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Applied Catalysis, 31(1987) 87-98

Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

REACTION

NETWORK

AND KINETICS

OF 0-XYLENE

V,CJ,/TiO2 (ANATASE)

CATALYSTS

Ramzi Y. SALEH and

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

that the desired

of reaction

of o-xylene

for o-xylene

in Figure

are also shown


phthalic

I,2 and 3, or 1 and 9) [2,4,6],

oxidation

1. The various
1 [l-7].

product

and phthalide

and other

to phthalic

of several

in Figure

anhydride

steps via o-tolualdehyde

0166-9834/87/$03.50

oxidation

has been the subject

anhydride

recent

which

includes

reaction

steps

can only be formed

0 1987 Elsevier Science Publishers B.V.

all
proposed

Some investigators

intermediates

investigators

over

investigations

propose

by a series

(reaction

steps

that phthalic

88

0
Maleic Anhydride

0
Maleic

Reaction
Investigators

Herten & Froment

& Foster

Yabrov & lvanov


Skrzypek et al.

FIGURE

Generalized

(anatase)

x
x

x
x

x
x

reaction

catalysts

Van Hove 8 Blanchard


Calderbank et al.
Wainwright

Steps

10

11

x
x

x
X

x
x

x
x

for o-xylene

reaction

12

network

and the various

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

may have affected

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

under very different

were

under non-isothermal

to resolve

of o-xylene
without

(reaction

and different

heat and mass

(reaction

for the formation

is that they were performed


studies

of o-xylene

have been proposed

step 12). The major

Some of these reaction

size tubular

examine

paths
series

byproduct:

one step reaction

the above

in one step from the oxidation

reaction

reaction

to

V,O,/TiO2
conditions.

EXPERIMENTAL
The unsupported

V205/Ti02

described

[8]. The TiO2

possessed

a surface

contain

(anatase)

(anatase)

catalysts

was obtained

were

prepared

from Mobay

area of Q9 m * g-'. The Ti02

(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

dried at 110C and calcined

were prepared

acid and impregnating

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

for this reaction

catalysts

unit previously

with

1.25 mole%

velocity

of 2760 h-' and between

320 and 370C.

obtained

by varying

temperature.

passed

through

the reaction

an o-xylene

bath. A slip stream


multicolumn

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

and 2 cm3 at the bottom).


inert with respect

was filled

Blank

to o-xylene

oxidation

effluent

was
The

with N2

located

(0.5 in.

at

the temperature

to the salt bath temperature


was packed
having

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

with 8 cm3 of 0.5 mm glass beads.


profile

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

the feed was being analyzed.

from the bottom.

of 0.4 - 0.7 mm) diluted

phthalic

ignored

by several

The

of the reactor

Other

5%. The reactor

while

After

conversions

were

on-line

to the reactor

CD, CO2 and water.

At each temperature

water

detector.

acid, were

bed. The feed was preheated

the reactor

ratio was found

observed

was fitted with a 0.125

A thermocouple
the catalyst

and entered

within

components.

for o-xylene

products

rate was

by a calibrated

bath. A slip stream

to five times followed

balance

316 stainless

RESULTS

reaction

were

flow

controlled

the feed was diverted

Hi Tech)

in very small quantities.

typically
carbon

The main

in conversion

conductivity

for all gases and organic

(DuPont

[8]. All catalysts

in a temperature

by the gas chromatograph

phthalide,

Changes

with a thermal

of o-

in air, at a space

feed was analyzed

equipped

was established,
salt

citraconic

described

o-xylene

Air at the desired

immersed

of the o-xylenelair

gas chromatograph

gas chromatograph
o-xylene

generator

for the oxidation

diameter

dilution

of the catalyst

beads

(2 cm3 at the top

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

and the phthalic

of o-xylene

to ~20%,

in Figure

of the catalyst

COx (CO2 and CO), and a tar by-

of o-xylene

are not present

is increased

decreases

of o-xylene,

for an unsupported

is presented

by Bond et al. [6]. In this low conversion

zero % as the conversion

the tar byproduct

conversion

conditions

the temperature

are o-tolualdehyde,

anhydride

of o-xylene

of o-xylene

isothermal

at low conversions

was also reported

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

and the selecti-

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

path will be provided

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

below when the V205 content

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

from the partial

is only observed

step since phthalic

at low conversions

phthalide.

intermediate

oxidation

are the

reactant.

the selectivity

towards

are both directly

from

of o-xylene

anhydride

that leads to phthalic

in the product
directly

products

The

that o-

from the o-xylene

o-xylene

is not the only

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

hyde [Z]. Maleic


of o-xylene

for 7%

conversion.

suggest

and maleic

since at very low conversions,

Studies

that phthalide

directly

in the reaction

phthalide

anhydride

anhydride

phthalide

are not derived

is an intermediate

phthalic

conversion

with o-xylene

with conversion

are the primary

anhydride,

in the conversion

anhydride,

some phthalic

of o-xylene

increases

products

COx and the tar byproduct

increase

phthalide

as a function

and phthalide

reaction

and that phthalic


products

phthalic

reaction

selectivity

catalyst.

produced

independently

for this parallel

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

all the COx is produced


from the partially

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

3 for the oxidation


catalysts.

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

et al. [7] suggest

microreactors

operating

[5]. It is, therefore,

anhydride

of o-xylene

that reaction

anhydride

over

over V205/Ti02

article
with the

of the experimental

apparatus

to study the oxidation

products

These

[6]

that their experimental


and non-isothermal
et al. [33, Yarbov
anhydride

studies,

catalyst-basket
close

review

reaction

[Z] and Bond and Konig

that phthalic

reactors

that these

and maleic

anhydride

at low conversions

time of the partial

oxidation

products

can be

however,

to the continuous

not surprising

reaction

network

are also consistent

[I], Calderbank

of o-xylene.

spinning

in the

as well as

the most probable

suggests

time of the reaction

[1,7],

anhydride,

in the literature,

and Froment

conditions,

in the reactor.

in their comprehensive

findings.

from the oxidation

bed reactors

agree with

catalysts

were obtained

data obtained

study suggest

and Blanchard

of Herten

results

oxidation

by Vanhove

(anatase)

is subof o-

via a series of consecutive

[4]. These findings

as described

and that very

This

non-isothermal

to phthalic

findings

and Foster

residence

The results

produced

reactor

proposed

from the direct

of o-xylene

synthesis

kinetic

that phthalic

but indirectly

by Wainwright

networks

over

for the oxidation

selectivity

demonstrates

The present

from o-xylene

time of the gases

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,

[S] and fluidized

microreactor

intermediate

products

on the walls

of these reactors

presence

of external

conducted

in integral

be to further
diffusion

convert

gradients

[I,71 are most


maleic

(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 V205 are also

of the surface

vanadium

of V205/Ti02

(anatase)

oxide

of

[8]. Below mono-

are present

of vanadium

of

as small

area of the TiOp

crystallites

to the monolayer

modifies

a monolayer
as well

(anatase)

species

oxide

temperatures

(anatase)

by forming

and the surface

coverage,

the vanadium

that Ti02

to the Ti02 support

to %1.9%

in addition

showed

of vanadium

at moderate

used in the present

vanadium

Above monolayer

above monolayer

amount

support

that two types

calcined

oxide phase

oxide content

(anatase)

increasing

have revealed
catalysts

coordinated

only the surface

on the support

species.

species

the vanadium

For the Ti02

layer coverage,

present

oxide

of V205. The relative

V205 depends,on

surface

during

investigations

of the supported

vanadium

support.

products.

employing

of these

catalysts.

are present

surface

anhydride

[IO], and the resulting

for the presence

at low conversions

conversion

this situation.

reactions,

oxidation

responsible

exacerbate

upon the

selectivity.

in the further

in temperature

fixed bed reactors

catalysts

anhydride)

and/or maleic

exothermic

in the investigations

likely

anhydride

result

could further

diffusion

(anatase)

and phthalic

[5] would

to phthalic

are known to be present

of V205/Ti02

phthalide

present

oxide

as VZ05

93

Tolualdehyde

Phthalide

0
A

.
.

1.9% V205/Ti02 (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

oxide was the active


possesses

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)

area and poor catalytic

catalysts
exhibit

Below monolayer
improvement

is shown

very

in Figure

similar

coverage

there

suggests

cover

is a
above

that the

all the exposed

titania

contents

are necessary

to assure

titania

sites.

The differences

in the

become

somewhat

more pronounced

due to the increased

of crystalline
performance

oxide monolayer

severity

V205, 21% V205/Ti02

because
possess

as complete

of the reaction
(anatase)

the V205 c%-ystallites become


a lower

[8,13,18].

4.

selecti-

in selectivity

(anatase),

selectivity

oxide

and intrinsically

vanadium

amounts

upon the C8-oxygenate

does not effectively

of these samples

Moderate

do not significantly

and phthalic

catalysts

higher vanadium

the catalytic

deposition).

surface

than 1.9% V205/Ti02

of the few remaining

performance

carbon

catalysts

[81. The slight

oxide monolayer

sites and that slightly

(combustion

of o-xylene.

in selectivity

inferior

reactions

of V205 content

(anatase)

very

in undesirable

conversion

over V205/Ti02

The 1.9%, 3% and 7% V205/Ti02

exhibit

less than a

selectivity)

of the low effective

The effect

possessing

however,

and that it

V205 for the oxidation

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

that the surface

oxidation

and selectivity

V205/Ti02

performance

(anatase)

also demonstrated

site for the partial

[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

into the reaction

over V,O,/TiO,

5 as a function

addition
(anatase).

These

are being compared

a monolayer

is slightly

of surface

to phthalic

anhydride

is also sensitive

for V,O,/TiO2

vanadium

mediate

was not observed

phthalide

vanadium

and phthalide

of o-xylene.

vanadium
amounts

monolayer,

oxide monolayer,

phthalide

(anatase)

of phthalide

selectivity

V205 may be related

to the slightly

(anatase)

catalyst.

identical

o-toIua\dehyde

suggests

that in the presence

reaction

step is enhanced

relative

reaction

step. The strong

dependence

content

is probably

produced

V20,-/Ti02 (anatase)
V205 content
monolayer

catalysts.

(anatase)

conversions

its formation

is primarily

The slight
oxide

but differing

oxide for moderate


The maleic

is also independent
associated

of the 21%

samples

o-xylene

amounts

anhydride

to phthalic

upon the V205

with the monolayer

intermediate

oxidation

constant

associated

selectivity

the

V205

observed

and suggests

of surface

over

with the
with

of crystalline

of V205 content

This

anhydride

that the phthalide

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

The CO, selectivity

catalysts.

high o-xylene

stream.

that COx formation

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,

The 3% and 7% V205/Ti02

selectivity,

crystalline

the phthalide

of the titania

of crystalline

in the product

intermediates

Bond and Konig did detect

and 21% V205/Ti02

V205/Ti02

crystalline

approximately

nature

3% V205/Ti02

upon increasing

selectivity

than unsupported,

(anatase),

V205 in addition

of crystalline

in

since the catalysts

The phthalide

oxide monolayer

to the specific

small amounts

7% V205/Ti02

concentrations

catalysts

over the range examined.

[6]. The phthalide

containing

species,

V205

of V 0 crystallites,
and
25
are in agreement with the obser-

containing

with their vanadium

impurities

the catalyst

oxide

crystalline

to the content

1.9% V205/TiO2

species,

may be related

associated

surface

oxide

formation

differences

(anatase)

[19]. For the catalyst

surface

of o-xylene,

lower for the

with V 0 content. These observations


25
made by Chandrasekharan
and Calderbank that the reaction

V205 catalysts

higher

At a given conversion

containing

increases
vation

from

3%, 7% and 21% V 0 /TiO


25
2
that the crystallites
slightly retard the con-

at the same conversion

stream

are less evident

to

oxide monolayer,

suggest

of' o-tolua'ldehyde

in the product

oxidation

are also obtained

stream

than the catalysts

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

in which the V 0 content of the catalyst is varied. The influence


25
upon the o-tolualdehyde
and phthalide selectivities
are presented

the o-tolualdehyde
catalyst

network

(anatase)

at
that

vanadium

oxide.

95
TABLE

0-xylene

oxidation

moderate

amounts

Reaction

step

o-xylene

reaction

steps and their corresponding

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

and V205 crystallites


phthalide
phthalic

-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

plot for o-xylene

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

or the V206 crystallites

to o-tolualdehyde

oxide monolayer.

anhydride

1.78

1.76

x IO-3,K

to o-tolualdehyde

of the surface

for the conversion

1.74

conversion

reaction

oxide monolayer

activity

phthalic

1.72

that the two sites

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

than the V205

[Z]. The V205 crystallites

of o-tolualdehyde

catalysts

over

is converted
appear

the relative

to

formation

96
TABLE

Apparent
Ti02

activation

(anatase)

energies

for the conversion

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

Bond and Konig


Skrzypek

(1977)

27

(1982)

27

et al.

(1985)

20-26

Saleh and Wachs

(1986)

32

of phthalide

compared

tolualdehyde

to phthalic

vanadium

to phthalic
anhydride

oxide monolayer

is associated

anhydride.
appears

and the partial

with both the surface


intermediate

this step apparently

can be performed

layer or the V205 crystallites.


vanadium

that the partial


mostly

associated

oxidation
vanadium
version

and V205 content


of o-xylene

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-

from the direct

oxide

catalysts.

is currently

is

with the surface

of this

understood.

reactive

sites

kinetics

to all reaction

activation

catalysts

gradients

oxidation,

to yield

lower [IO]. The somewhat

apparent

(anatase)

Diffusion

such as o-xylene

of o-xylene

products

catalyst is presented in Figure 6. An apparent


-1
1s determined for the conversion of o-xylene
reported

over V205/Ti02

the intrinsic

(anatase)

anhydride

1.

13-27 kcal mole-'.

reactions

of surface

area

suggests

Similarly,

is associated

and

oxide mono-

surface

to phthalic

COx selectivity

probable

anhydride

vanadium

and effective

that COx is primarily

steps and their most

and the V205 crystal-

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

plot for the conversion

the 7% V205/Ti02

this catalyst,

vanadium

to maleic

over the monolayer

of crystalline

non-selective

energy

anhydride

oxide monolayer.

activity

of o-

over the surface

to phthalic

the surface

compared

of the phthalide

with the surface

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

lites. The phthalide

of the surface

Thus,

energies

are listed

and these gradients

apparent

lower apparent

activation
activation

activation
over

for the conversion

in Table

can be present

for

2 and range

in highly

exothermic

have been shown to mask

energies
energies

that are significantly


for o-xylene

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,

and the number


The number

of exposed
containing

supported

vanadium

information

vanadium

ly over the monolayer.


20

V205/Ti02

however,

report

and

high
and the
of o-

by metals.

and V205/Ti02

for supported

The total number

catalysts

over V205/Ti02

molecule

of vanadium

sites

conditions

known.

metal

oxide

the turnover

occurs

rates

[211. The
us to determine

(anatase)

is given by the monolayer

sites for our experimental

oxides

in the case of

above also allow

of the o-xylene

has

are not generally

et al. determined

of o-xylene

an easy

The selective

do not work with metal

presented

oxide sites

of surface

and consequently

can be determined

conditions

selective

the number

and have been applied


Murakami

site per second)


because

rate is that it permits

of catalysis

over V205/A1203

since the oxidation

ponds to %2.5 x 10

to determine

usually

rate for the oxidation

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).

, for o-xylene conversion

of using the turnover

of exposed

catalysts

for a number

of molecules

the work of different

contributed

somewhat
and/or

catalysts.

have been developed

significantly

-1

apparent

anhydride

time of the reaction

kcal mole

for many different

[20]. The advantage

comparison

of o-xylene

4,6 and the present

activation

systems

that reported

that phthalic

on reaction

apparent

xylene

in the reactor

some of the determined

also claimed

et al. [7]

in some of these catalysts,

the same investigators

at low conversions

(see earlier

that appeared

present

influenced

energies

were present

catalysts

et al. [3] and Skrzpek

may have been present

The promoters

Interestingly,

activation

anhydride

(anatase)
studies

[I], Calderbank

may also have partially

activation

maleic

and Froment

catalysts.

of surface
almost

in the monolayer
of 1.96 gms of

exclusivecorres-

1.9%

(anatase).

The total amount of o-xylene converted for our experimental


17
corresponds to 3 x IO
o-xylene molecules/set
at 60% conversion which

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

rate for o-xylene


rates measured
well

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)

data are greatly

appreciated.

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