Design Data

Pure Component Properties

Properties of Toluene
Toluene (C7H8), otherwise known as toluol is a colorless clear liquid characterized by an
aromatic odor that can be associated with paint thinners. It is an aromatic hydrocarbon that
consists of a CH3 group attached to a phenyl group. It is less dense than water and is also
insoluble in it. Toluene is naturally occurring in small amounts in crude oil and is a byproduct in
gasoline production by catalytic reforming or ethylene cracking as well as a byproduct in coke
production form coal. Toluene is popularly used as a precursor to benzene via hydrodealkylation.
It is also commonly used to produce benzaldehyde and benzoic acid via oxidation. Apart from
these, Toluene is used as a solvent in paints, paint thinners, adhesives, leather tanners, octane
booster in gasoline and more. The representation of Toluene chemical structure is presented in
Figure

Figure

Toluene, as an aromatic hydrocarbon, reacts in electrophilic aromatic substitution. Due to

the methyl group which has larger electron releasing properties than if a hydrogen were in its
position, Toluene is more reactive to electrophiles compared to benzene. Also, it is Toluenes
methyl side chain which makes it susceptible to oxidation. Presented on Table are the physical
and thermodynamic properties of Toluene that are useful for the establishment of the mass and
energy balances of the process scheme.

Table 1.4.1.1. Physical and Thermodynamic Properties of Toluene (Haynes, 2015)

Property Value
Molecular Weight, g/mol 92.141
Freezing point, oC in air at 101.3 kPa -94.9
Boiling point, oC at 101 kPab 110.6
Density, g/cm3
 20oC 0.8623
25oC 0.867
Vapor pressure, 25oC, mmHg 28.4
Viscosity, absolute, 25oC inmPas(=cP) 1.165
Auto - ignition, oC 480
Heat of combustion, kJ/mol 3.910.3x103
Heat of vaporization, 25oC, kJ/mol 38.01
Solubility in H2O, 20oC, g/L H2O 0.52
Heat capacity J/molK 155.96
Critical point, oC, MPa 318.64, 4.109
Std enthalpy change of fusion KJ/mol 6.636
Std entropy change of fusion J/molK 37.25
Std enthalpy change of vaporization KJ/mol 38.06
Std entropy change of vaporization J/molK 87.30

Properties of Oxygen
Oxygen is an element with atomic symbol O; it is colorless, odorless and tasteless. Pure
oxygen is noncombustible however is plays a key role in the burning of combustible materials.
At standard temperature and pressure, it is present in the form dioxygen with the molecular
formula O2 where the double bond results fro low to high energy from Aufbaus principle.
Oxygen is the most abundant chemical element in the Earths biosphere by mass. 55% of Oxygen
is commercially used in the smelting of iron ores into steel. Another use is to produce ethylene
oxide via reaction with ethylene which can then be converted to ethylene glycol. Other
applications include that in the medical industry, metal welding and cutting, in water treatment
and more. Sources of highly concentrated oxygen promote rapid combustion although oxygen is
not the fuel, but merely the oxidant, it is the source of most of the chemical energy released in
combustion. Presented on Table are the physical and thermodynamic properties of Oxygen that
are useful for the establishment of the mass and energy balances of the process scheme.

Table 1.4.1.5. Physical Properties of Hydrogen

Color Colorless
Phase Gas
Molar mass 31.998 g/mol
Melting point 218.4 oC
Boiling point 182.96 C
Density at stp (0 C and 101.325 kPa) 1.429 g/L
Triple point 54.361 K, 0.1463 kPa
Critical point 154.581 K, 5.043 MPa
Heat of fusion (O2) 0.444 kJ/mol
Heat of vaporization (O2) 6.82kJ/mol
Molar heat capacity (O2) 29.378 J/(molK)
Properties of Benzoic Acid
Benzoic acid (C7H6O2) is a white crystalline solid organic compound and it is also an
aromatic carboxylic acid. It is slightly water soluble. Gum benzoin is a natural source of benzoic
acid however it is mostly produced by synthetic means. Benzoic acid salts known as benzoates
are commonly used as food preservatives in the form of sodium benzoate or potassium benzoate
and it is also an important precursor in the industrial synthesis of various other organic
compounds. Benzoic acid is produced commercially by oxidation of toluene with oxygen using
cobalt or manganese as catalyst. The chemical structure of Benzoic acid is presented in Figure

Figure
Benzoic acid cpntains carbon this it is an organic compounds also it is aromatic due to the
benzene ring in its chemical structure with alternating double bonds between each carbon. It is
classified as a carboxylic acid because it has a COOH, carboxyl, group in its structure. The
physical and thermodynamic properties of benzoic acid are presented in Table.

Table 1.4.1.1. Physical and Thermodynamic Properties of Benzoic Acid (Haynes, 2015)
Property Value
Molecular Weight, g/mol 122.12
Melting point, oC 122.41
Boiling point, oC at 101 kPa 249.2
Density, g/cm3
15oC 1.2659
130oC 1.0749
Vapor pressure, 25oC, Pa 0.16
Viscosity, absolute, 25oC inmPas(=cP) 1.26
Solubility in H2O, 25oC, g/L H2O 3.44
Specific Heat capacity J/molK 146.7
Std molar entropy J/molK 167.6
Std enthalpy of formation KJ/mol -385.2
Std enthalpy of combustion KJ/mol -3228
Thermodynamic Properties
Thermodynamic data are essential in the completion of the mass and energy balances which are
fundamental to the design objective. Presented here are the literature data that were used to
establish the balances across the whole plant process.
Table 1.4.1.1 List of Thermodynamic Properties of gaseous compounds (Green & Perry, 2008)
Name of Component Molecular Ideal gas Ideal has Ideal gas Heat
Formula Gibbs enthalpy of entropy, So capacity
energy of formation, (J/molK) Cp (J/
formation, fHo molK)
fGo (KJ/mol)
(KJ/mol)
Oxygen O2 - - 205.2 29.4
Methane CH4 -50.5 -74.6 186.3 35.7

Table 1.4.1.1 Molar Heat Capacities of Selected Liquids and Vapors (Green & Perry, 2008)
Name of Molecula Phase Cp A B C D
Component r Formula (approx.)
Toluene C6H5CH3 gas 103.8 -24.35 0.5125 -2.765e-4 4.99e-8
liquid 157.2 125.8 0.0565 1.359e-4
Methane CH4 gas 35.7 19.25 0.0521 1.197e-5 -1.132e-8
Water H2O gas 33.6 33.24 0.0192 1.055e-5 -3.596e-9
liquid 75.4 72.43 0.0104
Acetic Acid C2H4O2 gas 66.5 4.840 0.2549 -1.753e-4 4.949e-8
liquid 124.4
Benzene C6H6 81.7 -33.92 0.4739 -3.017e-4 7.13e-8
134.3 -6.21 0.5650 -3.141e-4

For approximate calculations the column labeled Cp approx. which is the heat capacity at 25oC.
For more accurate calculations, the polynomial expression Cp=A+BT+CT2+DT3 where Cp is in
J/gmolK and T is in K.
Table 1.4.1.Antoine Equation Constants for Selected Compounds (Green & Perry, 2008)
Name of Formula Range, A B C
o
Component C
Toluene C7H8 6 - 137 6.95464 1344.8 219.1
Acetic acid CH3COOH 7.38782 1533.31 222.309
3
Benzene C6H6 8 - 103 6.90565 1211.033 220.790
Benzoic acid C6H5COOH 96 - 250 7.3533 1771.4 145.67
Water H2O 0 60 8.10765 1668.21 235
60 - 150 7.96681 1474.67 228
 9
The constants are to be used in the Antoine equation for modeling saturation pressures of liquids
and solids. Constants should not be used outside the indicated temperature range.
B
Psat ( mmhg )= A O
T ( C)+ C
log 10

Vapor - Liquid Equilibrium Data

Following the oxidation reactor is a distillation step which is added with the main
purpose of recycling the unreacted Toluene back into the oxidation reactor. Distillation is
incorporated since it is applicable for separation of liquids with significantly different boiling
points from each other such as in this case. The components exiting from the oxidation reactor
that are to be fed into the distillation column are mainly the desired product Benzoic acid,
Toluene, acetic acid, Benzaldehyde and Benzene. Acetic acid, Toluene and a trace amount of
Benzene will exit as the overhead product considering that the distillation column is to be
operated at 150oC (403.15 K) and 1 atm and the aforementioned compounds have a boiling
points of 80.1 oC, 110.6oC and 118.1oC, respectively. The remaining Benzoic acid and
Benzaldehyde with higher boiling points of 249.2 oC and 178.1 oC, respectively will exit as the
bottoms product. Presented in Figures _ and _ are the P-x-y diagrams at set operating
conditions. These figures show that at 421.15 K and 1 atm, acetic acid and Toluene are
completely vaporized while Benzoic acid and Benzene remain completely liquid.
Mass Balance Calculations

The basis for the toluene feed is first set to 100kmol/hr. The recycled stream is not being
considered when calculating the mass balance at first. The composition and the mass flow of the
recycle stream is then obtained and the calculation is continued with the recycle stream. Lastly,
the calculated values are scaled up to achieve the desired mass flow rate. The goal, as stated in
the problem statement, is to produce the specified amount of 10,000 tons benzoic acid per year.
Considering that the plant is operational for 350 days per year, a production rate of 1,191 kg/
hour benzoic acid must be achieved.

The composition of the fresh toluene feed and oxygen feed are presented below. In order
to meet the required production rate, the mass flow rate of toluene feed coming from both the
fresh feed and recycled feed must be 967.4534 kg/hr and the total oxygen must be supplied 15%
in excess, with a mass flowrate of 579.5783 kg/hr.

Table. Composition by weight of fresh toluene feed

Component Mass flowrate [kg/hr] Mass fraction

Toluene 967.4534 0.9924
Methane 0.9160 0.0009
Water 0.4580 0.0005
Benzene 0.4580 0.0005
TOTAL: 5.5851 0.0057

Table. Composition by weight of oxygen feed

Component Mass flowrate [kg/hr] Mass fraction
Oxygen 579.5783 1.0000
TOTAL: 579.5783 1.0000

Table. Composition by weight of toluene feed from recycle

Component Mass flowrate [kg/hr] Mass fraction
Toluene Toluene 53.3106
Benzene Benzene 0.4580
Acetic Acid Acetic Acid 5.5851
TOTAL: TOTAL: 59.3536

Mass balance across Oxidation Reactor

 Reactor 1 will be operated at 140oC and 2.96 atm. At these conditions, 94.4% conversion
of toluene to benzoic acid will be achieved and the 98.4% selectivity for the catalyst (NHPI,
MnO2 and acetic acid). (Jiang, et al., 2011)

Figure
Downstream components

Benzoic acid=967.4534 kmol toluene ( 0.984 )( 0.944 ) ( 1kmol Bz . acid

)( 122.12 kg
1 kmol toluene kmol Bz . acid ) kg
=1,191.0993 Bz . acid
hr

Benzaldehyde=967.4534 kmol toluene ( 10.984 ) ( 1 kmol Benzaldehyde

1 kmol toluene )( 106.12 kg
kmol Benzaldehyde ) kg
=17,8285 Ben
hr

kmol toluene feed kg

Toluene unreacted=967.4534 (0.984 )(10.944)(92.14 )
hr kmol Toluene

kg
Mass of unreacted toluene=53.3106 toluene
hr

Overhead components
1.5 kmol O2
1,191.0993 kg Bz . acid
1kmol
( 122.12kg )( 1 kmol Bz . acid )( 1 kmol
32 kg
O )2
+17.8285 kg Benzaldehyde (
1 kmol Benzaldehyd
106. 12 kg
Oxygenunreacted =579.5783 kg O 2

kmol H 2 O
water =1,191.0993 kg Benzoic acid ( kmol
122.12kg )( )(
kmol Bz . acid
18.02
kg
)
kmol H 2 O
+17.8285 kg Benzaldehyde(1

The mass of the catalyst components NHPI, MnO2 and acetic acid do not take part or do not get
consumed by the oxidation reaction and therefore exit the reactor with the same mass.

Table. Summary of Downstream Product from the Oxidation Reactor

Component Mass flowrate [kg/hr] Mass fraction

 Benzoic Acid 1,191.0993 0.8069
Toluene 53.3106 0.0361
Benzaldehyde 17.8285 0.0121
Benzene 0.4580 0.0003
Acetic Acid 5.5851 0.0038
NHPI 171.2970 0.1160
MnO2 36.5148 0.0247
TOTAL: 1,476.0932 1.00

Table. Summary of Overhead Product from the Oxidation Reactor

Component Mass flowrate [kg/hr] Mass fraction

Oxygen 106.0564 0.3706
Methane 0.9160 0.0032
Water 179.1949 0.6262
TOTAL: 286.1673 1

The downstream product from the reactor are sent to the adsorption column for the removal of
the catalyst components NHPI and MnO2. The same components from the oxidation reactor
downstream products except the NHPI and MnO2 then enter a distillation column.

Following the oxidation reactor is a distillation step which is added with the main purpose of
recycling the unreacted Toluene back into the oxidation reactor. Acetic acid, Toluene and a trace
amount of Benzene will exit as the overhead product considering that the distillation column is to
be operated at 150oC (403.15 K) and 1 atm and the aforementioned compounds have a boiling
points of 80.1 oC, 110.6oC and 118.1oC, respectively. The remaining Benzoic acid and
Benzaldehyde with higher boiling points of 249.2 oC and 178.1 oC, respectively will exit as the
bottoms product.

Table. Summary of Overhead Product from the Distillation Column

Component Mass flowrate [kg/hr] Mass fraction

Toluene 53.3106 0.8982
Benzene 0.4580 0.0077
Acetic Acid 5.5851 0.0941
TOTAL: 59.3536 1.00

Table. Summary of Bottoms Product from the Distillation column

Component Mass flowrate [kg/hr] Mass fraction

Benzoic Acid 1191.0993 0.9853
 Benzaldehyde 17.8285 0.0147
TOTAL: 1208.9277 1.00

The bottoms product from the distillation column is sent to the hot water wash unit where
approximately 0.8 kg water is fed per kg of benzoic acid produced. For 1191.0933 kg/hr of
Benzoic acid 966.06996 kg/hr of water will be used. In this operation, the Benzaldehyde
component will be separated from the Benzoic acid water mixture. This Benzoic acid water
mixture is then sent to a centrifugal filter and then dryer, a concentrating step to remove the
water. The final product composition that exits from the dryer is 99.5 mole % Benzoic acid.
kg water kg mole
water removed=966.07
hr
1,191.0993 (
hr 122.12kg Bz . acid )( 0.05
0.95 )( 18.02
kg water
mole ) kg
=965.19 wate
hr

Table. Summary of Final Product from the dryer

Component Mass flowrate [kg/hr] Mass fraction

Benzoic Acid 1191.0993 0.9993
water 0.8830 0.0007
TOTAL 1191.9822 1.0000