Applied Catalysis A: General, 83 (1992) 75-86 75

Elsevier Science Publishers B.V., Amsterdam

APCAT 2227

Hydrodealkylation reaction of ethylbenzene over a

supported nickel-tungsten catalyst

Yosoon Songl, Gon Seo’ and Son-Ki Ihm

Department of Chemical Engineering, Korea Advanced Institute of Science and Technology,
373-1, Kusung-dong, Yusung-94, Taejeon 305-701 (South Korea)
(Received 14 August 1991, revised manuscriptreceived5 November 1991)

Abstract

The hydrodealkylationreaction of ethylbenxeneover a supportednickel-tungsten catalyst has been

studied. Over a supported nickel catalyst, the dominant ring opening reaction of benzene over 400°C
led to high methaneselectivity.On the other hand, over a cosupportednickel-tungstencatalyst,the ring
openingreactionwas suppressed,thus resultingin high benzeneselectivity.The activity and selectivities
of the hydrodealkylationreaction were dependent on the degree of reduction of tungsten. Using an
oxygen titration method, the presenceof nickel in the cosupportedcatalystawas confirmed to promote
the reduction of tungsten.The cosupported nickel-tungsten catalystssuppressedthe decomposition of
dioxane in temperature-programmeddesorption experimentsmore than the supportednickel catalyst.

Keywords: ethylbenzene,hydrodealkylation,nickel-tungsten.

INTRODUCTION

Since the demand for benzene in the petrochemical industry far exceeds
its production by distillation of crude oil, processes for the disproportionation
of to’luene and hydrodealkylation of alkylbenzene mixtures have been devel-
oped to fill the gap [ 11. Alkylbenzene mixtures are produced from catalytic
reforming or light alkene production processes as by-products. The separation
process of the alkylbenzene mixture into each component is not feasible eco-
nomically because the mixture is comprised of too many components and their
boiling points are too close. Therefore, the production of benzene by hydro-
dealkylation of the alkylbenzene mixture has an economic edge.
Selectivity to benzene is a crucial criterion in selecting a catalyst for the
hydrodealkylation process of the alkylbenzene mixture. The catalyst should

Correspondence to: Dr. S.-K. Ihm, Department of Chemical Engineering, Korea Advanced Insti-
tute of Science and Technology, 373-1, Kusung-dong, Yusung-94, Taejeon 305-701, South Korea.
‘Present address: Department of Chemical Technology, Chonnam National University Kwang-ju
500-757, South Korea.
76 Y. Song et al./Appl. Catal. A 83 (1992) 75-86

activate hydrogen in order to remove the alkyl groups from the alkylbenzene,
but this should not go so far as to destroying the benzene ring. Supported nickel
catalysts are reported to show good performance for hydrodealkylation of tol-
uene due to their ability to activate hydrogen [ 2-41. The hydrodealkylation of
ethylbenzene is also studied using supported nickel catalysts on silica, alumina
and silica-alumina [ 51. However, excessive activation of hydrogen results in
the hydrocracking of a benzene ring, so it is common practice to cosupport
other metals like chromium, cobalt, tungsten or molybdenum with nickel in
order to control the selectivity. It has also been reported that the acidity of the
support has a substantial effect on the selectivity. Results are available for
silica-alumina, zeolite, and Lewis-type acid catalysts [ 11.
Among the catalysts, supported nickel-tungsten catalysts showed not only
high activity for hydrodealkylation but also good benzene selectivity [ 51. The
selectivity varies depending on the ratio of the amount of nickel impregnated
to that of tungsten. Tungsten has varying states of oxidation (e.g. 6 + ,5 + ,4 +
and 0), and in general tends to defy reduction. The reduction state of tungsten
supported on y-alumina is reported to depend on the amount of tungsten oxide
impregnated, when impregnation exceeded the thickness of a monolayer, an
intermediate state W4+ is observed [ 61. In cosupported nickel-tungsten cat-
alysts, spillover of hydrogen from nickel to tungsten is known to promote the
reduction of tungsten [ 71.
This study aims to investigate the hydrodealkylation of ethylbenzene over
supported nickel-tungsten catalysts, focusing on the effect of tungsten upon
the activity and the selectivity of the reaction. The extent of the reduction of
the catalysts are examined by oxygen titration, and compared for differing
reduction treatments. The catalytic activity of nickel for decomposition is in-
vestigated through temperature-programmed desorption (TPD ) (decompo-
sition) of dioxane. These results are discussed in relation to the characteristics
of catalysts for hydrodealkylation.

EXPERIMENTAL

Preparation of catalysts

The catalysts were prepared by a conventional incipient wetness technique

using aqueous solutions of nickel nitrate (Wako, GR) and/or phosphotungstic
acid (Fluka, AG.). Solutions containing the required amount of metals to be
impregnated were absorbed into a silica-alumina support (Davidson Chemi-
cals, 400 m2/g, alumina content 13%) and a silica support (150 m”/g). They
were slowly dried in a rotary evaporator at 6O”C, and further in an oven at
120’ C for one day. The catalysts were calcined at 550’ C for 7 h in an air
environment to decompose the metal salts to either NiO or W03. The decom-
Y. Song et al.fAppl. Catal. A 83 (1992) 75-86 17

position was confirmed by measuring the weight loss during the calcination
process using a thermal gravimetric analyzer (Rigaku, Model CN807El) .
The naming convention for the prepared catalysts is as follows. The names
of the impregnated metals are followed by their weight percents in parentheses
with respect to the support. The support name is represented by /SA, which is
an abbreviation of silica alumina (for example, Ni-W (5 : 15) /SA).

Reaction

The hydrodealkylation reaction of ethylbenzene was carried out in a con-

ventional fixed-bed flow reactor. The reactor was made of a l/4 in O.D. stain-
less steel tube with catalysts packed in the middle. A thermocouple was in-
serted in the reactor to monitor and control the temperature of the catalyst
bed using a PID controller (Research Industry, Model 63911). All the flow
paths were heated to 200” C. Ethylbenzene (Wako GR. ) was introduced by a
metering pump (Sage Instruments, Model 341A) at atmospheric pressure into
a preheated gasifier, where the evaporated vapor was mixed with hydrogen
carrier gas. The partial pressure of ethylbenzene vapor was kept low (hydro-
gen-to-ethylbenzene ratio = 130 (in mols), W/F= 135 gcat*h/mol) in order to
prevent rapid deactivation of the catalysts. The reaction was also carried out
at an elevated pressure up to 10 atm using a back pressure control valve in-
stalled after the reactor exit. In this case, the reactant was fed using a high
pressure metering pump (Eldex Model A) at a rate of 1.0-2.0 ml/h. The hy-
drogen-to-ethylbenzene molar ratio was controlled at 6.5, and W/F at 6.11
gcat *h/gmol.
Catalyts were reduced with hydrogen before introducing the reactants. The
reduction temperature was 500 oC for the supported nickel catalyst, and 600’ C
for catalysts involving tungsten. The hydrogen pressure was maintained at the
same level as the reaction pressure.
The effluent product stream was introduced via a Valco six-port sampling
valve to a Varian 1420 gas chromatograph with a dual thermal conductivity
detector (TCD ) system. The separation column was 10% Pentorial-A on Un-
iport B.
The activity and selectivity to a given product for the hydrodealkylation
reaction were defined as follows. Conversion = [ 1- (number of mols of ethyl-
benzene consumed) / (number of mols of ethylbenzene fed) ] - 100. Selectivity
to a given product = (number of mols of the given product/number of mols of
ethylbenzene reacted) 100. Generally the hydrodealkylation reaction is ac-
l

companied by a ring opening reaction of benzene. Since every mol of hydro-

cracked ethylbenzene produces 8 mols of methane and ethane was not detected
in the product stream, the total mols of ethylbenzene converted can be calcu-
lated as follows: Number of mols of ethylbenzene reacted = number of mols of
benzene produced (a) +number of mols of toluene produced (b) + (number
of mols of methane produced - 2a-b ) /8. Thus the selectivity to ring opening
78 Y. Song et al./Appl. Catal. A 63 (1992) 75-66

is calculated from the last term of the above equation divided by the number
of mols of ethylbenzene reacted.

Characterization of catalysts

Oxygen titration
Oxygen uptake by catalysts reduced in the hydrogen flow was measured us-
ing a conventional TPD apparatus equipped with a TCD cell. The catalyst (0.1
g) packed in a Vycor tube (O.D. 6 mm) was reduced under the same conditions
as for the reaction experiments. The reduced catalyst was flushed with helium
at the same temperature for an hour, and at an elevated temperature of 625°C
for another hour. Then, oxygen was injected as a pulse, and the exit stream
was analyzed using a TCD cell. Though the oxygen may react slowly with tung-
sten at as low a temperature as 400” C, the reactor was maintained at 625 ‘C to
shorten the experiment time.

TPD of dioxane
TPD of dioxane was performed using a l/4 in. O.D. stainless steel tube. After
0.2 g of catalyst was reduced with hydrogen at 600’ C for three hours and cooled
in helium flow to 125”C, liquid dioxane was injected for adsorption on the
catalyst at 125°C. Desorption and/or decomposition of the dioxane was then
followed with the temperature rising at the rate of lO”C/min to 650°C. The
flow-rate of helium gas was maintained over 200 cm3/min to minimize dioxane
readsorption. The effluent stream from the catalyst bed was first detected by
a TCD cell, and then a part of the stream was introduced via a six-port sam-
pling valve into a gas chromatograph (Shimadzu 7AG) for composition anal-
ysis. The analysis was performed using a separation column of Porapak Q pro-
grammed from 60 to 180°C.

RESULTS AND DISCUSSION

Hydrodealkyhtion of alkylbenzene

Table 1 summarizes the effect of temperature on the conversion and product

distribution of the hydrodealkylation reaction of ethylbenzene and m-xylene
over Ni (5)/SA catalyst. The conversion of each reactant steadily increased
with the rising reaction temperature. Up to 400” C, the major product was tol-
uene with little sign of the ring-opening reaction taking place. Above 425 ‘C,
however, the ring opening proceeded to an appreciable extent for ethylbenzene,
and finally at 450” C all the rings were hydrocracked to form methane for both
ethylbenzene and toluene.
Fig. 1 shows the effect of tungsten coimpregnated with nickel on the con-
version and the selectivity of ethylbenzene at 550 oC and 1 atm. In contrast to
Y. Song et al. fApp1. Catal. A 83 (1992) 75-86 79

TABLE 1

Conversion and product composition from ethylbenzene and m-xylene over a Ni (5) /SA catalyst
at various temperatures

Catalyst: 0.04 g; W/F= 100 gcat*h/mol

Temp. Ethylbenzene m-Xylene

(“C)
Conv. Mol fraction Conv. Mol fraction
(%) (%)
Benz.” Tol.” RO.” Benz.” Tol.” RO.”

300 0 - 0 -
325 5 0.0 0.05 0.0 2 0.0 0.02 0.0
350 20 0.01 0.19 0.0 5 0.0 0.05 0.0
375 58 0.06 0.52 0.0 15 0.01 0.14 0.0
400 90 0.2 0.69 0.01 35 0.06 0.29 0.0
425 98 0.41 0.34 0.25 65 0.27 0.36 0.03
450 100 0.0 0.0 1.00 100 0.0 0.0 1.00

“Benz., Tol. and RO. represent benzene, toluene and ring opening products respectively.

0 0.2 0.4 0.6 0.8 1.0

W/(Ni+W)

Fig. 1. Hydrodealkylation reaction of ethylbenzene over Ni-W (5)/SA catalysts with various tung-
sten contents as mol at 550’ C. Conversion ( 0 ); selectivities to benzene ( 0 ) ; to toluene ( 0 ),
and to ring opening (A ).Reaction pressure: 1 atm. W/F= 135 gcat*h/mol. Hydrogen-to-ethyl-
benzene ratio (as mol) = 134.
80 Y. Song et al./Appl. Catal. A 83 (1992) 75-86

the complete ring opening over a nickel catalyst at this temperature, a ten-
dency for the preservation of the benzene ring is apparent over nickel-tungsten
catalysts. The tendency becomes more conspicuous with increasing tungsten
contents, but only at the expense of decreasing conversion.
Table 2 compares the performance of nickel-tungsten catalysts for hydro-
dealkylation of ethylbenzene obtained under two different reaction pressures.
Over a Ni-W (1.25 : 3.75) /SA catalyst used at 1 atm, severe coking occurred on
its surface unless the partial pressure of hydrogen is pretty high. Thus a very
diluent feed stream (ethylbenzene-to-hydrogen= l/134 in mols) was used to
avoid deactivation of the catalyst. At higher pressure, on the other hand, one
may use catalysts with more metal loading and a feed richer in ethylbenzene,
and still need not worry about any significant deactivation. In a reaction per-
formed at 10 atm and 6OO”C, a Ni-W (5: E)/SA catalyst, which has the same
Ni-to-W mol ratio as Ni-W (1.25: 3.75)/SA catalyst but four times more metal,
was used with a much more concentrated feed stream (ethylbenzene-to-hydro-
gen ratio = 1: 6.5)) and showed a much better performance in respect to con-
version and benzene selectivity than at 1 atm.
The experiments using a Ni-W (5: 15)/SA catalyst at 10 atm as described
above were repeated for various reaction temperatures. The conversion and
the selectivity to each product species are plotted against the temperature in
Fig. 2. The conversion of ethylbenzene showed a steady increase with rising
temperature. The selectivity to benzene showed a slight decrease due to the
increased ring opening at higher temperatures, but it still maintained 60% even
at 650°C.
The selectivity of the hydrodealkylation reaction over cosupported nickel-
tungsten catalysts depends on the reduction state of the metals. Table 3 shows
the conversion and the selectivities of ethylbenzene at 600°C over Ni-
W (5: 15)/SA catalysts which were reduced at the same temperature under a
hydrogen flow of 10 atm for varying periods of reduction time. Over the catalyst

TABLE 2

Conversion and product distribution of ethylbenzene over a Ni-W ( 1.25 : 3.75 )/SA catalyst and a
Ni-W(5:15)/SAcatalystat600°C

Catalysts Ni-W(1.25:3.75)/SA Ni-W(5:15)/SA

Pressure 1 atm 10 atm

W/F(gcat*h/mol) 13.5 6.11
Product distribution (mol fraction)
Benzene 0.064 0.27
Toluene 0.032 0.09
RO 0.060 0.07
Conversion ( % ) 16 43
Y. Song et al.fAppl. Catal. A 83 (1992) 75-86 61

100

80 -
a

500 550 600 650

Reaction TemperaturelocI

Fig. 2. Conversion and selectivities to benzene, toluene, and ring opening in the hydrodealkylation
reaction of ethylbenzene over a Ni-W (5: 15)/SA catalyst at various reaction temperatures. Con-
version (0 ). Selectivities to benzene ( 0 ), to toluene ( 0 ), and to ring opening ( A ). Reaction
pressure: 10 atm. Pretreatment at 600°C under a hydrogen flow of 10 atm for 3 h. W/F=6.11
gcat. h/mol. Hydrogen-to-ethylbenzene ratio (as mol) =6.5

TABLE 3

Conversion and selectivities in the hydrodealkylation reaction of ethylbenzene at 600” C over a

Ni-W (5 : 15 ) /SA catalyst reduced at 600 ’ C under a hydrogen flow of 10 atm for various reduction
times

Reduction time Conversion of ethylbenzene Selectivity (% )

(h) (%)
RO products Benzene Toluene

1 77 91 5 4
3 43 17 62 21
6 74 19 34 47

reduced for one hour, high conversion was observed, but the product mainly
consisted of methane as a result of the ring opening reaction. Having been
reduced for three hours, the catalyst showed a high selectivity to benzene at
the expense of a decreased conversion. When reduction was prolonged up to
six hours, the conversion was again high with little ring opening, but toluene
showed an edge over benzene in the product distribution.
The above results indicate the strong dependence of the catalytic behavior
of nickel-tungsten on reduction conditions. While nickel oxide is susceptible
82 Y. Song et al./Appl. Catal. A 83 (1992) 75-86

to reduction around 5OO”C,tungsten oxide needs a higher temperature to be

reduced, and passes through stages of 5 + and 4 + and then finally to metal.
Hence one may reasonably assume that nickel would be sufficiently reduced
at 600’ C, and accordingly that the degree of reduction of tungsten dictates the
selectivity behavior of cosupported nickel-tungsten catalysts. Unless reduced
long enough, nickel-tungsten catalysts were found to behave as if only nickel
were impregnated. Tungsten reduced for three hours had a negative influence
upon the hydrocracking activity of nickel for the benzene ring, thus leading to
a high benzene selectivity. Having been exposed to high pressure hydrogen for
six hours, the catalysts yielded toluene more than benzene.
Preservation of the benzene ring over cosupported nickel-tungsten catalyst
was ascribed to the suppression of the catalytic activity of nickel for hydro-
cracking in the presence of reduced tungsten. Though interaction between re-
duced tungsten and nickel might be the cause of this modification, the effective
oxidation state of tungsten in enhancing benzene selectivity is not clear. One
may recall another mechanism proposed in the literature which refers to the
promotion of o-adsorption of ethylbenzene in the presence of tungsten [4,8,9],
but the mechanism seems to need further verification.

Churacterization of the catalysts

Oxygen titration experiments were performed for supported metal catalysts

to examine the degree of reduction in relation to the treatment conditions. Fig.
3 shows the variation of oxygen uptake (oxygen-to-tungsten atomic ratio) of
the W (10) /SA catalyst with reduction temperature and time. After reduction
in hydrogen flow, the catalyst was titrated with oxygen at 625°C. For the cat-

Time lh)

Fig. 3. Variation of oxygen uptake (oxygen-to-tungsten atomic ratio) of tungsten of a W (lO)/SA

catallyst with reduction temperature and time. Reduction temperature 725°C ( 0 ), 625 “C ( 0 ) ,
525°C (A).
Y. Song et aL/Appl. Catal. A 83 (1992) 75-86 83

alyst reduced at 525”C, the oxygen uptake was very small (less than 3% ) re-
gardless of the duration. On the other hand, the uptake significantly increased
for catalysts treated at 625”C, reaching approximately 24% after three hours
reduction. Using this result, one might state, on a rough basis, that 24% of the
impregnated WO, was reduced to WOz. Similar results were obtained by Soled
et al. [lo], who reported that about 22% of WO, impregnated on an alumina
support was reduced to WOz at 600’ C. Also, no diffraction peak was observed
corresponding to tungsten in the X-ray diffraction (XRD) pattern of the cat-
alyst surface. Thus, it seems to be reasonable to postulate intermediate meta-
stable W4+ and W5+ states including a small amount of metal as representing
the reduction state of the catalyst reduced with hydrogen around 625’ C. When
the reduction temperature rose to 725 ’ C, a much higher level of oxygen uptake
was observed. After reduction for 36 h, the presence of metal in the supported
tungsten catalyst was confirmed by the observation of a W (110) diffraction
peak in the XRD pattern [ 111.
Similar titration experiments were conducted for the Ni(5)/SA catalyst.
The results are summarized in Table 4. Reduced at a comparatively low tem-
perature of 450’ C, the catalyst showed 90% oxygen uptake. This indicates that
90% of the nickel oxide was converted to the metallic state by reduction. Com-
paring with the results of Fig. 3, it is clear that nickel oxide is more easily
reduced to its metallic state than tungsten oxide.
Table 5 shows the oxygen uptake by cosupported nickel-tungsten catalysts
after reduction. Earlier results for nickel or tungsten catalysts are included to
facilitate the comparison. When reduced at low temperatures up to 500’ C, the
nickel-tungsten catalysts took up almost the same amount of oxygen as the
nickel catalysts. This is the expected result taking into account the resistance
of tungsten oxide to reduction at low temperature. For a high reduction tem-

TABLE 4

Amount of oxygen uptake at 625°C of supported, reduced nickel catalysts

Catalyst: Ni( 5)/S& pulse injection with a helium carrier gas (60 cm3/min)

Reduction treatment” Oxygen-to-nickel

(atomic ratio)
Temp. Time
(“C) (h)

450 3 0.90( kO.05)

500 3 0.90 ( f 0.03 )
500 12 l.OO( kO.03)
550 3 0.95 ( f 0.03)
660 3 1.00 ( ?I0.03)

“With hydrogen (60 cm3/min).

84 Y. Song et al./Appl. Catal. A 83 (1992) 75-86

TABLE 5

Amount of oxygen uptake of supported nickel and tungsten catalysts after reduction

Reduction treatment” temperature Amount of oxygen upt.akeb ( 10H5 mol)

(“C)
Ni-W(B:lO)/SA Ni(5)/SA W(lO)/SA

450 3.83 3.83 0.0

500 3.77 3.83 0.01
600 5.36 4.26 0.54

“With hydrogen (60 cm3/min) and for 3 h.

bPulse injection with a helium carrier gas (60 cm3/min).

perature of 6OO”C, the tungsten catalyst also took up a modest amount of ox-
ygen. It is noteworthy that the oxygen uptake of the nickel-tungsten catalyst
was larger than that of the nickel catalyst and the tungsten catalysts combined.
This seems to follow from the promoting action of reduced nickel metal toward
the reduction of tungsten oxide.
The rest of this section is concerned with temperature-programmed desorp-
tion of dioxane performed to investigate the catalytic role of tungsten in co-
supported nickel-tungsten catalysts. Ethylbenzene did not adsorb to a suffi-
cient extent enough to analyze the effluent using a gas chromatograph. In
addition, the adsorbed ethylbenzene left carbon deposits, making it difficult to
examine the interaction with active sites on the surface. On the other hand,
being a ring compound without double bonds, dioxane adsorbs on the surface
to a significant extent. Furthermore, the adsorbed dioxane is readily desorbed
from the nickel catalyst without affecting the active sites. Hence dioxane ap-
peared to be a suitable compound for investigating the effect of tungsten ad-
dition. Having oxygen atoms, dioxane molecules were expected to adsorb read-
ily on the empty sites once occupied by lattice oxygen of unreduced tungsten
oxides. However, it was not easy to compare the differing reduction treatments
in respect to the amount of dioxane adsorbed.
Fig. 4a shows the results of TPD of dioxane over a reduced Ni (5) /SA cata-
lyst. Each TPD curve was separated into two peaks on the basis of the GC
composition analysis of the effluent from the TCD cell. The first peak corre-
sponds to desorption without decomposition, and the second to desorption with
decomposition. They are referred to respectively as the desorption peak and
the decomposition peak in the following sections. The desorption peak ex-
tended up to 300’ C. Decomposition started around 200’ C with the peak max-
imum located near 350°C. The effluent gas from decomposition was trapped
using liquid nitrogen, and then analyzed using an NMR (JEOL PMXGOsi).
The decomposition product was found to consist mainly of acetaldehyde and
a trace amount of hydrocarbons.
Y. Song et al./Appl. Catal. A 83 (1992) 75-86 85

%_
-.

100 200 300 400 500 600

Temperature(“C)

Fig. 4. TPD profile of dioxane from supported nickel and nickel-tungsten on silica-alumina. (a)
Ni(5)/SAcatalystreducedat600°Cfor3h; (b) Ni-W(5:15)/SAcatalystreducedat600°Cfor
3 h; (c) silica-alumina support. Desorption peak (-); decomposition peak (---).

Compared with Fig. 4a, Fig. 4b shows the effect of adding tungsten to nickel
catalysts. A larger desorption peak extending to a higher temperature was ob-
tained than when nickel was impregnated. The decomposition peak was also
observed starting from 25O”C, but the total amount of products was much
smaller than in Fig. 4a. These differences can be ascribed to the suppression
of the decomposition activity of nickel in the presence of tungsten.
Fig. 4c shows the results obtained over a silica-alumina support without any
metal loading. On the whole, both peaks have smaller areas than over sup-
ported metal catalysts. The desorption peak extended as far as 500” C, and the
decomposition peak started only above 300 ’ C.
The TPD experiments of dioxane were also carried out using metal catalysts
supported on silica. Similar trends were observed except that the peak areas
were smaller compared with the cases of Fig. 4. Dioxane decomposed to a sig-
nificant extent near 320°C over the nickel supported catalysts, while the de-
composition was weakened when tungsten was added.

CONCLUSIONS

The present results on the hydrodealkylation reaction of ethylbenzene over

supported metal catalyst on silica-alumina can be summarized as follows.
86 Y. Song et al.fAppl. Catal. A 83 (1992) 75-86

(1) Nickel supported on silica-alumina shows a high conversion of ethyl-

benzene, but a low selectivity to benzene due to hydrocracking of the benzene
ring.
(2) When tungsten is coimpregnated with nickel, it suppresses the ring
opening reaction, leading to high benzene selectivity. The actual conversion
and selectivity vary depending on the reduction treatment.
(3) Tungsten is not so easily reduced as nickel, but its reduction was pro-
moted when coimpregnated with nickel due to the spillover of hydrogen.
(4) Nickel catalysts show a high activity for decomposition during temper-
ature-programmed desorption of dioxane, but the activity is suppressed in the
presence of tungsten.

ACKNOWLEDGEMENT

One of the authors, Yosoon Song, gratefully acknowledges the partial finan-
cial support of the Research Foundation of Chonnam National University.

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