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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 LEVH


Badger-Sherwin-Williams
(Low Air Ratio) (Low Energy von Hayden)
(Naphthalene-based)
Uses naphthalene as the primary raw
Uses ortho-xylene as the primary raw Uses ortho-xylene as the primary raw
Raw Materials Used material in producing PAN
material in producing PAN material in producing PAN

Naphthalene is a by-product produced


Ortho-xylene is readily available from Ortho-xylene is readily available from
Availability of Raw from coal tar and dependent on the
the cracking of xylene mixtures in the cracking of xylene mixtures in
Material manufacturing of coke which is not of
petroleum plants and refineries petroleum plants and refineries
high quantities

Primary sources:
Ortho-xylene: 95 – 96% Ortho-xylene: 95 – 96% Coal-tar naphthalene:
Purity of Raw Meta-xylene and para-xylene: 4% Meta-xylene and para-xylene: 4% Naphthalene: 92-96%
Materials Used in Sulfur: 0.5 – 1%
Process Feed impurities are converted to Feed impurities are converted to Tetralin: 2%
carbon oxides in the reactor. carbon oxides in the reactor. Petroleum naphthalene:
Naphthalene: 99-99.7%
Sulfur: 0.001%
Ratio of raw materials used is higher
Ortho-xylene reduces raw material Ratio of raw materials used is higher compared to LAR but is lower compared
costs by 25% and utility cost by 30% compared to LAR to LEVH
Raw material, Utility
and Equipment Cost Low air to o-xylene ratio is High air to o-xylene ratio is Air to naphthalene weight ratio is
9.5:1 20:1 10:1 to 12:1

Low amount of raw materials needed Large amount of raw materials Although the ratio of naphthalene to air
in the process decreases the needed in the process necessitates needed is lower compared to LEVH,

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capacity of equipments and allows additional capacity in some of the since it is an impure product, large
the reduction of capital costs and equipment, such as air compressor, amount of raw material is needed in
energy savings. reactor, gas-cooler and switch order to attain the desired amount of
condensers which increases the product thus increasing the cost of raw
capital cost and energy saving of the material
process.

Theoretical yield:
Theoretical yield: Theoretical yield:
1.15kg PAN/kg naphthalene
1.39kg PAN/kg o-xylene 1.39kg PAN/kg o-xylene
Commercial yield:
Product Yield Commercial yield: Commercial yield:
0.95kg PAN/kg naphthalene
1.09kg PAN/kg o-xylene 1.09kg PAN/kg o-xylene

Produces lower yields because


Produces higher yie1ds because all Produces higher yie1ds because all
naphthalene in not pure
carbon atoms appear in the product carbon atoms appear in the product

By-Products Fewer impurities are produced by the Fewer impurities are produced by the Wide range of by products
reaction reaction

Fluidized bed reactor


Types of Reactors (fluidized bed processes have been
Fixed-bed reactor Fixed-bed reactor
Used proved difficult to maintain and have
suffered from erosion problems and
excessive catalyst losses)
No extra condensing unit used. No extra condensing unit used.
Consists of an extra condensing unit The PAN is recovered from the The PAN is recovered from the process
(after-cooler) allows some of the PAN process through desublimation thus through desublimation thus decreases
Condenser used to be recovered from reaction gas by decreases the product quality and the product quality and requires
condensation rather than requires intensive purification process intensive purification process to achieve
desublimation. to achieve the desired quality. 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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