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SELECTIVE DISPROPORTIONATION OF TOLUENE TO PRODUCE BENZENE AND

P-XYLENE

Thesis · October 2018

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Abdal Kareem M.A Dawagreh

Al-Balqa Applied University
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 ABSTRACT

Toluene disproportionation reaction to produce benzene and xylenes is of

considerable importance due to the increasing demand of benzene and xylenes in
chemical industries. The demand of toluene is found to be the lowest, whereas, the
para-isomer of xylene is of greater significance due to its use in the manufacture of
polyester fiber and many petrochemicals. The commercial process for p-xylene
production from toluene involves the vapor phase disproportionation of toluene over a
variety of acid zeolites. Toluene disproportionation yields benzene and a mixture of
xylenes as initial products inside the zeolite pores. The products subsequently diffuse
out of the zeolite pores. Owing to its smaller size and very high diffusivity, p-xylene
diffuses out of the pores at a very high rate in comparison to o- and m-xylene. The
ortho- and meta-xylenes undergo isomerization reaction within the zeolite. Several
researchers have shown enhanced para-selectivity of zeolites by the use of modifier
agents such as Si, B, P and Mg. These modifier agents have been reported to (i)
partially block the pores, increase tortuosity and thereby delay the exit of larger
molecules of o- and m-xylenes, and (ii) block the unselective active sites and
inactivate the external active sites for secondary isomerization. The modification of
the zeolites by ion exchange has been reported to increase the acid strength when
pretreated by La3+ ion and increasing the initial toluene conversion and also the
hydrothermal stability.
Based on the fact that the ion exchange of a zeolite may lead to (i) selectivity
of the reactions based on the nature of the cation, (ii) blockage of the zeolite pore
mouth in proportion to the size of the exchanged ion, leading to shape selectivity for
the desired product (p-xylene in the present case), and also (iii) greater stability of the
exchanged zeolite than the modified form, the present work has been undertaken.
The present work deals with the preparation, characterization and activity tests
of the following catalysts for toluene disproportionation:

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(a) ZSM-5 zeolite ion-exchanged with several elements representing various
groups of the Periodic Table.

(b) -zeolites exchanged with Ni, Co, Ce, and H.

(c) Y-zeolites exchanged with H, Ni.

(d) ZSM-5 exchanged simultaneously with two different elements.
(e) 13X zeolite exchanged with Ce, La and also simultaneously with two different
elements, namely BaCe, CrCe, CrLa, FeCe, CrNi, ZnNi and ZnCe.
(f) Perovskite type oxide, namely LaCoO3, LaNiO3, BaFeO3, LaFeO3 .BaNi O3
(g) Ni/TiO2, Ni/MgO, Ni/ZrO2.

The ion-exchange of the zeolite powder was performed by mixing the powder
with the respective metal nitrate solutions having a metal content. The solution was
heated at 50oC for about 3h with constant stirring. The contents were further refluxed
under a total condenser at 95±5 oC for 15 h. The solid powder was then filtered, dried
at 110 oC overnight and calcined at 700oC for 10 h. The dried powder, in order to
make it suitable for tests in the reactor, was pelletized at 104 bar pressure, and then
broken and sieved to get the particles in the specific size range of 0.33 to 0.52 mm.
The catalytic activity tests were carried out in a down flow vertical silica glass
tubular reactor. The reactor tube having 1 cm inside diameter and 50 cm length was
heated electrically and the temperature was controlled to within ±1oC. The catalyst
particles were mixed with quartz particles of similar size range and packed in the
middle of the reactor tube. Above the catalyst bed quartz particles (0.95 - 1.14 mm
size) were packed serving the dual purpose of preheating as well as mixing the
reactants. Passing air through the reactor at 500 oC for 1h activated the catalyst. The
catalyst bed was cooled to the reaction temperature in the nitrogen atmosphere before
carrying out reaction tests.
The toluene feed was pumped into the reactor at a regulated rate using a
metering pump. The nitrogen gas was simultaneously introduced at the top of the

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reactor tube through a Y junction and a specified weight hourly space velocity
(WHSV) of the toluene feed was maintained.
The products from the reactor were passed through a set of glass condensers
fitted in series and cooled by ice-cold water. The liquid and gaseous products at each
reaction temperature were collected in sampling bottles for further analysis. The flow
rate of both the liquid and vapour were also recorded for overall mass balance. The
liquid product was analyzed by a gas-liquid chromatograph using a 4 m long stainless
steel column of 3.2 mm outside diameter packed with 7% Bentone-34 ± 5% Dinonyl
phthalate on Celite 545, 60-80 mesh. The oven temperature was kept at 90oC, and the
flow rate of nitrogen gas as the carrier was maintained at 30 ml min-1. The nitrogen to
toluene molar ratio was maintained at 5.9 in all the runs.
The zeolite samples were characterized by XRD for phase formation and
percent crystallinity, SEM for particle size, and atomic absorption spectrometer and
inductively coupled plasma (ICP) for elemental analysis. Infrared spectrograms of the
samples were also taken to estimate the relative strengths of Bronsted acid sites
(strong, weak and medium) and Lewis acid sites.

Results and Discussion

The XRD pattern of the zeolite samples indicated the crystalline structure of
the zeolite. However, the percent crystallinity calculated after ion exchange was found
to decrease due to partial dealumination of the zeolite.
Catalyst systems were studied for toluene disproportionation and the effects of
various parameters were observed. Effects of reaction temperature in the range of
300-600oC, time-on-stream studies at a fixed temperature of 550o for 5 h,
silica/alumina ratio (SAR) of the ZSM-5 zeolite catalysts at a fixed temperature,

carrier gas (N2, H2, Ar), type of zeolite (ZSM-5 with SAR-60, 90 & 235, - and Y- ),

percentage ion exchange, acidity of the catalysts and crystallinity of the catalysts were
investigated.

VII
 Na-form of the zeolite was first converted to H-form and subsequently
exchanged with different cations. The activity tests have been compared group wise
(belonging to the same group of the Periodic Table) as well as among the bests of
different groups. The toluene conversion, in general, was found to increase with
temperature upto 500 or 550oC and thereafter showed a decline. The maximum
toluene conversion obtained was around 35% with NiZSM-5 at 500oC and one
atmospheric pressure. The p-xylene in the xylenes product, in general, increased with
the reaction temperature. It varied between 90 and 97% when conversion was less
than 2% and 50-60% when conversion was between 15 and 30%. The percent p-
xylene yield, defined as mole p-xylene formed/mole toluene fed, also increased with
reaction temperature upto 500oC and then decreased. In general, it varied between 3
and 4% and in a particular case with a certain catalyst it was found to be as high as
9%. Benzene/xylene (B/X) ratio varied from less than 1 to 3.
Time-on-Stream studies were conducted at a 550oC for 5 hours and one
atmospheric pressure in the presence of different carrier gases (N2, H2, and Ar). In
general, the activity with all the three carrier gases remained almost unchanged with
time excepting that for nickel exchanged catalysts. The presence of nickel, it seems,
does not help in oxidizing the coke formed on the catalyst.
The toluene conversion was observed to be a little lower with nitrogen as the
carrier gas than with hydrogen. Argon showed a trend in between the above two
gases. However, p-xylene in the xylenes product was found to be the highest with
nitrogen as the carrier gas, followed by argon and hydrogen, respectively. The
sequence was found in reverse order for p-xylene yield, i.e., and hydrogen as the
carrier gas was the best followed by argon and nitrogen in that order.
HZSM-5 with three SAR (60, 90 and 235) were tested for their catalytic performance.
Para-xylene yield with nitrogen as the carrier gas followed the order SAR 60 > 90 >
235. Using Ni ZSM-5 catalyst and argon as the carrier gas a similar trend SAR 60 >

VIII
 907>235 was observed. In some cases, the activity of the zeolite having SAR=235
was observed to be a little higher than for SAR the zeolite having 60 and 90.
The acidity of the catalysts due to different cations present did not give a
definite trend for toluene conversion. For example, toluene conversion at 500oC was
found to increase in general with the increase in acidity (measured as mmol KOH/g)
for most of the catalysts having less than 4% of metal ion-exchange. With higher
exchange, however, the trend was reversed. At 550oC, the toluene conversion
increased with acidity.
The loading of nickel on a ZSM-5 was varied from 2% to 12%. Exchanged
catalysts with 4% nickel solution showed greater toluene conversion in comparison to
6, 10 and 12 percent in that order. The p-xylene in the xylenes product was minimum
with 4% loading, whereas, the p-xylene yield was the best obtained with this loading.
The results, thus, indicate 4% as the optimum Ni-concentration for exchange. The
results have also been confirmed with other catalytic components.

ZSM-5, -zeolite and Y-zeolite were used with and without exchange for the

comparison of catalytic activity. The results with, for example, 4% nickel exchange
catalysts showed toluene conversion in the order: ZSM-5 (SAR=60) > ZSM-5

(SAR=90) > zeolite > Y-zeolite. Para-xylene in the xylenes product for the same

catalysts had the order: zeolite > ZSM-5 (SAR=235) > ZSM-5 (SAR=90) > Y-

zeolite, whereas, the p-xylene yield was obtained in the order: ZSM-5 (SAR 60) >

zeolite >ZSM-5 (SAR=90) > ZSM-5 (SAR 235) > Y-zeolite.

Many catalysts based on 13X zeolites (single as well as double exchange),

perovskites and Ni/TiO2 etc. as mentioned above were tested to explore their activity
for toluene disproportionation. The results, however, were found discouraging in

comparison to the ZSM-5 and zeolites.

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