A single, packed-bed, catalytic tube-type reactor using a licensed catalyst for the LAR (Low Air

Ratio) process is preferred. The reactor must be capable of producing 50000 mT/year of phthalic
anhydride from pure o-xylene and air. The conversion of o-xylene should be essentially 100%
with approximately 79% selectivity for PAN. The composition of the products must be
controlled to maximise the concentration of phthalic anhydride and minimise the formation of
impurities. The feed is available at 205'C from preheating equipment and should leave the
reactor at not more than 4000C. The surplus heat should be removed with an appropriate coolant.
Any hot-spots in the reactor must be controlled to protect the catalyst, coolant and products from
potential damage. The vessel should be able to withstand an internal explosion of o-xylene or
phthalic anhydride caused by auto-ignition (or otherwise) which could cause a pressure rise of
180OkPa. It must also be possible to access the tubes in order to replace the catalyst when it
becomes deactivated.
The LAR process selectively oxidises o-xylene to phthalic anhydride over a proprietary catalyst
(based on vanadium pentoxide) in a tubular fixed-bed reactor. Although little specific
information is available that is directly applicable to the LAR process, several studies have been
performed on the traditional process which uses the same type of reactor. Many design
considerations are the same for both reactors. The advantage of the new catalyst (the LAR
proprietary catalyst) is that it is able to operate at a significantly higher o-xylene concentration
without either reducing the selectivity for the partial oxidation reaction which produces phthalic
anhydride or increasing the formation of by-products. The LAR catalyst can oxidise feeds with
o-xylene concentrations up to 134g/N m3 while traditional catalysts operate on only 40-70g/N
m3 . Thus, substantially less air (which is mostly inert) is required and much of the downstream
equipment can be reduced in size and duty. However, the heat released by the reaction is also
concentrated in a small part of the reactor and difficulties arise in adequately dissipating the heat
to prevent excessive temperatures in the reactor.

Catalyst Properties

The catalyst is a combination of vanadium pentoxide, titanium dioxide and small amounts of
certain proprietary compounds which improve the range of operating conditions. It is prepared
by heating a suspension containing the compounds, and spray coating the suspension onto a
support which can be either 6 mm porcelain spheres, or similar sized steatite rings. The surface
area available for reaction is about 10-12m2/g. A selectivity for phthalic anhydride of 78.8% is
claimed, producing a yield of 110% by weight of o-xylene feed. The maximum safe loading of
hydrocarbon is 0. 192 kg/m2/S.

Kinetics

The vapour-phase oxidation of o-xylene over a vanadium pentoxide catalyst is essentially first
order with respect to the o-xylene concentration. However, above a maximum o-xylene
concentration (which depends only on the specific type of catalyst and is independent of
temperature while the catalyst remains activated) the catalyst deactivates irreversibly and the
reaction rate decreases rapidly. Deactivation occurs when the valence-state of vanadium changes.
New developments have focussed on finding additives to prevent this from happening. The LAR
catalyst can sustain the reaction up to a concentration of 2.77 mole % o-xylene, compared with
only 1.0-1.4% in other catalysts.
There are at least three significant reaction mechanisms which occur at the temperatures
encountered within the reactor. Below 370'C, the reaction is first order with respect to the
oxygen concentration and the rate constant is low. The selectivity for phthalic anhydride is high
but conversion of the feed may not be complete and the product is likely to undergo further
combustion. Between 37WC and 4400C, the reaction is first order with respect to the
hydrocarbon. The rate constant is significantly higher, the selectivity remains high and the o-
xylene conversion is essentially complete. Above 440'C (and below 550'C), the reaction is also
first order with respect to hydrocarbon concentration but conforms to a third reaction
mechanism. The activation energy is substantially less, the rate constant is higher and, because
the activation energy is low, the reaction rate is almost independent of temperature. The
selectivity for phthalic anhydride begins to decrease at higher temperatures as side reactions and
complete oxidation become more likely. The catalyst is irreversibly deactivated if the surface
temperature exceeds 500'C. There will be a temperature drop from the gas to the catalyst surface
of 10-50'C. Thus, the maximum allowable gas temperature is 510-550
0
C. The gas temperature in
the reactor should, therefore, be controlled so that the bulk of the reaction occurs from 440-
5100C.
Key Results
1-The LAR catalyst, compared with traditional catalysts, can operate at significantly higher
hydrocarbon concentrations without deactivating.
2- At reaction temperatures of 440-510'C, the reaction rate is first order with respect to
hydrocarbon concentration and essentially independent temperature. At lower temperatures, the
reaction is much slower and dependent on the partial pressure of oxygen, and the PAN yield is
reduced.
3-At higher temperatures, the catalyst can deactivate irreversibly.