sites.
The differences
in the
become
somewhat
more pronounced
of crystalline
performance
oxide monolayer
severity
because
possess
as complete
of the reaction
(anatase)
[8,13,18].
4.
selecti-
in selectivity
(anatase),
selectivity
oxide
and intrinsically
vanadium
amounts
of these samples
Moderate
do not significantly
and phthalic
catalysts
higher vanadium
the catalytic
deposition).
surface
performance
carbon
catalysts
oxide monolayer
(combustion
of o-xylene.
in selectivity
inferior
reactions
of V205 content
(anatase)
very
in undesirable
conversion
over V205/Ti02
exhibit
less than a
selectivity)
The effect
possessing
however,
and that it
anhydride
(anatase)
(o-xylene
because
catalysts
vanadium
and phthalic
and possibly
in V205/Ti02
performance
upon the
of hydrocarbons
than crystalline
oxide,
conversion
sites result
intermediates
of such catalysts
(anatase)
vanadium
(o-xylene
titania
V205
catalysts
oxidation
and selectivity
V205/Ti02
performance
(anatase)
also demonstrated
[8,13,18].
of crystalline
studies
activity
monolayer
catalytic
of V205/Ti02
selectivities.
selectivity
than the
94
Additional
insights
phthalic
anhydride
reaction
studies
of V205 content
in Figure
over V,O,/TiO,
5 as a function
addition
(anatase).
These
a monolayer
is slightly
of surface
to phthalic
anhydride
is also sensitive
for V,O,/TiO2
vanadium
mediate
phthalide
vanadium
and phthalide
of o-xylene.
vanadium
amounts
monolayer,
oxide monolayer,
phthalide
(anatase)
of phthalide
selectivity
to the slightly
(anatase)
catalyst.
identical
o-toIua\dehyde
suggests
reaction
step is enhanced
relative
reaction
dependence
content
is probably
produced
V20,-/Ti02 (anatase)
V205 content
monolayer
catalysts.
(anatase)
conversions
its formation
is primarily
The slight
oxide
but differing
is also independent
associated
of the 21%
samples
o-xylene
amounts
anhydride
to phthalic
intermediate
oxidation
constant
associated
selectivity
the
V205
observed
and suggests
of surface
over
with the
with
of crystalline
of V205 content
This
anhydride
is fairly
exhibit
selectivity.
selectivity
is primarily
in
from 7% to 21%
to phthalic
step during
much higher
decrease
the o-tolualdehyde
statement
containing
oxide
exhibit
selectivity
of the phthalide
for
to the
vanadium
(anatase)
phthalide
and its
was detected
content
to the o-tolualdehyde
reaction
and these
The catalysts
(anatase),
lower $-oxygenate
catalysts.
high o-xylene
stream.
vanadium
however,
(anatase).
the vanadium
the earlier
of
inter-
support
V205 in addition
to the surface
of V205 crystallites
in a parallel
and suggests
of surface
in V205/Ti02
supports
a monolayer
catalyst,
intermediate,
selectivity,
crystalline
the phthalide
of the titania
of crystalline
in the product
intermediates
V205/Ti02
crystalline
approximately
nature
3% V205/Ti02
upon increasing
selectivity
than unsupported,
(anatase),
V205 in addition
of crystalline
in
The phthalide
oxide monolayer
to the specific
small amounts
7% V205/Ti02
concentrations
catalysts
containing
species,
V205
of V 0 crystallites,
and
25
are in agreement with the obser-
containing
impurities
the catalyst
oxide
crystalline
to the content
1.9% V205/TiO2
species,
may be related
associated
surface
oxide
formation
differences
(anatase)
surface
of o-xylene,
V205 catalysts
higher
At a given conversion
containing
increases
vation
from
stream
to
oxide monolayer,
suggest
of' o-tolua'ldehyde
in the product
oxidation
stream
vanadium
results
conversion.
in the product
approximately
(anatase),
to the surface
version
of o-xylene
selectivity
containing
1.9% V205/Ti02
of o-xylene
catalysts
the o-tolualdehyde
catalyst
network
(anatase)
at
that
vanadium
oxide.
95
TABLE
0-xylene
oxidation
moderate
amounts
Reaction
step
o-xylene
reaction
of crystalline
V20S in V205/Ti02
reactive
(anatase)
Most Probable
o-tolualdehyde
-f phthalide
phthalic
anhydride
reactive
sites
Surface
vanadium
Surface
vanadium
oxide monolayer
Surface
vanadium
oxide monolayer
o-tolualdehyde
o-tolualdehyde
sites for
catalysts.
oxide monolayer
-f phthalic
anhydride
anhydride
-f maleic
and COx
o-xylene
COx
21
*0-
ii!
s!
10
E,I
- 32 22
I kcalfmole
,
1.68
1.66
study
reveals
the o-xylene
oxidation
the surface
vanadium
the surface
to either
slightly
of a-xylene
of o-xylene
vanadium
retard
the conversion
with temperature
in V205/Ti02
network.
vanadium
of o-xylene
reaction
can be performed
however,
occurs
The o-tolualdehyde
or phthalide
[8,13].
oxide monolayer
[8,13],
for the 7%
(anatase)
The initial
to o-tolualdehyde
oxide monolayer.
anhydride
1.78
1.76
x IO-3,K
to o-tolualdehyde
of the surface
1.74
conversion
reaction
oxide monolayer
activity
phthalic
1.72
oxidation
the partial
oxidation
2 (Anatase)
\,
1.70
catalyst.
crystallites
(anatase)
partial
30-
Arrhenius
higher
oxide monolayer
40-
cantly
oxide monolayer
vanadium
V205/Ti02
The above
vanadium
Surface
50-
l/Temp.
affect
Surface
1.64
FIGURE
oxide monolayer
7%V205/T10 .
:\
60
z
s^
._
r?
:
E
0
is
vanadium
9000
80
70
Surface
anhydride
almost
suggests
by either
The signifi-
that the
exclusively
intermediate
and enhance
step of
of o-tolualdehyde
catalysts
over
is converted
appear
the relative
to
formation
96
TABLE
Apparent
Ti02
activation
(anatase)
energies
to products
over v205/
catalysts.
Investigators
Herten
of o-xylene
Apparent
-1
mole
and Froment
(1968)
Calderbank
et al. (1977)
Wainwright
and Hoffmman
activation
energies/kcal
16
26 at 370-440C
14 at 440-550C
(1977)
27
(1982)
27
et al.
(1985)
20-26
(1986)
32
of phthalide
compared
tolualdehyde
to phthalic
vanadium
to phthalic
anhydride
oxide monolayer
is associated
anhydride.
appears
can be performed
associated
oxidation
vanadium
version
The above
reaction
reaction
are listed
in Table
An Arrhenius
suggests
V205
(anatase)
Previously
with
produced
vanadium
the over-
o-xylene
for moderate
The origin
not well
corresponding
con-
oxide
catalysts.
is currently
is
of this
understood.
reactive
sites
kinetics
to all reaction
activation
catalysts
gradients
oxidation,
to yield
apparent
(anatase)
Diffusion
such as o-xylene
of o-xylene
products
over V205/Ti02
the intrinsic
(anatase)
anhydride
1.
reactions
of surface
area
suggests
Similarly,
is associated
and
oxide mono-
surface
to phthalic
COx selectivity
probable
anhydride
vanadium
and effective
oxide monolayer.
anhydride
unfortunately,
to phthalide
to V205 crystallites
intermediate
constant
in V205/Ti02
step,
of 32 f 2 kcal mole
of o-xylene
from
The fairly
the 7% V205/Ti02
this catalyst,
vanadium
to maleic
of crystalline
non-selective
energy
anhydride
oxide monolayer.
activity
of o-
to phthalic
the surface
compared
of the phthalide
of phthalic
oxidation
amounts
oxidation
oxidized
by either
The higher
occur
oxidation
of o-tolualdehyde
oxide monolayer
is further
oxide monolayer
the partial
to primarily
oxidation
vanadium
of the surface
Thus,
energies
are listed
apparent
lower apparent
activation
activation
activation
over
in Table
can be present
for
2 and range
in highly
exothermic
energies
energies
conversion
97
reported
suggest
by Herten
that diffusion
used by these
however,
gradients
investigators.
energies.
lower apparent
non-isothermal
discussion
to minimize
conditions
residence
(references
energies,
27-32
absence
of phthalic
anhydride
and/or maleic
over V205/Ti02
Turnover
rates
(anatase)
(the number
are routinely
measured
chemisorption
techniques
atoms
between
chemisorption
techniques,
of exposed
containing
supported
vanadium
information
vanadium
V205/Ti02
however,
report
and
high
and the
of o-
by metals.
and V205/Ti02
for supported
catalysts
over V205/Ti02
molecule
of vanadium
sites
conditions
known.
metal
oxide
the turnover
occurs
rates
[211. The
us to determine
(anatase)
oxides
in the case of
of the o-xylene
has
et al. determined
of o-xylene
an easy
The selective
presented
oxide sites
of surface
and consequently
can be determined
conditions
selective
the number
of catalysis
over V205/A1203
ponds to %2.5 x 10
to determine
usually
oxide
per active
oxide catalysts
vanadium
study)
catalysts
investigators,
in metal
catalysts.
of reactions
of active
reacted
unfortunately,
oxide monolayers
oxide
The kinetic
products
at low conversions
sites
and experimental
the turnover
The number
anhydride
metallic
to the progress
sites,
over V205/Ti02
network).
of exposed
catalysts
for a number
of molecules
contributed
somewhat
and/or
catalysts.
significantly
-1
apparent
anhydride
kcal mole
comparison
of o-xylene
activation
systems
that reported
that phthalic
on reaction
apparent
xylene
in the reactor
also claimed
et al. [7]
at low conversions
(see earlier
that appeared
present
influenced
energies
were present
catalysts
The promoters
Interestingly,
activation
anhydride
(anatase)
studies
[I], Calderbank
activation
maleic
and Froment
catalysts.
of surface
almost
in the monolayer
of 1.96 gms of
exclusivecorres-
1.9%
(anatase).
conditions
is achieved
at 325C (see Figure 6). From these figures one obtains a turnover
-3
-1 -1
o-xylene molecules site
for the present experimental
s
rate of $1 x 10
conditions.
The present
with
for
study
oxidation
the
the turnover
reports
the first
over V205/TiO2
supported
vanadium
rates measured
determination
(anatase)
oxide
for metal
of the turnover
catalysts.
The turnover
monolayer
catalysts
catalysts
[20].
agree
very
98
ACKNOWLEDGEMENTS
The assistance
catalysts,
of C.C. Chersich
and P. Chiasson
in the preparation
in obtaining
the catalytic
of the V205/TiO2
(anatase)
appreciated.
REFERENCES
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P.H. Calderbank, K. Chandrasekharan
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