Technological Institute of the Philippines

Process Selection
 Technological Institute of the Philippines

Process Selection

Following the initial feasibility and market evaluation, the next stage is the
comparison of the alternative process routes for the manufacture of the chemical.
Selection of the appropriate process is an important decision, as all the subsequent
works depends upon this choice.

There are three possible processes for the manufacture of phthalic anhydride:
the Badger-Sherwin-Williams (naphthalene-based process), the Low Energy von Hayden
(LEVH) process and the Low Air Ratio (LAR) process. Summarized below are the
process description for each.

Process 1: Production of Phthalic Anhydride from the Oxidation of Naphthalene

(Badger-Sherwin-Williams Process)

The feed materials for this process include air and petroleum-based
naphthalene. The feeds are preheated before reaction to 400℃ for naphthalene and
240℃ for air. The weight ratio of air to naphthalene fed to the reactor is 10:1 to 12:1,
which places the mixture within the explosive limits.

Figure 6.1 Process Flow Chart for Badger-Sherwin-Williams Process

In this process, filtered air is compressed and heated to 149oC. The hot air then
enters the bottom of the reactor and passes through an air distributor plate before
entering the fluidized catalyst bed. Liquid naphthalene is pumped from the storage tank
and injected directly into the fluidized bed. The naphthalene is immediately vaporized
and dispersed throughout the bed upon contact with the hot catalyst and reaction air.

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Aside from being a naphthalene-based process and employing a different type

of reactor, the main difference of Badger-Sherwin-Williams process from the other two is
the catalyst filter after the fluidized bed reactor. The entrained catalyst particles are
separated from the gas stream by specially designed porous ceramic filter elements.
Process air is used to periodically blow back the filters, and the catalyst particles are
returned directly to the reactor bed.

Process 2: Production of Phthalic Anhydride from Oxidation of Ortho-xylene via

Low Air Ratio (LAR) Process

Feed materials used in this process consist of ortho-xylene and air. The xylene
feed contains 95-96% by weight o-xylene, the remainder consisting of meta- and para-
xylenes. Only the o-xylene can form phthalic anhydride.

Figure 6.2 Process Flow Chart of LAR Process

There are three principal steps in the production of phthalic anhydride via LAR
process: reaction, condensation and purification. The basic process consists of mixing a
stream of vaporized ortho-xylene with compressed air and then feeding this stream into a fired
heater and then into an isothermal reactor were the crude product is obtained. Here,
steam is generated which is used as utility in the plant.

Process 3: Production of Phthalic Anhydride from Oxidation of Ortho-xylene via

Low Energy von Hayden (LEVH) Process
The key difference between the LAR and the LEVH process is the presence of an
extra condensing unit (after-cooler) in the former which allows some of the phthalic
anhydride to be recovered from the reaction gas by condensation rather than sublimation.

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 Technological Institute of the Philippines

Figure 6.3 Process Flow Chart of LEVH Process

The higher air to o-xylene ratio which is used in the LEVH process necessitates
additional capacity in some items of equipment, such as the air compressor, the reactor,
the gas-cooler and the switch condensers.

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Evaluation of the Three Processes
Shown below is a summary of the characteristics of each of the three processes in the production of phthalic anhydride.
Table 6.1 Evaluation of the Three Processes
Constraints LAR
(Low Air Ratio)
Uses ortho-xylene as the primary raw
Raw Materials Used
material in producing PAN
Ortho-xylene is readily available from
Availability of Raw
the cracking of xylene mixtures in
Material
petroleum plants and refineries
Ortho-xylene: 95 – 96%
Purity of Raw Meta-xylene and para-xylene: 4%
Materials Used in
Process Feed impurities are converted to
carbon oxides in the reactor.
Ortho-xylene reduces raw material
costs by 25% and utility cost by 30%
Raw material, Utility
and Equipment Cost Low air to o-xylene ratio is
9.5:1
Low amount of raw materials needed
in the process decreases the
LEVH
(Low Energy von Hayden)
Uses ortho-xylene as the primary raw
material in producing PAN
Ortho-xylene is readily available from
the cracking of xylene mixtures in
petroleum plants and refineries
Ortho-xylene: 95 – 96%
Meta-xylene and para-xylene: 4%
Feed impurities are converted to
carbon oxides in the reactor.
Ratio of raw materials used is higher
compared to LAR
High air to o-xylene ratio is
20:1
Large amount of raw materials
needed in the process necessitates
Badger-Sherwin-Williams
(Naphthalene-based)
Uses naphthalene as the primary raw
material in producing PAN
Naphthalene is a by-product produced
from coal tar and dependent on the
manufacturing of coke which is not of
high quantities
Primary sources:
Coal-tar naphthalene:
Naphthalene: 92-96%
Sulfur: 0.5 – 1%
Tetralin: 2%
Petroleum naphthalene:
Naphthalene: 99-99.7%
Sulfur: 0.001%
Ratio of raw materials used is higher
compared to LAR but is lower compared
to LEVH
Air to naphthalene weight ratio is
10:1 to 12:1
Although the ratio of naphthalene to air
needed is lower compared to LEVH,
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 capacity of equipments and allows
the reduction of capital costs and
energy savings.
Theoretical yield:
1.39kg PAN/kg o-xylene
Product Yield Commercial yield:
1.09kg PAN/kg o-xylene
Produces higher yie1ds because all
carbon atoms appear in the product
By-Products Fewer impurities are produced by the
reaction
Types of Reactors
Fixed-bed reactor
Used
Consists of an extra condensing unit
(after-cooler) allows some of the PAN process through desublimation thus
Condenser used to be recovered from reaction gas by
condensation rather than
desublimation.
additional capacity in some of the
equipment, such as air compressor,
reactor, gas-cooler and switch
condensers which increases the
capital cost and energy saving of the
process.
Theoretical yield:
1.39kg PAN/kg o-xylene
Commercial yield:
1.09kg PAN/kg o-xylene
Produces higher yie1ds because all
carbon atoms appear in the product
Fewer impurities are produced by the
reaction
Fixed-bed reactor
No extra condensing unit used.
The PAN is recovered from the
decreases the product quality and
requires intensive purification process intensive purification process to achieve
to achieve the desired quality.
since it is an impure product, large
amount of raw material is needed in
order to attain the desired amount of
product thus increasing the cost of raw
material
Theoretical yield:
1.15kg PAN/kg naphthalene
Commercial yield:
0.95kg PAN/kg naphthalene
Produces lower yields because
naphthalene in not pure
Wide range of by products
Fluidized bed reactor
(fluidized bed processes have been
proved difficult to maintain and have
suffered from erosion problems and
excessive catalyst losses)
No extra condensing unit used.
The PAN is recovered from the process
through desublimation thus decreases
the product quality and requires
the desired quality.
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 Technological Institute of the Philippines

Process Selection Conclusion

From the presented descriptions of the three processes, Low Air Ratio is selected.
Table 5.2 shows the criteria and the rating for each, 1 being the highest.

Table 6.2. Ranking of Process Selection (Rate: 1-3, 1 being the highest)

Naphthalene-
Criteria Percentage LAR LEVH
based
Raw Materials Availability 10 1 1 2
Purity of Raw Materials 10 1 1 2
Raw Material Cost 15 1 2 2
Utility and Equipment Cost 20 1 3 2
Product Yield 15 1 1 2
By-Products 10 1 1 2
Reactor Used 10 1 1 2
Product Quality Improvement 10 1 2 2
Score 100 1 1.65 2

Low air ratio (LAR) has been selected as the main production process because of
its advantages in comparison with LEVH and Naphthalene-based processes. Its main
advantages are the following: the supplies of naphthalene in the Philippines are
diminishing because of the lower coke consumption, resulting to low coal tar and
naphthalene production while the availability of o-xylene increases form refinery
operation.
The ratio of o-xylene to air has been reduced from 20:1 to 9.5:1 which lowers
the raw material costs by 25% and utility cost by 30%. It also reduces the size and duty
of some equipment like; air preheater, reactor and switch condenser which decreases the
capital cost.
An after cooler is also employed to increase the recovery of liquid PAN which
upsurges the product quality by reducing the concentration of impurities entering the
product stream in the condensers. O-xylene LAR process also produces higher product
yie1ds. Its theoretical yield is 1.39kg PAN/kg o-xylene compared to only 1.15kg PAN/kg
naphthalene in naphthalene based process.
Because of the developments done in Low Air Ratio (LAR) process, the cost of
producing phthalic anhydride became significantly cheaper, which lessens the final
selling price produced lower than other processes.

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