Separator

Eliminate difference in composition

After the reactor, the reaction mixtures resulting from the catalytic oxidation of n-butane in the
vapor phase for the production of maleic anhydride generally contain other substances.The
gaseous reaction mixture contains about 0.5 to about 2% by volume of the anhydride together
with by products such as carbon monoxide, carbon dioxide, water vapor, inert gases (nitrogen),
unreacted oxygen and n-butane. Therefore, it is necessary to separate out the unwanted
components and to obtain a higher purify desired product, MAN.

Several determinants, such as temperature, pressure, phase, other physical as well as

chemical properties and other conditions of the stream are essential to be aware of when
selecting the separation process. In separation, volatility is e the fundamental principle is used
to separate the components. This implies that components with lower boiling point are removed
as the top products; components with higher boiling point are removed as the bottom products.
The liquid-gas critical points are key constants in the determination of fluid behaviour for
separation. The data below will aid in separator design decisions making.

Table 1: Boiling Point of Each Component at Different Pressure (Perry and Chilton, 2008)
Boiling point (°C) Critical constant
Reactant / Chemical 101 115 204 304 Tc,°C Pc, kPa
Product Formula kPa kPa kPa kPa
Maleic Anhydride C4H2O3 202 207 232 249 448 7280
(MAN)
N-Butane C4H10 -1 2 19 32 152 3790
Nitrogen N2 -196 -195 -190 -186 -145 384
Oxygen O2 -183 -182 -176 -171 -119 5046
Water H2O 100 103 120 134 374 22060
Carbon dioxide CO2 -87 -86 -76 -68 31 7376
Carbon monoxide CO -192 -191 -185 -181 -140 3496
Dibutyl phthalate C16H22O4 337 343 370 391 524 1600
Separator: Flash separator (Sharon part)

According to the general heuristic of separation, it is always preferred to separate the

most plentiful components early. Therefore, nitrogen gas (which is the most abundance
unreacted product) is removed first via two-phase separation unit. The reaction mixture leaving
the

Separator: Distillation column (Man purification)

According to heuristic also advises to save the most difficult separation for last. In this case,
purification of MAN will be conducted last.

Separator: Absorber Column

Generally, the uncondensed vapour stream from the separator contain about 1 volume percent
maleic anhydride and about 10 volume percent water vapor plus other gases compound. MAN
is the valuable product and cannot be ignored, therefore it is required to be recover. A
separation unit must be placed after the separator to separate MAN from the vapour stream.

Since the component MAN to be separated is in vapour form. Heuristic 11 is applied

in selection of separation system whereby it stated that the separation of vapour mixture is
recommended to use partial distillation, cryogenic distillation, adsorption, membrane
separation and/or desublimation (Seider et al., 2009). Absorption technique is the most feasible
solution. It separates the different components based on the exchange of atoms and molecules
between solvent and vapor component individually. The most optimum solvent used comprises
of dibutyl phthalate and about 1.25 percent phthalic anhydride by weight. The solvent will only
absorb the MAN leaving most of the water, acetic acid, acrylic acid, inert gases (nitrogen),
unreacted n-butane, carbon monoxide and carbon dioxide in the gaseous form. No reaction will
occur in the solvent and MAN will retain its original property (Quin, 2002).

Absorber tower is use for recovery of MAN. The most suitable operating unit will be
packed bed absorber column. The packing present (i.e. Ceramic Raschig rings, Berl Saddles)
inside the packed bed column will increase the contact time between the vapor phase and the
liquid phase components in order to enhance their separation efficiency and mass transfer of
maleic anhydride. Ceramic Raschig rings and Saddles are relatively low in cost, moderate
pressure drops and high vapor capacity. In addition, ceramic has superior wettability, corrosion
resistance at elevated temperature (Pérez and Segura, 2016). Absorber column shell and heads
are usually fabricated out of high alloy steel such as stainless steels to withstand corrosion. To
increase the strength and corrosion resistance, cladding and linings with rubber or cement are
usually implemented (Kletz, 2009).

Figure: Ceramic Raschig Rings and Berl Saddles Packing Material (Kletz, 2009)

Figure: Typical Layout of Packed Bed Absorber (Pérez and Segura, 2016)

Vapor gas is introduced from the lower section of the absorber column in order to have
the MAN be absorbed by the solvent dibutyl phthalate in counter current flow from the other
vapor components. By looking at table 1, the inlet gas to the absorption tower the product gas
should be cooled to a temperature between preferably between about 150 °C with a pressure
around 200 kPa to encounter pressure drop in the absorber. Most packed-bed absorbers are
designed to safely avoid flooding conditions and to operate in the preloading region, with a
gas-pressure drop limit of 4 kPa/m of packed depth. The pressure drop of this 10-tray absorber
column is estimated to be 90 kPa as there is a lot of packing materials within the absorber
(Oliva, Dissertation and Perales, 2017). The temperature must be above the dew point of the
water in the gaseous reaction mixture. As well as to make sure the mixture is in vapour form
to drive up the column. This temperature will also prevent the solvent dibutyl phthalate to
vaporise as it is way below the its boiling point of 370 °C at 204 kPa. If the gaseous reaction
mixture is at a temperature below the dew point of water, maleic anhydride, or other
components, these materials will accumulate on the walls of the equipment and block the gas
flow (Quin, 2002).

The solvent inlet will be introduced at the top to the absorption tower through spraying
to increase the contact area at a temperature below 75 °C. The solvent inlet is preferably at a
temperature between about 20° and 40 °C (Brown, Henry, 1997) and at a pressure of 113.3 kPa
(Pérez and Segura, 2016). The temperature is in accordance to Table 1 as low temperature
solvent will be encounter for the energy transfer from contacting the gas mixtures, solvent
would not be vaporised. The solvent will only absorb the MAN leaving most of the water,
acetic acid, acrylic acid, inert gases (nitrogen), unreacted n-butane, carbon monoxide and
carbon dioxide in the gaseous form.

The liquor leaving the column should contain about 5 to 45 weight percent maleic
anhydride, more preferably between 15 to 25 weight percent. If the ratio of lean solvent to
product gas is too large, unnecessarily large quantities of absorption liquor must be processed
in subsequent steps to recover the maleic anhydride. On the other hand, if the ratio of lean
solvent to product gas is too low, excessive losses of maleic anhydride may occur. The ideal
ratio should be about 0.1 to 0.2 kilograms of solvent per cubic meter of gaseous reaction
mixture (Brown, Henry, 1997).

The rest unabsorbed overhead gasses are free of MAN. They are either exhaust into the
atmosphere or to an incinerator. Since the off-gas from the absorber contains unreacted n-
butane from the reaction, it is logical to recover and recycle it back to the reactor. Unfortunately,
air is used to oxidise the n-butane in the feed. Most of the inert gas is unreacted and the butane
concentration in the off-gas is so low, diluted mainly by the large quantity of nitrogen, that the
cost of recovery is prohibitive. Direct recycle of the off-gas is not possible because the nitro
gen build-up cannot be tolerated. (Marshall, 1972).

The liquor solvent-rich-maleic anhydride from the bottom stream is gathered for further
recuperation and purification (Oliva, Dissertation and Perales, 2017).

Table 2: Absorption Tower Operating Condition

Parameter Range Reference
Gas inlet
Temperature 150 °C
(MAN, n-butane, carbon
monoxide, carbon dioxide, (Quin, 2002)
water, acrylic and acrylic acids, Pressure 115 kPa
polymeric tars)
(Brown, Henry,
Temperature 20 - 40°C
1997)
Solvent inlet (Dibutyl phthalate) (Oliva,
Pressure 113.3 kPa Dissertation and
Perales, 2017)
(Brown, Henry,
liquid outlet 25 wt% of MAN
1997)
Temperature 90 °C (Oliva,
Absorption column Dissertation and
Pressure 113.3 kPa
Perales, 2017)
Solvent to gas ratio 0.1-0.2 kg solvent/m3 of gas (Quin, 2002)
(Oliva,
Dissertation and
Pressure drop Pressure 90 kPa
Perales, 2017).

Separator: Distillation Column (Solvent recovery)

In order to save the operating cost, it is essential to recover the solvent after the absorber unit.
Therefore, it is necessary to put a separator unit after the absorber. According to heuristic 9,
the liquid mixture is separated using distillation and stripping tower, liquid-liquid extractors
and other similar operators (Seider et al., 2009). In this case, distillation tower is used to
separate the MAN from the solvent in one-step operation, and the solvent is thereafter recycled
to the absorption tower. The distillation column separation is decided due to their high
difference in boiling points between solvent and MAN. Besides, a distillation column is
suggested for multicomponent separation as there are a small amount of impurities in the
solvent other than MAN such as water, carbon dioxide, and n-butane.

The light key is MAN with lower boiling point while the heavy key is dibutyl phthalate.
The relative volatility between the MAN light key (LK) and dibutyl phthalate, heavy key (HK)
is calculated based on the decided inlet temperature.

The inlet to the distillation column is mostly solvent containing the dissolved MAN.
From table 1, the temperature should be around 150 °C at low pressure of 200 kPa to encounter
for pressure drop in the unit. The feed inlet is mostly liquid. Hence high pressure is not needed
to liquified the mixture to reduce the condenser and boiler duty. Energy and operating cost are
saved. To recover the solvent, the inlet temperature is set to 150 °C above the dew point of
water so that water will be separated as top product.

The solvent is then separated from through the distillation column. The top products
exit at 200 °C with a condenser pressure of 110 kPa. Most of the MAN, water and other
impurities exit as top product. The temperature and pressure at the bottom of the stripping
column is important since its controls the maleic anhydride content in the solvent that is
recycled to the absorber. If the temperature of the solvent at the bottom of the distillation
column is less than about 200° C, the amount of maleic anhydride in the solvent will be high
and it prevents the solvent from being as efficient in the absorption step; however, when the
solvent temperature is too high, excessive decomposition of the dibutyl phthalate
occurs (James, 1976).

The solvent from the distillation column exits the bottom at a temperature of 345 °C
slightly above the boiling point, at a reduced pressure of 120 kPa due to pressure drop.
MAN concentration in the solvent is expected to be less than about 1 weight percent. Thereafter,
the solvent will be cooled, preferably filtered, and then recycled to the absorption tower (James,
1976). The top product MAN will be combined with the separator liquid outlet to be further
purified.

Material construction for distillation column should be

 Table 3: Antoine parameter for HK and LK
A B C Reference
LK C4H2O3
3.799 1431 -101.93 (Stull, 1947)
(MAN)
HK C16H22O4 (Hammer and
(dibutyl 4.306 2083 -131.7 Lydersen,
phthalate) 1957)

Determination of 𝑃𝑖′ by using Antoine Equation:

𝐵
𝑙𝑛 𝑃𝑖′ (𝑏𝑎𝑟) = 𝐴 −
𝑇(𝐾) + 𝐶

Determination of the vapour-liquid equilibrium ratio, 𝐾𝑖 by Raoult’s Law:

𝑦𝑖 𝑝𝑖 /𝑃 𝑃𝑖′
𝐾𝑖 = = =
𝑥𝑖 𝑝𝑖 / 𝑃𝑖′ 𝑃𝑠𝑦𝑠𝑡𝑒𝑚

Where,
𝑦𝑖 = vapour pressure
𝑥𝑖 = liquid pressure
𝑃𝑖′ = vapour pressure of component i (bar)
𝑝𝑖 = patial pressure of component i (bar)
𝑃𝑠𝑦𝑠𝑡𝑒𝑚 = Pressure of system

Determination of relative volatility, 𝛼𝑖 :

𝐾𝐿𝐾
𝛼=
𝐾𝐻𝐾

Table 4: Operation Conditions and Relative Volatilities (James, 1976)

Temperature Pressure Relative
𝑲𝑳𝑲 𝑲𝑯𝑲
(°C) (kPa) Volatility, 𝜶
150 204 0.2539 0.02851 8.906
Inlet temperature: 150°C = 423 K, A= MAN, B= dibutyl phthalate.

1431
LK: 𝑙𝑛 𝑃𝐴′ (𝑏𝑎𝑟) = 3.799 − 423+(−101.93)

𝑃𝐴′ = 0.5179 𝑏𝑎𝑟

2083
HK: 𝑙𝑛 𝑃𝐵′ (𝑏𝑎𝑟) = 4.306 − 423+(−131.7)

𝑃𝐵′ = 0.058 𝑏𝑎𝑟

𝑃𝑠𝑦𝑠𝑡𝑒𝑚 = 204 kPa = 2.04 bar

𝑃𝐴′ 0.5179 𝑏𝑎𝑟

𝐾𝐿𝐾 = = = 0.2539
𝑃𝑠𝑦𝑠𝑡𝑒𝑚 2.04 𝑏𝑎𝑟

𝑃𝐵′ 0.058 𝑏𝑎𝑟

𝐾𝐻𝐾 = = = 0.0285
𝑃𝑠𝑦𝑠𝑡𝑒𝑚 2.04 𝑏𝑎𝑟

Relative volatility, 𝛼𝑖 :
0.2539
𝛼= = 8.906
0.0285
Flowsheet:
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