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Simulation and Optimization of the Production of Phthalic Anhydride from O-

Xylene

Conference Paper · April 2014

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 Simulation and Optimization of the Production of Phthalic Anhydride
from O-Xylene
Abhideep Singhai, Dipankar Kalita, Ashwin Nenmini Utkarsh Maheshwari

Department of chemical engineering

Birla Institute of Technology and Science, Pilani (Raj.)

Abstract
Phthalic anhydride is the organic compound with the formula C6H4(CO)2O. It is the
anhydride of phthalic acid. This colourless solid is an important industrial chemical,
especially for the large scale production of plasticizers for plastics. This report illustrates a
way of producing phthalic anhydride (PA) in a continuous plant, with 99.8 % wt purity,
through the oxidation of o-xylene. Maleic anhydride is also obtained as a by-product of the
process with 99.5% wt purity. The process was simulated using the process simulator
software ASPEN Plus and improving the purity of Phthalic anhydride obtained by
introduction of suitable equipments. Simulation and optimization of the process is done using
the new pathway.

anhydride. With an annual production of

1. Introduction
Throughout the last years, the rising
awareness that fossil resources will come
to an end at some point has led to rising
prices for these fossil fuels. The oil price
took a stunning development from about
20 US$/barrel in 1999 to currently well
above 100 US$/barrel in 2011.[1]
Consequently, the optimization of existing
chemical processes yields substantial
economic impact and also reduces the
emission of pollutants. Recently, it was
pointed out that catalytic selective
oxidation plays an important role in
process intensification and the improved
usage of fossil resources[2]. Several
processes based on selective oxidation
have been important industrially over the
last decades. One of these processes is the
oxidation of o-xylene to phthalic
4.5 million tons in 2005, phthalic
anhydride is a significant commodity in
chemical industry. Applications are mainly
in the manufacture of phthalate
plasticizers, phthalocyanine dyes,
polyester resins and numerous fine
chemicals. Historically, the feedstock for
phthalic anhydride production was
naphthalene, which has gradually been
replaced by o-xylene throughout the past
50 years. Considering the quantities
produced on an industrial scale, even an
increase of 1% in selectivity has a
substantial economic effect.[3]
Historically, phthalic anhydride (PA) was
produced in slurry phase from naphthalene
feedstock from as early as 1872. The
industrial breakthrough as important
commodity was made when the production
process was modified to oxidize vaporized
naphthalene over vanadia catalyst. Since
 the 1960s o-xylene has replaced Fig:1 Main Application of PA in industry
naphthalene as feedstock more and more.
Several different o-xylene production 2.1 Uses
processes are documented in literature.
• In the manufacture of alkyd resins for
Although alternative processes such as
paints and varnishes.
fluidized bed processes or slurry phase
• In the manufacture of unsaturated
processes were developed, still today the
polyester resins.
fixed bed catalytic process is most
• Phthalic anhydride finds applications as
common.
Dye intermediate and also in the
2. Major Outlets manufacture of pigments.
• It is used in the manufacture of
tetrachlorophthalic anhydride which finds
PA is an important chemical intermediate. applications in reactive fire retardant in
Its major outlets are phthalate plasticizers, unsaturated polyesters.
unsaturated polyesters and alkyd resins for
• The major outlet of phthalic anhydride are
surface coatings while its smaller volume
plasticizers which are added to polymers to
applications include polyester polyols,
facilitate processing and to increase the
pigments, dyes, sweeteners and flame
flexibility and toughness of the final
retardants. The major outlet for phthalic
product by internal modification of the
anhydride (PA), accounting for just over
polymer molecule.
half of production, is in the manufacture of
phthalate plasticizers, the main product
being dioctyl phthalate (DOP) which is 2.2 Phthalic anhydride (PA) Market
used as a plasticizer in polyvinyl chloride
(PVC).[4] Hence, the consumption of PA Global demand for PA was forecasted by
is mainly dependent on the growth of consultants to have been around 3,600,000
flexible PVC, which is sensitive to general tonnes/year in 2006 with worldwide
economic conditions as it is consumed in growth rates expected to be around 3.0-
the construction and automobile industries. 3.5%/year over the next five years.[4] This
growth is led by the Asia-Pacific region
where demand is forecast to increase at
4.0-4.5%/year. Demand growth in the US
and Western Europe is much lower at 1.0-
1.5%/year.

2.3 Plasticizers

Plasticizers are organic esters added to

polymers to facilitate processing and to
increase the flexibility and toughness of
the final product by internal modification
of the polymer molecule. Flexible
polyvinyl chloride (PVC) accounts for 80–
90% of world plasticizer consumption.
Flexible applications for PVC accounted
for 35% of PVC consumption in 2005.
From 2002 to 2005, world capacity for
plasticizers grew at an average annual rate
of 3.8%, a much higher rate than world
consumption, which grew at an average
annual rate of 2.0% during the same
period.[4] The following pie chart shows
world consumption of plasticizers and the
large percentage of consumption
accounted for Other Asia, excluding Japan.
Fig 2: World consumption of plasticizers
2.4 PVC Market
The consumption of PA is mainly
dependent on the growth of flexible PVC,
which is sensitive to general economic
conditions as it is consumed in the
construction and automobile industries.
The United States, Western Europe and
China are the major consumers of PVC, as
shown in Figure The PVC is mainly used
in building & construction sector (67%).
The major applications are profiles (29%)
and pipes & fittings (26%)[4]
Fig 3: World consumption of PVC
3. Properties of Phthalic Anhydride
Molten phthalic anhydride has a
penetrating odour and its vapours irritate
the eyes and mucous membranes. Solid
phthalic anhydride is in the form of
colourless acircular crystals or flakes and
has a faint aromatic odour. Phthalic
anhydride is soluble in hot water, benzene,
carbon disulfide, and alcohol and is
slightly soluble in water and ether and is
hydrolyzed by water in a strongly
exothermic reaction. Feedstock for the
production of plasticizers and polyester
resins, as well as intermediate for organic
syntheses.
Physical Properties:[5]
• Molecular formula- C8H4O3
• Molar mass- 148.1 g/mol
• Appearance- white flakes
• Density- 1.53 g/cm3, solid
• Melting point- 131 °C
• Boiling point -295 °C
• Solubility in water-
0.62 g/100g (20—25 °C);19.0 g/100g (100
°C)
• Flash point-152 °C
4. Organic Synthesis
 Phthalic anhydride is a versatile
intermediate in organic chemistry, in part
because it is bifunctional and cheaply
available. It undergoes hydrolysis and
alcoholysis. Hydrolysis by hot water
forms ortho-phthalic acid.[5] This process
is reversible. Phthalic anhydride re-forms
upon heating the acid above 180 °C.
Hydrolysis of anhydrides is not typically a
reversible process. However, phthalic acid
is easily dehydrated to form phthalic
anhydride due to the creation of a
thermodynamically favorable 5-membered
ring.
5. Methods of Production of Phthalic
Anhydride
The chemical reactions for catalytic oxidation of O-Xylene is as follows:[6]
The chemical reactions involved in PA production from Naphthalene are:[6]
5.1 Phthalic anhydride on an industrial
scale is produced with O-Xylene as the
feedstock due to the following reasons:
• The feedstock is cheaper
Phthalic anhydride is produced by the
catalytic oxidation of:-
• Ortho-xylene
• Naphthalene
The processes for producing phthalic
anhydride by o-xylene or naphthalene are
the same except for reactors, catalyst
handling, and recovery facilities required
for fluid bed reactors. The catalysts used
for both the reactions are V2O5 and the
temperature ranges employed are of the
order of 340-385°C and pressures below 1
bar.
• The effluent produced from Naphthalene
contains more percentage of particulates
than that from O-Xylene.
• % yield from Naphthalene is less as
compared to O-Xylene.
Fig 4: Flow sheet of phthalic anhydride production process via O-xylene oxidation[4]
Fig5: Flow sheet obtained from the Simulation on Aspen Plus process simulator
6. Production Process
• The raw o-xylene is pre-heated and mixed
with a compressed air stream. Then, it
enters on an isothermal reactor were the
crude product is obtained.
• In the reactor, a molten salt is used to
remove the heat generated. The salt is then
fed to a steam generator, where 18 bar
steam (medium pressure steam) is
generated at 300 ºC.
• The stream leaving the reactor is
condensed and the liquid fraction is
• First reaction is the main reaction and it is
separated from the off gases.
• In order to obtain the MA, the stream is
• Second reaction refers to the formation of
condensed again and the condensables are
mixed with the previous liquid phase.
• The resulting stream is heated and once
• Reactions third and fourth represent the
again the vapor phase is separated from the
liquid one, which is fed to the first
distillation column, where the major
fraction of water is mainly removed. The
bottom stream, which is now composed
8. Emissions And Controls
exclusively by PA and MA, is cooled and
fed to the second distillation column where
the MA by-product stream is obtained on
top while the PA final product on the
bottom, both purified.[4]
7. Reactions
The main reaction of interest is the partial
oxidation of cumene to produce phthalic
anhydride. This reaction can be carried out
heterogeneously (using a solid catalyst).
The reactor types that you should consider
are a packed bed and a fluidized bed. For a
Fluidized Bed design the bed/reactor
temperature may be assumed to be
isothermal (i.e. the solids are well mixed).
No matter what reactor configuration is
used the formation of by-products cannot
be helped. Using the catalyst vanadium
and titanium oxide eliminate most by-
products the most notable exception is
maleic anhydride. In addition, o-xylene
and both anhydrides can be further
oxidized to give carbon dioxide and water.
(1) C8 H10 + 3O2 → C8 H 4 O3 + 3H 2O
(2) C8 H10 + 7.5O2 → C 4 H 2 O3 + 4 H 2 O + 4CO2
(3) C8 H 10 + 10.5O2 → 8CO2 + 5 H 2 O
(4) C8 H10 + 6.5O2 → 8CO + 5 H 2 O
assumed a 70% selectivity.[4]
the by-product MA and a 10% selectivity
is considered.
complete and incomplete combustions of
o-xylene with 15% and 5% selectivity.
The major contributor of emissions is the
reactor and condenser effluent which is
vented from the condenser unit.
Particulate, sulfur oxides (for o-xylene-
based production), and carbon monoxide
make up the emissions, with carbon
monoxide comprising over half the total.
The most efficient (96 percent) system of
control is the combined usage of a water
scrubber and thermal incinerator.[6] A
thermal incinerator alone is approximately
95 percent efficient in combustion of
pollutants for o-xylene-based production,
and 80 percent efficient for naphthalene-
based production. Thermal incinerators
with steam generation show the same
efficiencies as thermal incinerators alone.
Scrubbers have a 99 percent efficiency in
 collecting particulates, but are practically Reflux Ratio 0.2 6
ineffective in reducing carbon monoxide
emissions. In naphthalene-based
Feed stage 10 50
production, cyclones can be used to
control catalyst dust emissions with 90 to
Pressure(bar) 1 0.5
98 percent efficiency.[6]

9. Discussion and conclusion

It has been observed that by increasing the
On the modeling and simulation of the number of stages of the distillation column
whole process using Aspen Plus simulator, the yield of phthalic ahydride could be
we have found out that the purity of reached upto 98% and as obtained from
Phthalic Anhydride can be enhanced by simulation and optimization, the purity of
the introduction of 2 distillation columns. Phthalic Anhydride was found to be
Without the two columns,a purity of 99.2%. As simulating a set of switch
around 99 % is obtained. But the needs of condensers is extremely difficult, a simple
the industry led to the introduction of the heat-exchanger was used for the required
two columns, which increases the purity to conditions of the outlet reactor’s stream. In
99.2%.According to the specified this project, indirect energy integration
conditions, we have also studied the was opted by producing medium pressure
varying effect of stages of distillation steam in the reactor. This steam was used
column. We have found that maximum to heat all the necessary streams in the
yield can be obtained using the number of process. Also, exceeding is sold to
trays as given in the column below. Also, optimize the plant’s profit. The process has
the optimum reflux ratio is obtained. . been studied and optimized at best
operating conditions to get the maximum
productivity of phthalic anhydride. The
temperature ranges employed for the
Distillation Distillation process are of the order of 340-385°C and
column 1 column 2 pressures below 1 bar. At these conditions,
we get the highest percentage of yield of
Trays 18 65 phthalic anhydride from the O-xylene
feedstock. In this process, a successful
Height(m) 9 19.5 simulation was made in order to achieve
the yield of phthalic anhydride(PA),
Diameter(m) 0.5(bottom) 1 including purity of PA and annual
production.
0.2(top)

Tray 0.5 0.3

spacing(m)
 10. References

1. Dipl.-Ing. Robert Marx, Kinetics of the

Selective Oxidation of O-Xylene to
Phthalic Anhydride, January 27, 2012
2. http://www.oil-price.net/, 1-5-2011
3. Cavani, F., Catalytic selective oxidation:
The forefront in the challenge for a more
sustainable chemical industry, Catalysis
Today 157, 8-15, 2010
4. Acácio Mendes, Ana Rita Seita, Design of
Phthalic Anhydride Production Process
Student Contest Problem Competition
2009 – EURECHA, Instituto Superior
Técnico – Av. Rovisco Pais, 1049-001,
Lisboa, Portugal.
5. http://en.wikipedia.org/wiki/Phthalic_anhy
dride.
6. Engineering And Cost Study Of Air
Pollution Control For The Petrochemical
Industry, Vol. 7: Phthalic Anhydride
Manufacture From Ortho-xylene, EPA-
450/3-73-006g, U. S. Environmental
Protection Agency, Research Triangle
Park, NC, July 1975.
7. Blechschmitt, K., Reuter, P., Wirth, F. and
Hornberger, P., Phthalic anhydride from
oxylene or naphthalene, DE2546268A1
(16-10-1975), assigned to BASF AG
8. Hara, T., Catalyst and process for the
manufacture of phthalic anhydride from
naphthalene or 1,2-xylene, EP286448A2
(11-4-1988), assigned to Nippon Steel

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