GAZI UNIVERSITY FACULTY OF ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING

CHE451CHEMICAL ENGINEERING DESIGN I

REACTOR DESIGN FOR PHTHALIC ANHYDRIDE PRODUCTION

GROUP E

191142039 Serra KERMAN

191142043 Hafize Tuğçe ÖNAL (EDITOR)

191142049 Sait SEVİNÇ

201142024 Dila KARA (LEADER)

201142039 Efsane YAYLI

Submitted to:

Prof. Dr. SENA YAŞYERLİ

Res. Asst. İREM KOÇYİĞİT ÇAPOĞLU

14.12.2023

ANKARA

i
 ABSTRACT

The aim of this project is to design a reactor that produces high purity phthalic anhydrate at a
rate of 75,000 metric tons/year by oxidation of o-xylene in the presence of vanadium pentoxide
catalyst in an environmentally, cost-effective, feasible and safe manner.
In this design, the physical and chemical properties of the chemicals in the reaction were
determined. The operating conditions of the reactor were determined as 300˚C, 5 bars to
increase the production rate and efficiency. It was determined that the reactants used in the
reaction were in the gas phase at the specified temperature and pressure. In the study, enthalpy
was calculated which is -1137,6x103 j/mol and it was seen that the reactions occurring during
oxidation were exothermic reactions. The constant value of the equilibrium was checked to
determine whether the reaction is irreversible or reversible. The equilibrium constant value was
calculated as 1.88x1099 for 25 ˚C and the very high Keq value showed that the reaction would
be in the forward direction, that is, irreversible. The catalyst employed in the design project was
vanadium pentoxide. The utilization of vanadium pentoxide can be attributed to its ability to
exhibit high selectivity during the oxidation reaction of o-xylene. This characteristic proves as
it aids in minimizing the production of unwanted by-products. It was decided that the reactor
would operate isothermally in order to balance the temperature, prevent the catalyst from
getting sintering, and control the conversions. The reactor is operating as heterogeneous phase
and the phase of catalyst inside the reactor is solid. Multitubular fixed bed reactor was chosen
and its service life is determined as 10 years. The material of the reactor was chosen carbon
steel. Next, as a result of the research, it was concluded that the conversion in the industry was
0,1 and the selectivity was 0,8. Material balances were established using the given reactions,
and the volume was calculated as 50 m3 using the design equation for the multitubular packed
bed reactor. Tube diameters were chosen as 3/4 inch according to TEMA standards. Using
POLYMATH, the length of the reactor was calculated as 12 meters and the diameter was 2,3
meters and the number of tubes was 700. The low pressure drop across the reactor is a limiting
parameter during design. Therefore, the pressure drop was determined as 1,39x10-3 bar for each
tube, showing that our design was acceptable. For the cooling reasons heat transfer fluid was
used and it is chosen as Dowtherm MX.
The annual cost of the reactor was determined as 1,04x103 $/year. Annual cost of the catalyst
was found to be 1,35x105 $/year and the annual cost of utility is 1,57x105 $/year.
One of the most important parts of this design was to keep the o-xylene and air entry rate below
the upper flammability limit for safety. Therefore, the feed composition of the phthalic

ii
anhydride reactor was determined as 1% o-xylene and 99% air by volume. Controlling reactant
flows ensures that the process is managed efficiently, safely and to ensure product quality.
Especially in this process, air and o-xylene levels must be controlled to prevent the risk of
explosion. Flow measurement devices should be used in the process.

iii
 TABLE OF CONTENTS

ABSTRACT ...........................................................................................................................

1. INTRODUCTION ............................................................................................................1

2. METHOD OF ATTACK ..................................................................................................3

3. CALCULATIONS ............................................................................................................4

3.1. Thermodynamic Calculation for Main Reaction ...................................................................... 4

3.2. Thermodynamic Calculation for Side Reaction ....................................................................... 6
3.3. Material Balance for Reactor Design ......................................................................................... 9
3.4. Energy Balance for Reactor Design .......................................................................................... 15
3.5. Cost Calculation ............................................................................................................................ 16

4. RESULT AND DISCUSSION ........................................................................................ 18

5. CONCLUSION ............................................................................................................... 26

6. NOMENCLATURE ....................................................................................................... 27

7.REFERENCES ................................................................................................................ 28

APPENDICES .................................................................................................................... 29

i
 LIST OF FIGURES

Figure 1. Xa1 vs 1/-rT graph................................................................................................. 13

Figure 2.. Flow sheet of the reactor design ............................................................................ 22

ii
 LIST OF TABLES

Table 1. Reactor Design Method ............................................................................................3

Table 2. Properties of Components in Main Reaction (298K) [1] ...........................................4
Table 3. Heat Capacities Coefficient of Component in Main Reaction (j/molK) [1]................4
Table 4. Properties of Components in Side Reaction (298K) [1].............................................6
Table 5. Heat Capacities Coefficient of Component in Side Reaction (j/mol.K) [1] ................7
Table 6. Molar Flow Rates of Components ..........................................................................11
Table 7. Summary Table for Catalyst .................................................................................... 20
Table 8. Summary Table for Reactor .................................................................................... 21
Table 9. Specification for Fixed Bed Reactor ........................................................................ 21
Table 10. Specification for V2O5 catalyst .............................................................................. 22
Table 11.Flow summary table for flow sheet of the reactor design shown in Figure 1 ...........23

iii
1. INTRODUCTION

Phthalic anhydride is an important industrial chemical, especially for the large-scale production
of plasticizers for plastics.
• It is used in the production of plastics such as polyvinyl chloride or PVC and resins.
• It is also used in the production of paints, inks, varnishes, and coatings.
• It is used in some syntheses in the pharmaceutical industry.
In 2022, the worldwide production volume was estimated to be about 180 thousand tons per
year.
The complex problem of this project is to design a reactor for o-xylene oxidation to phthalic
anhydride over Vanadium(Ⅴ)oxide catalyst safely, environmentally friendly, technical feasible
and at minimum cost to form phthalic anhydride from o-xylene at a rate of 75,000 metric
tons/year.
The reactor is the heart of a chemical process. It is the only place in the process where raw
materials are converted into products, and reactor design is a vital step in the overall design of
the process. The design of the process involves the selection of the appropriate reactor type for
a particular process and an outline of the steps to be followed in the design of a reactor.
The selection of the best reactor type for a given process is subject to a number of major
considerations. Such design aspects, for example, include [1];
 temperature and pressure of the reaction.
 need for removal or addition of reactants and products.
 required pattern of product delivery (continuous or batchwise).
 catalyst use considerations, such as the requirement for solid catalyst particle
replacement and contact with fluid reactants and products.
 relative cost of the reactor.
 the form of the energy provided.
 the contacting phases (homogeneous or heterogenous).

In a heterogeneous reaction two or more phases exist, and the overriding problem in the reactor
design is to promote mass transfer between the phases [2].
In this design project, the combination of phases is in gas-solid: where the solid act as a catalyst
and reactants and products acts as a gas. For catalytic gas-solid reactions, fixed bed reactors,
fluidized bed reactors and multitubular fixed bed reactors can be chosen.

1
The reaction has been selected to be conducted in a multitubular fixed bed reactor, taking into
account its highly exothermic and heterogeneous nature. Tube diameters were chosen as 3/4
inch according to TEMA standards.
The features of this type of reactors are as follows [1];
 simplicity and ease of catalyst access for maintenance and regeneration
 improve both heat transport and control, resulting in improved performance
while maintaining the relative simplicity of this reactor arrangement.
 good thermal control and uniform residence time distribution
Exothermic reactions release heat which causes an increase in temperature. Rapid rising of
temperature is hard to control and requires additional equipment and leads to catalyst
degradation and sintering which is not a wanted situation for the reaction’s efficiency. For these
reasons working conditions are chosen as isothermal and non-adiabatic. At the same time, the
approach of the reactor is in the form of plug flow.

O-xylene is a flammable and explosive chemical. O-xylene and air ratio should be between
specified flammability limits. In order to operate safely, reaction mixture must be kept below
the lower explosive limit of 1 mol% of o-xylene in air. As a result of the research, it was
concluded that the conversion in the industry was 0,1 and the selectivity was given in the
assignment as 0,8.
In this project, a reactor has been designed to produce phthalic anhydride by oxidation of o-
xylene with vanadium pentoxide catalyst in an environmentally, economically, technically
feasible and safe manner. In this context, all calculations have been made and costs have been
calculated.

2
2. METHOD OF ATTACK

Various calculations were made in the reactor project designed to ensure the safe and
economical conversion of o-xylene to phthalic anhydride. The steps followed during the design
are shown in Table 1.

Table 1. Reactor Design Method

Collect physical and chemical properties data for each chemical.

Determine the main and side reaction.
Determine the working conditions for reaction.
Material and Energy Balance.
Determine the reactor type.
Making the solution with the polymath program.
Determine the size of reactor.
Determine the utility for reactor design.
Cost of the proposed design, capital and operating.

3
3. CALCULATIONS

3.1. Thermodynamic Calculation for Main Reaction

C8H10 + 3O2C8H4O3 + 3H2O

Table 2. Properties of Components in Main Reaction (298K) [1]

∆𝐇f (kJ/mol) ∆𝐆f (kJ/mol) 𝐓c (K) 𝐏c(𝐚𝐭𝐦)

C8H10 19 122,09 630,37 36,85
O2 0 0 154,58 72,44
C8H4O3 -393,13 -329 791 46,58
H2O -241,8 -228,6 647,13 55,26
N2 0 0 126,10 33,49

Table 3. Heat Capacities Coefficient of Component in Main Reaction (j/molK) [1]

A 𝐁 𝐂 𝐃
C8H10 0,182 5,1344x10-1 -2,0212x10-4 -2,1615x10-8
O2 29,526 -8,8999x10-3 3,8083x 10-5 -3,2629x10-8
C8H4O3 40,083 3,6084x10-2 9,5956x10-4 -1,2341x10-6
H2O 33,933 -8,4186x10-3 2,9906x10-5 -1,7825x10-8
N2 29,342 -3,5395 x 10-3 1,0076 x10-5 -4,311610-9

∆𝐶𝑝 = 𝑎 + 𝑏𝑇 + 𝑐𝑇 2 [Appendix B]

Gibbs Free Energy of Reaction

∆𝐺 = ∆𝐺𝑝𝑟𝑜𝑑𝑢𝑐𝑡 - ∆𝐺𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡

Δ𝐺𝑀𝑎𝑖𝑛 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = (∆𝐺𝑃𝐴 + ∆𝐺𝐻2 𝑂 ) - (∆𝐺𝑂𝑥𝑦𝑙𝑒𝑛𝑒 + ∆𝐺𝑂2 )

4
 𝑘𝐽 𝐽
= (-329 – 3x228,6) - (122,09 + 0) = - 1136,8 𝑚𝑜𝑙 = −1136,8𝑥103 𝑚𝑜𝑙

Since Gibbs Free energy at reference temperature is negative, the reaction occurs
spontaneously.

Enthalpy of Reaction
∆𝐻 = ∆𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡 - ∆𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡
Δ𝐻𝑀𝑎𝑖𝑛 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = (∆𝐻𝑃𝐴 + ∆𝐻𝐻2 𝑂 ) - (∆𝐻𝑂𝑥𝑦𝑙𝑒𝑛𝑒 + ∆𝐻𝑂2 )
𝑘𝐽 𝐽
= (-393,13 – 3x241,82) - (19 + 0) = - 1137,6 𝑚𝑜𝑙 = −1137,6𝑥103 𝑚𝑜𝑙

Specific Heat of Reaction

(∆Cp)reaction = (∆Cp)products − (∆Cp)reactants(J/mol.K)

∆Cpmain reaction = (∆Cp)products − (∆Cp)reactants

∆A = Aproducts − Areactants

= (40,083 + 3x33,933) − (0,182+ 3x29,526) = 53,122

∆B = Bproducts − Breactants

= [(3,6084x10−2 − 3𝑥8,4186𝑥10−3 ) − (5,1344x10−1 − 3𝑥8,8999𝑥10−3 )]= −0,4759

∆C = Cproducts − Creactants
= [(9,5956x10−4 + 3𝑥2,9906𝑥10−5 ) − (-2,0212x10−4 + 3𝑥3,8083𝑥10−5 )] = 1,137x10-3

∆𝐶𝑝 = 𝑎 + 𝑏𝑇 + 𝑐𝑇 2 = 53.122 – 0,4759T + 1,137x10−3 𝑇 2

Equilibrium Constant (at reference temperature at 𝟐𝟗𝟖 𝐊)

−∆𝐺°
𝐾298 = exp ( ) [3]
𝑅𝑇

𝑘𝐽
−1136,8
𝐾298 = exp( 8,314𝑥10−3 𝑘𝐽𝑚𝑜𝑙 ) = 1,88 x 1099
𝑥 298𝐾
𝑚𝑜𝑙𝐾

K ≫1 According to this value, it is understood that the reaction is irreversible at 298 K.

5
Calculation of ∆𝐇𝐓

𝑇
∆𝐻𝑇 = ∆𝐻298 + ∫ ∆𝐶𝑝 𝑑𝑇 [3]
298
573
𝐽 3
∆𝐻𝑇𝑚𝑎𝑖𝑛 = −1137.6𝑥10 + ∫ (53.122 − 0.4759T + 1.137 ∗ 10−3 𝑇 2 ) 𝑥𝑑𝑇
𝑚𝑜𝑙 298

𝐽 5732 − 2982
∆𝐻𝑇 = −1137.6𝑥103 + 53.122(573 − 298) − 0.4759 + 1.137
𝑚𝑜𝑙 2
5733 − 2983
∗ 10−3 )
3

𝐽 𝑘𝐽
∆𝐻𝑇𝑚𝑎𝑖𝑛 = −1118113.9 = −1118.11 𝑚𝑜𝑙
𝑚𝑜𝑙

Since enthalpy of reaction is negative at operating temperature, the reaction is exothermic.

3.2. Thermodynamic Calculation for Side Reaction

C8H10+7,5 O2  C4H2O3 + 4H2O + 4CO2

Table 4. Properties of Components in Side Reaction (298K) [1]

∆𝐇f (kJ/mol) ∆𝐆f (kJ/mol) 𝐓c (K) 𝐏c(𝐚𝐭𝐦)

C8H10 19 122,09 630,37 36,85
O2 0 0 154.58 49,77
H2O -241.8 -228.6 647.13 217,66
C4H2O3 -398,3 -355 721 71,84
CO2 -393,5 -394,4 304,19 72,85
N2 0 0 126,10 33,49

6
Table 5. Heat Capacities Coefficient of Component in Side Reaction (j/mol.K) [1]

A 𝐁 𝐂 𝐃
C8H10 0,182 5,1344x10-1 -2,0212x10-4 -2,1615x10-8
O2 29,526 -8.8999x10-3 3,8083x 10-5 -3,2629x10-8
H2O 33,933 -8.4186x10-3 2,9906x10-5 -1.7825x10-8
C4H2O3 -72,015 1,0423 -1,8716x10-3 1,6527x10-6
CO2 27,437 4,2315x10-2 -1,9555x10-5 3,9968x10-9
N2 29,342 -3,5395 x 10-3 1,0076 x10-5 -4,311610-9

∆𝐶𝑝 = 𝑎 + 𝑏𝑇 + 𝑐𝑇 2 [Appendix B]

Gibbs Free Energy of Reaction

∆𝐺 = ∆𝐺𝑝𝑟𝑜𝑑𝑢𝑐𝑡 - ∆𝐺𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡

Δ𝐺𝑆𝑖𝑑𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = (∆𝐺𝑀𝐴 + ∆𝐺𝐻2 𝑂 + ∆𝐺𝐶𝑂2 ) - (∆𝐺𝑂𝑥𝑦𝑙𝑒𝑛𝑒 + ∆𝐺𝑂2 )

𝑘𝐽 𝐽
= (-355 – 4x228,6 – 4x394,4) - (122,09 + 7.5x0) = - 2969.01 𝑚𝑜𝑙 = −2969.01𝑥103 𝑚𝑜𝑙

Enthalpy of Reaction
Δ𝐻𝑆𝑖𝑑𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = (∆𝐻𝑀𝐴 + ∆𝐻𝐻2 𝑂 + ∆𝐻𝐶𝑂2 ) - (∆𝐻𝑂𝑥𝑦𝑙𝑒𝑛𝑒 + ∆𝐻𝑂2 )
𝑘𝐽 𝐽
= (-398.3 – 4x393.51-4x241.8) – (19 + 0) = -2953.54 𝑚𝑜𝑙 = -2953.54 𝑥103 𝑚𝑜𝑙

Specific Heat of Reaction

(∆Cp) reaction = (∆Cp) products − (∆Cp) reactants(J/mol.K)

∆Cp = (∆Cp) − (∆Cp)

side reaction products reactants

∆A = Aproducts − Areactants

= (-72.015 + 4x33.933 + 4x27.437) − (0.182+ 7.5x29.526) = -48.162

7
∆B = Bproducts − Breactants

= [(1.0423 +4x4.2315x10−2 − 4𝑥8.4186𝑥10−3 ) − (5.1344x10−1 − 7.5𝑥8.8999𝑥10−3 )]

= 0.7311

∆C = Cproducts − Creactants
= [(−1.8716𝑥10−3 − 4𝑥1.9555𝑥10−5 + 4𝑥2.9906𝑥10−5 ) − (-2.0212x10−4 +
7.5𝑥3.8083𝑥10−5 )] = -1.91𝑥10−3

∆𝐶𝑝 = 𝑎 + 𝑏𝑇 + 𝑐𝑇 2 = -48.162 + 0.7311T -1.91∗ 10−3 𝑇 2

Calculation of ∆𝐇𝐓

𝑇
∆𝐻𝑇 = ∆𝐻298 + ∫ ∆𝐶𝑝 𝑑𝑇 [3]
298
573
𝐽 3
∆𝐻𝑇𝑠𝑖𝑑𝑒 = −2953.54 𝑥10 +∫ −48.162 + 0.7311T − 1.91 ∗ 10−3 𝑇 2 𝑑𝑇
𝑚𝑜𝑙 298

𝐽 5732 −2982
∆𝐻𝑇𝑠𝑖𝑑𝑒 = −2953.54 𝑥103 𝑚𝑜𝑙 +  − 48.162(573 − 298) + 0.7311 − 1.91 ∗
2
5733 −2983
10−3 )
3
𝐽 𝑘𝐽
= -2982145.48 𝑚𝑜𝑙 = -2982.1 𝑚𝑜𝑙

8
3.3. Material Balance for Reactor Design

C8H10 + 3O2 → C8H4O3 + 3H2O (Main Reaction)

C8H10 + 7.5O2 → C4H2O3 + 4H2O + 4CO2 (Side Reaction)

FA
FB
FAO FC
FBO FD
REACTOR
FIO FE
FF
FI

𝐶8 𝐻10 = A
𝑂2 = B
𝐶8 𝐻4 𝑂3 = C
𝐻2 𝑂 = D
𝐶4 𝐻2 𝑂3 = E
𝐶𝑂2 = F
𝑁2 = I

𝐹𝐴 = 𝐹𝐴0 − 𝐹𝐴0 𝑥𝐴1 − 𝐹𝐴0 𝑥𝐴2

𝐹𝐵 = 𝐹𝐵0 − 3𝐹𝐴0 𝑥𝐴1 − 7.5𝐹𝐴0 𝑥𝐴2
𝐹𝐶 = 𝐹𝐴0 𝑥𝐴1
𝐹𝐷 = 3𝐹𝐴0 𝑥𝐴1 + 4𝐹𝐴0 𝑥𝐴2
𝐹𝐸 = 𝐹𝐴0 𝑥𝐴2
𝐹𝐹 = 4𝐹𝐴0 𝑥𝐴2
𝐹𝐼 = 𝐹𝐼𝑂

𝑘𝑔 1 𝑘𝑚𝑜𝑙 1 𝑦𝑒𝑎𝑟 1 ℎ𝑜𝑢𝑟 1000 𝑚𝑜𝑙 𝑚𝑜𝑙 𝐶8 𝐻4 𝑂3

75000000 𝑦𝑒𝑎𝑟 𝑥 148.117 𝑘𝑔 𝑥 𝑥 x = 17.58
8000 ℎ𝑜𝑢𝑟 3600 𝑠 1 𝑘𝑚𝑜𝑙 𝑠

9
 𝑥𝐴1
= 0.8
𝑋𝐴1 + 𝑋𝐴2

𝑋𝐴1 + 𝑋𝐴2 = 0.1

𝑋𝐴1 = 0.08
𝑋𝐴2 = 0.02

𝐶8 𝐻10 1
= 100
𝐶8 𝐻10 +𝐴𝑖𝑟

𝑚𝑜𝑙
𝐹𝐴0 𝑥𝐴1 = 17.58 = 𝐹𝐴0 𝑥0.08
𝑠

𝑚𝑜𝑙
𝐹𝐴0 = 219.75
𝑠

𝑚𝑜𝑙
𝐹𝐵0 = 𝐹𝐴0 𝑥99𝑥0.21=4568.60
𝑠
𝑚𝑜𝑙
𝐹𝐼𝑂 = 𝐹𝐴0 𝑥99𝑥0.79 = 17186.65 𝑠

𝑚𝑜𝑙
𝐹𝐴 = 219,75 − 17.58 − 4.395 = 197.78 𝑠
𝑚𝑜𝑙
𝐹𝐵 = 4568.60 − 52.74 − 32.96 = 4482.9 𝑠
𝑚𝑜𝑙
𝐹𝐶 = 17,58 𝑠
𝑚𝑜𝑙
𝐹𝐷 = 52.74 + 17.58 = 70.32 𝑠
𝑚𝑜𝑙
𝐹𝐸 = 4.395 𝑠
𝑚𝑜𝑙
𝐹𝐹 = 17.58 𝑠
𝑚𝑜𝑙
𝐹𝐼 = 17186.65 𝑠

10
Table 6. Molar Flow Rates of Components

Components Feed Products

kmol/h
A 791,75 712,575
B 16460,48 16151,69
C - 63,288
D - 253,36
E - 15,835
F - 63,34
I 61922,76 61922,76

11
−𝑟𝑇 = −𝑟𝐴1 − 𝑟𝐴2
−27900
= (2,25𝑥1011 𝑒 1,987𝑥573

−27000 𝐹𝐴0 (20,79 − 4,385𝑋𝐴1 ) 𝐹𝐴0 (1 − 0,75𝑋𝐴1 )

+ 4,12𝑥1011 𝑒 1,987𝑥573 ) 𝑥 ( )𝑥( ) 𝑥(5 𝑎𝑡𝑚)2
𝐹𝐴0 (100 − 0,125𝑋𝐴1 ) 𝐹𝐴0 (100 − 0,125𝑋𝐴1 )

Design Equation and Volume

12
𝑡=0
𝑋𝐴 = 0

0,8
𝑑𝑋𝑎
𝑉 = 791,75 ∫
0 −𝑟𝐴

Simpson 1/3 Rule:

𝑛−1 𝑛−2
ℎ
𝐼 = (𝑓0 + 4 ∑ 𝑓𝑖 + 2 ∑ 𝑓𝑖 + 𝑓𝑛 )
3
𝑖=1,3,5.. 𝑖=2,4,6…

𝑅𝑒𝑎𝑐𝑡𝑜𝑟 𝑉𝑜𝑙𝑢𝑚𝑒 = 48,6𝑚3 ≅ 50𝑚3 (APP D.1.)

XA1-1/rT Graph
1.2

0.8
-1/rT

0.6
X1
0.4

0.2

0
0 0.2 0.4 0.6 0.8 1 1.2
XA1

Figure 1. Xa1 vs 1/-rT graph

13
Pressure Drop

For pressure drop, Ergun Equation is used.

150𝜇𝜗∆𝐿 (1 − 𝜀)2 1,75𝜌𝜗 2 ∆𝐿 (1 − 𝜀)

∆𝑃 = + [3]
𝐷𝑝2 𝜀3 𝐷𝑝 𝜀3

Inlet velocity:

For mass flow rate,

1ℎ
𝑚𝑜−𝑥𝑦𝑙𝑒𝑛𝑒 = 791,75 𝑘𝑚𝑜𝑙⁄ℎ 𝑥 106,16 𝑘𝑔⁄𝑘𝑚𝑜𝑙 𝑥 = 23,34 𝑘𝑔/𝑠
3600 𝑠

1ℎ
𝑚𝑜𝑥𝑦𝑔𝑒𝑛 = 16440,48 𝑘𝑚𝑜𝑙⁄ℎ 𝑥 32 𝑘𝑔⁄𝑘𝑚𝑜𝑙 𝑥 = 146,2 𝑘𝑔/𝑠
3600 𝑠

1ℎ
𝑚𝑛𝑖𝑡𝑟𝑜𝑔𝑒𝑛 = 61922,76 𝑘𝑚𝑜𝑙⁄ℎ 𝑥 28 𝑘𝑔⁄𝑘𝑚𝑜𝑙 𝑥 = 481,62 𝑘𝑔/𝑠
3600 𝑠

𝑚𝑡𝑜𝑡𝑎𝑙 = 651,16 𝑘𝑔⁄𝑠

The volumetric flow rate was found by dividing the mass flow of the mixture by the density
of the mixture.

𝑚 651,16 𝑘𝑔⁄𝑠
𝑄= = = 207,38 𝑚3 ⁄𝑠
𝜌 3,14 𝑘𝑔⁄𝑚3

The volumetric flow rate was divided by the area and the superficial velocity was calculated.

Tube inside diameter was chosen from TEMA standards as ¾’’ 18 BWG. (APP F.)

𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑡𝑢𝑏𝑒𝑠 = 700 , 𝑟𝑒𝑎𝑐𝑡𝑜𝑟 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟 = 2,3𝑚 (𝑓𝑜𝑢𝑛𝑑 𝑏𝑦 𝑢𝑠𝑖𝑛𝑔 𝑝𝑜𝑙𝑦𝑚𝑎𝑡ℎ)

[APP D.1.]

14
 207,38 𝑚3 ⁄𝑠
𝑄 700
𝜗= = = 0,071 𝑚⁄𝑠
𝐴 2,3 𝑚 2
𝜋( 2 )

So, the pressure drop is calculated.

𝜀 = 0,5
Dp= ½” spheres= 0,0127m
𝜇𝑚𝑖𝑥𝑡𝑢𝑟𝑒 = 3,02𝑥10−5 𝑘𝑔⁄𝑚. 𝑠 [APP C.1.]
𝜌𝑚𝑖𝑥𝑡𝑢𝑟𝑒 = 3,14 𝑘𝑔⁄𝑚3 [APP C.2.]
𝜗 = 0,071 𝑚⁄𝑠
∆𝐿 = 11 m

150𝜇𝜗∆𝐿 (1 − 𝜀)2 1,75𝜌𝜗 2 ∆𝐿 (1 − 𝜀)

∆𝑃 = +
𝐷𝑝2 𝜀3 𝐷𝑝 𝜀3

150(3,02𝑥10−5 𝑘𝑔⁄𝑚. 𝑠)(0,071 𝑚⁄𝑠)(11𝑚) (1 − 0,5)2

∆𝑃 =
(0,0127)2 (0,5)3
1,75(0,071 𝑚⁄𝑠)2 (3,14 𝑘𝑔⁄𝑚3 )(11𝑚) (1 − 0,5)
+ = 139,84𝑃𝑎
0,0127 (0,5)3
= 1,39𝑥10−3 𝑏𝑎𝑟 𝑓𝑜𝑟 𝑒𝑎𝑐ℎ 𝑡𝑢𝑏𝑒

3.4. Energy Balance for Reactor Design

𝑇𝑅 𝑇
∫𝑇 ∑ 𝐹𝑖 𝐶𝑝𝑖 𝑑𝑇 + ∫𝑇 𝑓 ∑ 𝐹𝑖 𝐶𝑝𝑖 𝑑𝑇 + Q = -Δ𝐻𝑅 𝐹𝑖𝑜 𝑥𝐴
𝑖 𝑅

𝐹𝐴𝑖 = Initial molar flow rate of o-xylene

𝐹𝐴𝑜 = Final molar flow rate of o-xylene

Reference temperature is taken as 300 C

15
 573𝐾
∫573𝐾 (𝐹𝐴𝑖 𝐶𝑝𝐴 ) + (𝐹𝐵𝑖 𝐶𝑝𝐵 ) + (𝐹𝐼 𝐶𝑝𝐼 )𝑑𝑇 +
573𝐾
∫573𝐾 (𝐹𝐴𝑓 𝐶𝑝𝐴 ) + (𝐹𝐵𝑓 𝐶𝑝𝐵 ) + (𝐹𝐶𝑓 𝐶𝑝𝐶 ) + (𝐹𝐷𝑓 𝐶𝑝𝐷 )+(𝐹𝐸𝑓 𝐶𝑝𝐸 ) + (𝐹𝐹𝑓 𝐶𝑝𝐹 ) + (𝐹𝐼𝑓 𝐶𝑝𝐼 )𝑑𝑇
+ Q = (Δ𝐻𝑀𝑎𝑖𝑛 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝐹𝐴𝑖 𝑥𝐴1 ) + (Δ𝐻𝑆𝑖𝑑𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝐹𝐴𝑖 𝑥𝐴2 )
Q = (Δ𝐻𝑀𝑎𝑖𝑛 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝐹𝐴𝑖 𝑥𝐴1 ) + (Δ𝐻𝑆𝑖𝑑𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝐹𝐴𝑖 𝑥𝐴2 )

𝑘𝐽 𝑚𝑜𝑙 𝑘𝐽 𝑚𝑜𝑙
Q = ( −1118.11 𝑥 15.82 ) + (-2982.1 𝑚𝑜𝑙 x 3.956 )
𝑚𝑜𝑙 𝑠 𝑠
𝑘𝐽
Q= -29485.69 = -29485.69 kW
𝑠

Utility

Utility: Dowtherm MX [6]

Boiling Point: 308 oC [6]
Heat Duty(Q) = -29485.69 kW
Mass Flow Rate of Utility: mu
𝑄 = ṁ𝑢 ×𝐶𝑝×Δ𝑇
Δ𝑇 assumption was made
Δ𝑇= 220 oC = 493 K
𝐶𝑝=2,520 kj/kgK
ṁ𝑢 = 23.73 kg/s

3.5. Cost Calculation

Catalyst cost
Mass of catalyst:

𝑅𝑒𝑎𝑐𝑡𝑜𝑟 𝑉𝑜𝑙𝑢𝑚𝑒 = 48,6𝑚3 ≅ 50𝑚3

𝑏𝑢𝑙𝑘 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 = 1350 𝑘𝑔⁄𝑚3

𝑘𝑔 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡 = 𝑏𝑢𝑙𝑘 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑥 𝑟𝑒𝑎𝑐𝑡𝑜𝑟 𝑣𝑜𝑙𝑢𝑚𝑒 [2, p:629-633]

16
𝑘𝑔 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡 = 1350 𝑘𝑔⁄𝑚3 𝑥 50𝑚3 = 67500 𝑘𝑔 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡

1 𝑘𝑔 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡 𝑐𝑜𝑠𝑡 𝑖𝑠 20$ [5]

𝑠𝑒𝑟𝑣𝑖𝑐𝑒 𝑙𝑖𝑓𝑒 𝑖𝑠 10 𝑦𝑒𝑎𝑟𝑠

20 $⁄𝑘𝑔 𝑥 67500 𝑘𝑔 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡

= 1,35𝑥105 $⁄𝑦𝑒𝑎𝑟 (2023 𝑎𝑛𝑛𝑢𝑎𝑙 𝑐𝑜𝑠𝑡)
10 𝑦𝑒𝑎𝑟𝑠

Reactor Cost

5𝑥103 $
𝐶𝑜𝑠𝑡2002 = 10 𝑦𝑒𝑎𝑟𝑠 = 5𝑥102 $⁄𝑦𝑒𝑎𝑟 (2002 𝑎𝑛𝑛𝑢𝑎𝑙 𝑐𝑜𝑠𝑡) (APP E.1.)

𝐶𝐸𝑃𝐶𝐼
𝐶𝑜𝑠𝑡2023 = 𝐶𝑜𝑠𝑡2002 𝑥 𝐶𝐸𝑃𝐶𝐼2023 (APP E.2.)
2002

824,4
𝐶𝑜𝑠𝑡2023 = (5𝑥102 $) 𝑥 = 1,04𝑥103 $ (2023 𝑎𝑛𝑛𝑢𝑎𝑙 𝑐𝑜𝑠𝑡)
395,6

Utility Cost

Cost of Dowtherm MX for 55 gallons = 3190,57 $ [7]

Density of Dowtherm MX = 959,5 kg/m3
55 gallons = 14473,68 m3
14473,68 m3 x 959,5 kg/m3 =13875920,8 kg

𝑘𝑔 3190,57$ 8000 ℎ𝑜𝑢𝑟 3600𝑠

23,73 utility 𝑥 𝑥 𝑥
s 13875920,8 𝑘𝑔 𝑢𝑡𝑖𝑙𝑖𝑡𝑦 1 𝑦𝑒𝑎𝑟 1ℎ𝑜𝑢𝑟
= 157143,6 $⁄𝑦𝑒𝑎𝑟 = 1,57𝑥105 $⁄𝑦𝑒𝑎𝑟 (2023 𝑎𝑛𝑛𝑢𝑎𝑙 𝑐𝑜𝑠𝑡)

17
4. RESULT AND DISCUSSION

The objective of this design is to create a reactor that can efficiently generate 75,000 metric
tons per year of high purity phthalic anhydride through the oxidation of o-xylene. This process
will be facilitated by the utilization of a vanadium pentoxide catalyst, ensuring optimal results.
Moreover, the design aims to achieve this production rate in an environmentally friendly
manner, while also being cost-effective and safe.

First, the physical and chemical properties of all chemicals were found, and the critical
temperatures and pressures that should be taken into consideration for each chemical were
determined. Then, the main reaction and side reactions were found through literature research.
The reaction in the production of phthalic anhydrate generally takes place between 300°C and
400°C. Pressure is also an important parameter in the process. A pressure of 1 to 5 atmospheres
is usually used. In this design, the operating conditions of the reactor were determined as 300°C
and 5 bar to increase the reaction rate and optimize product efficiency. Vanadium pentoxide
catalyst was used as the catalyst in the design project. Reasons for using vanadium pentoxide;
it provides high selectivity in the oxidation reaction of o-xylene, which can reduce the formation
of undesirable by-products, this catalyst allows the production of phthalic anhydrate with high
efficiency and is stable up to 400 °C and it is also a widely used and preferred catalyst in
industry. Selectivity was taken as 80%. Based on the reaction operating conditions and the
selectivity of the catalyst, other side reactions were neglected and only the maleic anhydrate
side reaction was taken as a basis. Gibbs free energy was calculated and -1136,8x103 j/mol
found. When the Gibbs free energy is negative, this indicates that a reaction in the system tends
to be spontaneous. After, ΔH was calculated at the reaction temperature and -1118,11 kj/mol
found. If ΔH is negative, this indicates that the reaction is exothermic. That is, during the
reaction, the system releases energy to its surroundings. Then, Keq was calculated and it was
understood that the reaction was irreversible because Keq was very high. Chemical reactors form
the heart of any chemical plant. Here, the raw materials are chemically converted into the final
products.

Most chemical reactions involve two or more phases, including liquids, gases and/or solids, in
contact. In this design project, the combination of phases is in gas-solid: where the solid act as
a catalyst and reactants and products acts as a gas.

18
According to the catalytic gas-solid reactors, fixed-bed reactors, multitubular fixed-bed reactors
and fluidized-bed reactors can be chosen as reactor types. Multitubular fixed-bed reactor type
is chosen for this design. Since heat transfer between the tubes is more efficient, temperature
control can generally be better maintained. A multitude of tubes provides a high surface area,
which can enhance reaction rates.

Exothermic reactions proceed by releasing heat and, when operated under adiabatic conditions,
cause rapid temperature increase. Increasing temperature is difficult to control, requires
additional equipment for effective control, requires extra cost, so non-adiabatic conditions were
chosen. As the temperature increases, sintering can occur, potentially leading to catalyst
degradation and the formation of hot spots. It is therefore important to prevent temperature
increases that require isothermal conditions. To keep to temperature constant the reactor system
should be cooled. Dowtherm MX chosen as utility.

Dowtherm MX heat transfer fluid contains a mixture of alkylated aromatics and is designed for
use as an alternative to hot oils in liquid phase heat transfer systems.

• It exhibits better thermal stability than hot oils and it’s low-temperature pumpability is
significantly better than typical hot oil.

• Throughout its operating range, the low viscosity of Dowtherm MX contributes to heat
transfer efficiency.

• It is also non-corrosive to common metals and alloys such as carbon steel.

Next, as a result of the research, it was concluded that the conversion in the industry was 0.1.
The feed composition for the phthalic anhydride reactor is crucial in order to prevent any
potential explosions. This is because the production of phthalic anhydride involves the vapor
phase oxidation of o-xylene, which is a flammable substance. To ensure safety, the lower and
upper flammability limits of o-xylene must be considered when determining the feed
composition. The lower explosion limit for o-xylene in air is 1% by volume, meaning that if the
percentage of o-xylene in the mixture falls below this limit, the mixture is too weak to burn and
there is no risk of explosion. On the other hand, the upper explosion limit is 6% by volume,
indicating that if the percentage of o-xylene exceeds this limit, the mixture becomes too delicate
to burn and there no risk of explosion. The range between the lower and upper explosion limits
is known as the flammability range, and it is within this range that an explosion is possible.
Therefore, the percentage of o-xylene in the feed must be either lower than the lower explosion

19
limit or higher than the upper explosion limit to ensure safety. Additionally, it is important to
note that the feed to the reactor should be oxygen-rich in order to maintain the activity of the
vanadium pentoxide catalyst. Low oxygen levels can reduce the catalyst's effectiveness and
potentially lead to the formation of hot spots. To prevent this, the percentage of air in the feed
must be lower than the lower explosion limit of o-xylene, which is 1%. Based on these
considerations, the feed composition for the phthalic anhydride reactor has been determined as
1% o-xylene and 99% air by volume. This composition ensures safe operability and minimizes
the risk of explosions. Selectivity was taken as desired product/total product. Material balance
was made using selectivity, conversion and flammability limits. Using rate expression, a design
equation for PFR was written and the volume was found to be 50 m3.

3/4 inch tube diameter was determined from TEMA standards (APP F.) Then, using
POLYMATH, the number of tubes of the reactor was determined as 700, its diameter was 2,30
meters and its length was 12 meters but the reactor length was taken as 11 meters to comply
with TEMA standards(APP D.1.). It was discussed that it would not be feasible to use 2,3 meter
diameter PFR when there is no conversion change on the y-axis in PFR. Pressure drop is a
crucial factor to consider in the design of a reactor. This particular parameter leads to an increase
in pressure drop as the diameter decreases. A pressure drop of 1,39x10-3 bar was observed. The
duration of the service life was established to be 10 years. The purchased cost of the reactor
was determined as 1,04x104$ (APP E.1). Using bulk density, the mass of the catalyst was
calculated as 67500 kg and annual cost of the catalyst was found to be 1,35x10 5 $/year . The
annual cost of utility is 1,5x105 $/year.

Table 7. Summary Table for Catalyst

Catalyst
Working Temperature Range 300˚C - 400˚C
Working Pressure Range 1-10 atm
Phase Solid
Particle Diameter ½” Spheres
Selectivity %80
Service Life 10 years

20
Table 8. Summary Table for Reactor

Reactor
Working Temperature 300 °C
Working Pressure 5 bar
Phase Solid
Surface Area 15,52 m2
Selectivity %80
Service Life 10
years

Table 9. Specification for Fixed Bed Reactor

MULTITUBULER FIXED BED PLUG

FLOW REACTOR
Identification Item: Reactor
Function: It provides the necessary reactions to obtain the desired product.
Operation: Isothermal system, exothermic reaction
Type : Fixed Bed Plug Flow Reactor
Horizontal
Carbon Steel
Working Temperature (°C) 300
Working Pressure (bar) 5
Reactor Diameter (m) 2,3
Reactor Length (m) 11
Cross-Sectional Area (m2) 15,52
Reactor Volume (m3) 48
Utility: V2O5 catalyst

21
Table 10. Specification for V2O5 catalyst

CATALYST
Identification Item: Solid Catalyst
Function: It speeds up a chemical reaction, or lowers the temperature or pressure needed to
start one, without itself being consumed during the reaction.
Operation: Isothermal , exothermic reaction
Catalyst Name V2O5
Working Temperature (°C) 300
Working Pressure (bar) 5
Shape Spherical catalyst pellet
Diameter (m) 0,0127
Occupancy Percentage 100 % filled with active catalyst
Void fraction 0.5
Service Life (year) 10
Density of catalyst (g/cm³) 3,36
Weight of catalyst (kg) 67500
Volume of catalyst (m3) 28125

Multitubular
Fixed Bed
Reactor

Figure 2.. Flow sheet of the reactor design

22
 Table 11.Flow summary table for flow sheet of the reactor design shown in Figure 1
FEEDS PRODUCTS
Stream O- O2 N2 Phthalic Maleic O-xylene O2 N2 CO2 H2O
xylene Anhydride Anhydride
Phase Gas Gas Gas Gas Gas Gas Gas Gas Gas Gas
Temperature 300 300 300 300 300 300 300 300 300 300
(ºC)
Molar 791,75 16460,48 61922,76 63,28 15,83 712,575 16151,69 61922,76 63,34 253,36
Flowrate
(kmol/h)

For risk assessment, since phthalic anhydride is produced through vapor phase oxidation of o-
xylene, the feed to the reactor contains o-xylene and air. O-xylene is flammable, and explosion
is possible when mixed with air. To prevent a possible explosion, the lower and upper
flammability limits of o-xylene should be taken into account when determining the feed
composition. The lower explosion limit for o-xylene by volume in air is 1% and the upper
explosion limit is 6%. Below the lower explosion limit, the mixture is too weak to burn and
There is no risk of explosion. Above the upper explosion limit, the mixture is too delicate to
burn and there is no risk of explosion. The range between the lower and upper explosion limits
is called the flammability range and an explosion is possible in this range. Therefore, the
percentage of o-xylene in the feed must be lower than the lower explosion limit or higher than
the upper explosion limit. Since low oxygen reduces the activity of the vanadium pentoxide
catalyst, the feed to the reactor must be oxygen-rich feed to prevent hot spot formation. In other
words, the percentage of air in the feed must be lower than the lower explosion limit of o-xylene
(1%) to ensure safe operability. Therefore, the feed composition of the phthalic anhydride
reactor was determined as 1% o-xylene and 99% air by volume.
The main reaction in o-xylene oxidation also includes external side reactions. Another risk is
that the desired conversion rate cannot be achieved as a result of these side reactions. Another
point that should be taken into consideration is the vanadium pentoxide catalyst included in the
reaction so that the reaction in the reactor can occur quickly. The efficiency of the catalyst is an
important point. Since the decrease in catalyst efficiency will indirectly affect the selectivity,
the reaction and reactor operation will be negatively affected.
Solid catalysts, which promote a reaction without participating in it, are normally contained
within grids and are termed fixed beds. The fixed-bed reactors may have single or multiple beds
and can have exothermic or endothermic reactions, with most reactions requiring a constant
temperature (isothermal) through each bed. This frequently requires the injection of these

23
reaction systems, temperature indication and sensor location through the beds are extremely
important to prevent a reaction runaway and product yield or quality changes [4].
In all reactors, pressure increases are a major concern since the vessel pressure rating must not
be exceeded. These pressure increases may be a result of poor process control, malfunction or
a runaway reaction. Consequently, pressure relief systems are required to maintain vessel
integrity by preventing reactor over pressuring. Relief valve discharges must be carefully
designed to maintain adequate relief under all conditions, including relief-valve maintenance.
Multiple valves may be required. Should a relief valve be designed to discharge into the
atmosphere, the discharge point should be elevated above all nearby structures and a dispersion
analysis should be conducted to ensure adequate protection for workers and nearby
communities [4].
Shutdown can be expensive and involve production loss, magnetic driven mixers and newer
seal systems have been introduced to reduce maintenance and reactor shutdowns [4].
It is important to remember that the oxidation of o-xylene can lead to exothermic reactions,
posing risks such as burning and explosions. Therefore, it is essential to provide protective
equipment to ensure the safety and well-being of individuals. Additionally, the design should
incorporate mechanisms for pressure and temperature control. It is worth noting that the
production of phthalic anhydride through o-xylene oxidation takes place in the gas phase.
Consequently, the emission of non-reactive substances into the atmosphere is facilitated. Air
pollution is induced by the discharge of carbon dioxide during the process of combustion. It has
been demonstrated that exposure to gases exceeding the permissible threshold can result in
detrimental effects on human health, including skin damage. Hence, it is imperative to ensure
that the released gases are either discharged or eliminated in a regulated fashion. In designing
the system, careful consideration should be given to the potential fire hazards that may arise
from the combustion reaction. Additionally, measures must be implemented to safeguard
against the potential decomposition of phthalic anhydrate by providing adequate heat
protection. In terms of evacuation systems, the pressure relief system can be designed to connect
with the overall system that supplies the flare. This configuration effectively minimizes the
potential risk of exposing individuals in the surrounding vicinity. Although O-xylene and
phthalic anhydrate are known to be corrosive chemicals, the decision to utilize carbon steel
pipes was made due to cost considerations. The inclusion of relief valves is also crucial in
ensuring system safety. Moreover, the installation of burst discs beneath these relief valves is
imperative to mitigate environmental risks. Furthermore, it is advisable to incorporate a flow
meter to accurately measure the o-xylene and air ratio.

24
Sudden pressure changes in the reactor are undesirable and cause various safety problems. High
pressure can create safety risks in reactor systems. Reactors have designed maximum operating
pressures, and if these values are exceeded, there may be a danger of explosion. A sudden
change in pressure can increase the reaction rate. In this case, the reaction may accelerate
uncontrollably and lead to the formation of undesirable byproducts. Sudden pressure changes
can damage equipment inside the reactor. This may cause damage to machines and equipment
malfunctions. Actions must be taken to prevent and manage sudden pressure changes.
Automatic pressure control systems should be used to monitor and control the pressure in the
reactor. These systems can automatically intervene and reduce the pressure in case of a pressure
exceeding the specified safety limits. Using pressure safety valves automatically opens and
reduces the pressure in cases exceeding a certain pressure level. These valves provide safety in
cases of overpressure in the system. In addition, the pressure in the reactor must be constantly
monitored and operators must constantly evaluate the situation in the reactor using the systems
in the control room. Finally, using automatic security alarm systems can detect situations that
exceed established safety limits and alert operators. This gives operators the chance to intervene
quickly.
Controlling reactant flows ensures that the process is managed efficiently, safely and to ensure
product quality. Especially in this process, air and o-xylene levels must be controlled to prevent
the risk of explosion. Flow measurement devices should be used in the process.

25
5. CONCLUSION

In conclusion, the reactor design is made for safe and economical formation of phthalic
anhydride accompanied by vanadium pentoxide catalyst 75 million kilograms per year at 300C
5 bars and the relevant calculations are given. For reactor to operate safely, the lower explosion
limit was considered which is 1 mol % o-xylene in air. The operating conditions are chosen as
isothermal and non-adiabatic. Selection of material of construction for reactor is important to
maintain operational safety and decreasing annual costs and so carbon steel is chosen for
providing balance between cost and corrosion resistance. Volume of reactor have been
calculated as 48,6 m3 with 2,3 meters diameter and 12 meters length but when adapted to TEMA
standards, the length was chosen as 11m. Particle diameter was given as ½” spheres, tube inside
diameter was chosen from TEMA standards as ¾’’ 18 BWG and pressure drop is found as
1,39x10-3 bars for each tube. For utility, Dowtherm MX was chosen. Q is calculated as -
29485.69 kW.

As a result of the whole design, reactor cost has been determined as 1,04x10 3 $/year. Mass of
the catalyst has been found as 67500kg and the annual cost is 1,35x10 5 $/year. Annual utility
cost has been calculated as 1,57x105 $/year.

26
6. NOMENCLATURE

A Area
Cp Specific heat
ΔH Enthalpy, kJ/kg.mol
D Diameter of reactor, m
FI Flow rate for feed component
de Equivalent Diameter
K Reaction equilibrium constant
R Ideal gas constant
M Molecular Weight
V Volume, m3
Z Lenght of the reactor in the direction of flow, m

Greek symbols
𝜀 Void fraction, dimensionless
𝜌 Density
𝜌 bulk Bulk density, kg catalyst/m3 reactor volume
𝑚 mass flow rate
𝜇𝑚𝑖𝑥𝑡𝑢𝑟𝑒 mixture viscosity
Dp particule diameter
𝜗 volumetric flow rate
𝜌𝑚𝑖𝑥𝑡𝑢𝑟𝑒 density of mixture

27
7.REFERENCES

[1] Yaws, C. L. (1999). Chemical properties handbook. McGraw-Hill Education.

[2]Peters, M.,S., Timmerhaus, K.,D, West, R.,E. (2004). Plant Design and Economics for
Chemical Engineers, (5th edition). Boston; Mc Graw Hill
[3] Geankoplis, C., J., 1993 ,“Transport Processes and Unit Operations”, 3 rd Edition, Prentice-
Hall International Inc., New Jersey,
[4] “Encyclopaedia of Occupational Health and Safety”,1998,Vol. 3, 4 th Ed., Geneva,
International Labour Office, 77.12-77.13.
[5] https://www.alibaba.com/product-detail/Epoch-High-Purity-99-5-
vanadium_1600285834359.html?spm=a2700.7724857.0.0.7ca02d976vltmn
[6] DOWTHERM MX Heat Transfer Fluid Product Technical Manual
[7] https://www.dow.com/en-us/pdp.dowtherm-mx-heat-transfer-fluid.75600z.html#overview
Access Date: 10.12.2023
[8] CHEMCAD Software Program
[9] Polymath Software Program
[10] Bird, R., B., Stewart, W., E., Lightfoot, E., N., 2002, “Transport Phenomena”, 2nd
Edition, John Wiley and Sons Inc, New York
[11] TEMA Standards

28
APPENDICES

29
APPENDIX A. Physical and Chemical Properties of Chemicals

Physical and Chemical Properties of O-xylene

Density 880 kg/m3
Molecular weight 106.17 g/mol
Melting point -24°C
Boiling point -144.4°C
Critical temperature 630,37 K
Flash point 35°C
Flammable/Toxic Flammable gases
Lower and upper explosive Lower: 0.90% Upper: 6.7%
(flammable) limits
Autoignition Temperature 465°C

Physical and Chemical Properties Phthalic Anhydride

Density 1,53 g/cm3
Molecular weight 148.12 g/mol
Melting point 131-134°C
Boiling point 284°C
Critical temperature 46,58
Flash point 152°C
Lower and upper explosive Lower: 1.70% Upper: 10.50%
(flammable) limits
Autoignition Temperature 580°C

30
Physical and Chemical Properties Maleic anhydride
Density 1,48 g/cm3
Molecular weight 98.06 g/mol
Melting point 52.8°C
Boiling point 202°C
Critical temperature 721 K
Flash point 103.33°C
Lower and upper explosive Lower: 1.4% Upper: 7.1%
(flammable) limits
Autoignition Temperature 465°C

Physical and Chemical Properties Oxygen

Density 1,329 kg/m3
Molecular weight 32 g/mole
Melting point -218.4°C
Boiling point -183°C
Critical temperature -118.15°C
Flash point Product does not sustain
combustion.

Physical and Chemical Properties Nitrogen

Density 1,153 kg/m3
Molecular weight 28,02 g/mol
Melting point -210.01°C
Boiling point -196°C
Critical temperature -146.95°C
Flash point Product does not sustain
combustion.

31
APPENDIX B. Properties of Components [1]
APPENDIX B.1. Heat Capacity of Organic and Inorganic Compounds

32
APPENDIX B.2. Critical Properties of Organic and Inorganic Compounds

33
APPENDIX B.3. Enthalpy of Formation of Organic and Inorganic Compounds

34
APPENDIX B.4. Gibbs Energy of Formation of Organic and Inorganic Compounds

35
APPENDIX C. Calculation on Viscosity and Density of Mixture

APPENDIX C.1. Viscosity of gas mixture [10]

Chapman-Enskog Equation [10]:

𝑁
𝑥𝛼 𝜇𝛼
𝜇𝑚𝑖𝑥𝑡𝑢𝑟𝑒 = ∑
∑ 𝑥𝛽 𝜙𝛼𝛽
𝛼=1

−0,5 0,5 2
1 𝑀𝛼 𝜇𝛼 𝑀𝛽 0,25
𝜙𝛼𝛽 = (1 + ) [1 + ( ) ( ) ]
√8 𝑀𝛽 𝜇𝛽 𝑀𝛼

Viscosity calculation [8]

Viscosities for inlet stream compounds at operation conditions [8]

Compounds Compound Viscosity Mole Mole Molecular
No (Pa.s) Number Fraction Weight
(kmol) (kg/kmol)
C8H10 1 1,1969x10-5 791,75 0,01 106,16
O2 2 3,334x10-5 16460,48 0,207 32
N2 3 2,8611x10-5 61922,76 0,782 28
Total 79174,99

Viscosities for outlet stream compounds at operation conditions [8]

36
 Compounds Compound Viscosity Mole Mole Molecular
No (Pa.s) Number Fraction Weight
(kmol) (kg/kmol)
C8H10 1 1,1969x10-5 712,57 8,99x10-3 106,16
O2 2 3,334x10-5 16151,69 0,20 32
N2 3 2,8611x10-5 61922,76 0,78 28
C4H2O3 4 1,5253x10-5 63,28 7,99x10-4 98,06
H2O 5 2,0343x10-5 253,36 3,19x10-3 18
CO2 6 2,6481x10-5 63,34 7,99x10-4 44
C8H4O3 7 1,1787x10-5 63,28 7,98x10-4 148,1
Total 79230,28

Data for Chapman-Enskog equation:

𝛼 𝛽 𝑀𝛼 ⁄𝑀𝛽 𝑀𝛽 ⁄𝑀𝛼 𝜇𝛼 ⁄𝜇𝛽 𝜙𝛼𝛽 𝑁

∑ 𝑥𝛼 . 𝜙𝛼𝛽
𝛽=1

1 1 1 1 1
1 2 1,14 0,877 1,16 1,008 0,422
1 1 1 1 1
2 2 0,877 1,14 0,86 0,989 1,552

Except O2 and N2, the mole fractions of the compounds were neglected because they were too
low.
𝑁
𝑥𝛼 𝜇𝛼
𝜇𝑚𝑖𝑥𝑡𝑢𝑟𝑒 = ∑
∑ 𝑥𝛽 𝜙𝛼𝛽
𝛼=1

(0,2 𝑥 3,334𝑥10−5 ) (0,78 𝑥 2,8611𝑥10−5 )

𝜇𝑚𝑖𝑥𝑡𝑢𝑟𝑒 = + = 1,58𝑥10−5 + 1,44𝑥10−5
0,422 1,552
= 3,02𝑥10−5 𝑘𝑔⁄𝑚. 𝑠

37
APPENDIX C.2. Density of gas mixture

𝜌𝑚𝑖𝑥𝑡𝑢𝑟𝑒 = 𝑃𝑥𝑀𝑎 = 𝜌𝑥𝑅𝑥𝑇

(5 𝑎𝑡𝑚)𝑥(106 𝑔⁄𝑚𝑜𝑙 )
𝜌𝑜−𝑥𝑦𝑙𝑒𝑛𝑒 = = 11,28 𝑔⁄𝐿 = 11,28𝑘𝑔⁄𝑚3
(0,082 𝑎𝑡𝑚. 𝐿⁄𝑚𝑜𝑙. 𝐾 )𝑥(573𝐾)

(5 𝑎𝑡𝑚)𝑥(32 𝑔⁄𝑚𝑜𝑙 )
𝜌𝑜𝑥𝑦𝑔𝑒𝑛 = = 3,4 𝑔⁄𝐿 = 3,4 𝑘𝑔⁄𝑚3
(0,082 𝑎𝑡𝑚. 𝐿⁄𝑚𝑜𝑙. 𝐾 )𝑥(573𝐾)

(5 𝑎𝑡𝑚)𝑥(148 𝑔⁄𝑚𝑜𝑙 )
𝜌𝑝ℎ𝑡ℎ𝑎𝑙𝑖𝑐 𝑎𝑛ℎ𝑦𝑑𝑟𝑖𝑑𝑒 = = 15,75 𝑔⁄𝐿 = 15,75 𝑘𝑔⁄𝑚3
(0,082 𝑎𝑡𝑚. 𝐿⁄𝑚𝑜𝑙. 𝐾 )𝑥(573𝐾)

(5 𝑎𝑡𝑚)𝑥(18 𝑔⁄𝑚𝑜𝑙 )
𝜌𝑤𝑎𝑡𝑒𝑟 = = 1,92 𝑔⁄𝐿 = 1,92 𝑘𝑔⁄𝑚3
(0,082 𝑎𝑡𝑚. 𝐿⁄𝑚𝑜𝑙. 𝐾 )𝑥(573𝐾)

(5 𝑎𝑡𝑚)𝑥(44 𝑔⁄𝑚𝑜𝑙 )
𝜌𝑐𝑎𝑟𝑏𝑜𝑛 𝑑𝑖𝑜𝑥𝑖𝑑𝑒 = = 4,68 𝑔⁄𝐿 = 4,68 𝑘𝑔⁄𝑚3
(0,082 𝑎𝑡𝑚. 𝐿⁄𝑚𝑜𝑙. 𝐾 )𝑥(573𝐾 )

(5 𝑎𝑡𝑚)𝑥(98 𝑔⁄𝑚𝑜𝑙 )
𝜌𝑚𝑎𝑙𝑒𝑖𝑐 𝑎𝑛ℎ𝑦𝑑𝑟𝑖𝑑𝑒 = = 10,43 𝑔⁄𝐿 = 10,43 𝑘𝑔⁄𝑚3
(0,082 𝑎𝑡𝑚. 𝐿⁄𝑚𝑜𝑙. 𝐾 )𝑥(573𝐾 )

(5 𝑎𝑡𝑚)𝑥(28 𝑔⁄𝑚𝑜𝑙 )
𝜌𝑛𝑖𝑡𝑟𝑜𝑔𝑒𝑛 = = 2,98 𝑔⁄𝐿 = 2,98 𝑘𝑔⁄𝑚3
(0,082 𝑎𝑡𝑚. 𝐿⁄𝑚𝑜𝑙. 𝐾 )𝑥(573𝐾)

𝜌𝑚𝑖𝑥𝑡𝑢𝑟𝑒 = ∑ 𝜌𝐴 𝑥𝐴

𝜌𝑚𝑖𝑥𝑡𝑢𝑟𝑒 = (11,28𝑥8,99𝑥10−3 ) + (3,4𝑥0,2) + (15,75𝑥7,98𝑥10−4 ) + (1,92𝑥3,19𝑥10−3 ) +

(4,68𝑥7,99𝑥10−4 ) + (10,43 𝑥7,99x10−4 ) + (2,98𝑥0,78)

𝑘𝑔
𝜌𝑚𝑖𝑥𝑡𝑢𝑟𝑒 = 3,14 𝑚3

38
APPENDIX D. Polymath
APPENDIX D.1. Polymath Software Result

POLYMATH Report No Title

Ordinary Differential Equations 12-Ara-2023

Calculated values of DEQ variables

Variable Initial value Minimal value Maximal value Final value
1 z 1,0E-06 1,0E-06 12, 12,
2 X1 1,0E-05 1,0E-05 0,0831936 0,0831936
3 X2 1,0E-05 1,0E-05 0,0206267 0,0206267
4 FA0 712,5839 712,5839 794,8921 794,8921
5 FT1 7,055E+06 7,055E+06 7,87E+06 7,87E+06
6 R 1,987 1,987 1,987 1,987
7 T 573, 573, 573, 573,
8 FT2 7,055E+06 7,055E+06 7,87E+06 7,87E+06
9 FA1 712,575 712,575 712,575 712,575
10 FB1 1,481E+06 1,481E+06 1,652E+06 1,652E+06
11 rA1 0,0109728 0,0098346 0,0109728 0,0098346
12 FA2 712,5483 712,5483 713,2547 713,2547
13 FB2 1,481E+06 1,481E+06 1,652E+06 1,652E+06
14 rA2 0,0027182 0,0024387 0,0027182 0,0024387
15 V 48, 48, 48, 48,
16 rt 1236,076 0,3572414 1236,076 0,3572414
17 n 700, 700, 700, 700,
18 r 0,01905 0,01905 0,01905 0,01905
19 S 8,374E-05 8,374E-05 1002,581 1002,581
20 Sr 9,595E+06 15,7444 9,595E+06 27,66036
21 P 5, 5, 5, 5,
22 u 0,0003 0,0003 0,0003 0,0003
23 den 3,6 3,6 3,6 3,6
24 v 3319,764 3319,764 3319,764 3319,764
25 e 0,5 0,5 0,5 0,5
26 dp 0,0127 0,0127 0,0127 0,0127
27 DP 1,828E-05 1,828E-05 218,868 218,868
28 XA 2,0E-05 2,0E-05 0,1033865 0,1033865
29 Pressure 4,999982 -213,868 4,999982 -213,868

39
Differential equations
1 d(X1)/d(z) = S * (rA1) / FA0
2 d(X2)/d(z) = S * (rA2) / FA0

Explicit equations
1 FA0 = (712575/1000) / (1 - (125 / 100) * X1)
2 FT1 = FA0 * (9901 + (125 / 1000) * X1)
3 R = (1987/1000)
cal/(mole*K)

4 T = 573
K

5 FT2 = FA0 * (9901 + (5 / 10) * X2)

6 FA1 = FA0 * (1 - (125 / 100) * X1)
7 FB1 = FA0 * (2079 - (4875 / 1000) * X1)
8 rA1 = (412/100) * (10 ^ 11) * exp(-27000 / (R * T)) * (FA1 / FT1) * (FB1 / FT1) * (5) ^ 2
9 FA2 = FA0 * (1 - 5 * X2)
10 FB2 = FA0 * (2079 - (195 / 10) * X2)
11 rA2 = (225/100) * (10 ^ 11) * exp(-27900 / (R * T)) * (FA2 / FT2) * (FB2 / FT2) * (5) ^ 2
12 V = 48
m^3

13 rt = (V/((31416 / 1000) * z)) ^ (1 / 2)

radius of reactor

14 n = 700
Tube nuber

15 r = 1905 / 100000
tube radius m

16 S = 2 * (314 / 100) * r * z * n
area m^2

17 Sr = (314/100) * 2 * rt * z + (314 / 100) * 2 * rt ^ 2

cylinder reactor surface area m^2

18 P = 5
19 u = 3 / 10000
viscosity (Pa.s)
20 den = 360 / 100
density(Kg/m3)

v = ((113 / 100) * 99 * (2896 / 100) + (113 / 100 * 1 * 106) * (1 / den) * ((31416 / 10000) * 1 / (r ^ 2)) * (1 /
21
3600))
velocity (m/s)

22 e = 5 / 10
void fraction
23 dp = (127/10000)
particle diameter (m)

DP = z * (9869 / 1000000000) * ((150 * u * v * ((1 - e) ^ 2) / ((dp ^ 2) * (e ^ 3))) + (1.75 * (1 - e) * den * (u

24
^ 2) / (dp * (e ^ 3))))
25 XA = X1 + X2
26 Pressure = P - DP

40
General
Total number of equations 28
Number of differential equations 2
Number of explicit equations 26
Elapsed time 0,000 sec
Solution method RKF_45
Step size guess. h 1
Truncation error tolerance. eps 1

APPENDIX D.2. Polymath Software Equations

rA1 = (412/100) * (10 ^ 11) * exp(-27000 / (R * T)) * (FA1 / FT1) * (FB1 / FT1) * (5) ^ 2
rA2 = (225/100) * (10 ^ 11) * exp(-27900 / (R * T)) * (FA2 / FT2) * (FB2 / FT2) * (5) ^ 2

R = (1987/1000) # cal/(mole*K)
T = 573 # K
FA0 = (712575/1000) / (1 - (125 / 100) * X1)
FA1 = FA0 * (1 - (125 / 100) * X1)
FB1 = FA0 * (2079 - (4875 / 1000) * X1)
FT1 = FA0 * (9901 + (125 / 1000) * X1)
FA2 = FA0 * (1 - 5 * X2)
FB2 = FA0 * (2079 - (195 / 10) * X2)
FT2 = FA0 * (9901 + (5 / 10) * X2)

V = 48 # m^3
rt = (V/((31416 / 1000) * z)) ^ (1 / 2) # radius of reactor
n = 700 # Tube nuber
S = 2 * (314 / 100) * r * z * n # area m^2
r = 1905 / 100000 # tube radius m
Sr = (314/100) * 2 * rt * z + (314 / 100) * 2 * rt ^ 2 # cylinder reactor surface area m^2

z(0) = 0.000001
z(f) = 12

X1(0) = 0.00001
d(X1)/d(z) = S * (rA1) / FA0

X2(0) = 0.00001
d(X2)/d(z) = S * (rA2) / FA0

P = 5 # bar

u = 3 / 10000 # viscosity (Pa.s)

den = 360 / 100 # density(Kg/m3)
v = ((113 / 100) * 99 * (2896 / 100) + (113 / 100 * 1 * 106) * (1 / den) * ((31416 / 10000) * 1 / (r ^ 2)) * (1 /
3600)) # velocity (m/s)
e = 5 / 10 # void fraction
dp = (127/10000) # particle diameter (m)
DP = z * (9869 / 1000000000) * ((150 * u * v * ((1 - e) ^ 2) / ((dp ^ 2) * (e ^ 3))) + (1.75 * (1 - e) * den * (u ^ 2)
/ (dp * (e ^ 3))))
XA = X1 + X2
Pressure = P – DP

41
APPENDIX D.3. X1 and X2 Graph

APPENDIX D.4. Polymath With Energy Balance Not Working

POLYMATH Report No Title

Ordinary Differential Equations 12-Ara-2023

Calculated values of DEQ variables

Variable Initial value Minimal value Maximal value Final value
1 z 1,0E-06 1,0E-06 12, 12,
2 X1 1,0E-05 1,0E-05 0,0074264 0,0074264
3 X2 1,0E-05 1,0E-05 0,0017 0,0017
4 T 518, 518, 518,0001 518,0001
5 FA0 712,5839 712,5839 719,2207 719,2207
6 FT1 7,055E+06 7,055E+06 7,121E+06 7,121E+06
7 R 1,987 1,987 1,987 1,987
8 FT2 7,055E+06 7,055E+06 7,121E+06 7,121E+06
9 FA1 712,575 712,575 712,575 712,575
10 FB1 1,481E+06 1,481E+06 1,495E+06 1,495E+06
11 rA1 0,0008847 0,0008765 0,0008847 0,0008765
12 FA2 712,5483 712,5483 713,1354 713,1354
13 FB2 1,481E+06 1,481E+06 1,495E+06 1,495E+06
14 rA2 0,0002015 0,0001998 0,0002015 0,0001998
15 V 48, 48, 48, 48,
16 rt 1236,076 0,3572414 1236,076 0,3572414
17 n 700, 700, 700, 700,
18 r 0,01905 0,01905 0,01905 0,01905

42
19 S 8,374E-05 8,374E-05 1002,581 1002,581
20 Sr 9,595E+06 15,7444 9,595E+06 27,66036
21 P 5, 5, 5, 5,
22 u 0,0003 0,0003 0,0003 0,0003
23 den 3,6 3,6 3,6 3,6
24 v 3319,764 3319,764 3319,764 3319,764
25 e 0,5 0,5 0,5 0,5
26 dp 0,0127 0,0127 0,0127 0,0127
27 DP 1,828E-05 1,828E-05 218,868 218,868
28 XA 2,0E-05 2,0E-05 0,0090844 0,0090844
29 Pressure 4,999982 -213,868 4,999982 -213,868
30 FA 712, 712, 712, 712,
31 FB 1651, 1651, 1651, 1651,
32 FC 63, 63, 63, 63,
33 FD 253, 253, 253, 253,
34 FE 15, 15, 15, 15,
35 FF 63, 63, 63, 63,
36 FB0 1,646E+04 1,646E+04 1,646E+04 1,646E+04
37 FI 6,192E+04 6,192E+04 6,192E+04 6,192E+04
38 Ta 518, 518, 518, 518,
39 Tb 518, 518, 518, 518,
40 CpA 205,5172 205,5172 205,5172 205,5172
41 CpB 32,90572 32,90572 32,90572 32,90572
42 CpC 297,0316 297,0316 297,0317 297,0317
43 CpD 34,22248 34,22248 34,22248 34,22248
44 CpE -7,177E+04 -7,177E+04 -7,177E+04 -7,177E+04
45 CpF 45,03676 45,03676 45,03676 45,03676
46 CpI 30,12924 30,12924 30,12924 30,12924
47 DeltaH1 -1118, -1118, -1118, -1118,
48 DeltaH2 -2982, -2982, -2982, -2982,
49 U 100, 100, 100, 100,
50 Do 0,01905 0,01905 0,01905 0,01905
51 Q 0 -1,588901 0 -1,575915

43
Differential equations
1 d(X1)/d(z) = S * (rA1) / FA0
2 d(X2)/d(z) = S * (rA2) / FA0
d(T)/d(z) = S * (Q + (-1 * rA1 * DeltaH1 - rA2 * DeltaH2)) / ((FA * CpA) + (FB * CpB) + (FC * CpC) +
3
(FD * CpD) + (FE * CpE) + (FF * CpF) + (FI * CpI))
Energy Balance

Explicit equations
1 FA0 = (712575/1000) / (1 - (125 / 100) * X1)
2 FT1 = FA0 * (9901 + (125 / 1000) * X1)
3 R = (1987/1000)
cal/(mole*K)

4 FT2 = FA0 * (9901 + (5 / 10) * X2)

5 FA1 = FA0 * (1 - (125 / 100) * X1)
6 FB1 = FA0 * (2079 - (4875 / 1000) * X1)
7 rA1 = (412/100) * (10 ^ 11) * exp(-27000 / (R * T)) * (FA1 / FT1) * (FB1 / FT1) * (5) ^ 2
8 FA2 = FA0 * (1 - 5 * X2)
9 FB2 = FA0 * (2079 - (195 / 10) * X2)
10 rA2 = (225/100) * (10 ^ 11) * exp(-27900 / (R * T)) * (FA2 / FT2) * (FB2 / FT2) * (5) ^ 2
11 V = 48
12 rt = (V/((31416 / 1000) * z)) ^ (1 / 2)
13 n = 700
Tube nuber

14 r = 1905 / 100000
m

15 S = 2 * (314 / 100) * r * z * n
16 Sr = (314/100) * 2 * rt * z + (314 / 100) * 2 * rt ^ 2
17 P=5
18 u = 3 / 10000
viscosity (Pa.s)
19 den = 360 / 100
density(Kg/m3)

v = ((113 / 100) * 99 * (2896 / 100) + (113 / 100 * 1 * 106) * (1 / den) * ((31416 / 10000) * 1 / (r ^ 2)) * (1 /
20
3600))
velocity (m/s)
21 e = 5 / 10
void fraction
22 dp = (127/10000)
particle diameter (m)
DP = z * (9869 / 1000000000) * ((150 * u * v * ((1 - e) ^ 2) / ((dp ^ 2) * (e ^ 3))) + (1.75 * (1 - e) * den * (u
23
^ 2) / (dp * (e ^ 3))))
24 XA = X1 + X2
25 Pressure = P - DP
26 FA = 712
27 FB = 1651
28 FC = 63
29 FD = 253

44
30 FE = 15
31 FF = 63
32 FB0 = 16460
33 FI = 61922
34 Ta = 518
K

35 Tb = 518
K

36 CpA = 182 / 1000 + 5 * 10 ^ -1 * T - 2 * 10 ^ -4 * T ^ 2

37 CpB = 29 - 8 * 10 ^ -3 * T + 3 * 10 ^ -5 * T ^ 2
38 CpC = 40 + 3 * 10 ^ -2 * T + 9 * 10 ^ -4 * T ^ 2
39 CpD = 33 - 8 * 10 ^ -3 * T + 2 * 10 ^ -5 * T ^ 2
40 CpE = -72015 + 1 * T - 1 * 10 ^ -3 * T ^ 2
41 CpF = 27 + 4 * 10 ^ -2 * T - 1 * 10 ^ -5 * T ^ 2
42 CpI = 29 - 3 * 10 ^ -3 * T + 1 * 10 ^ -5 * T ^ 2
43 DeltaH1 = -1118
44 DeltaH2 = -2982
45 U = 100
W/m^2.K
46 Do = 1905 / 100000
m

47 Q = U * (4 / Do) * (Ta - T)
W/m

General
Total number of equations 50
Number of differential equations 3
Number of explicit equations 47
Elapsed time 0,000 sec
Solution method RKF_45
Step size guess. h 1
Truncation error tolerance. eps 1

45
APPENDIX D.5. Polymath Isothermal Temperature Graph

APPENDIX D.6. Polymath Software Equations

rA1 = (412/100) * (10 ^ 11) * exp(-27000 / (R * T)) * (FA1 / FT1) * (FB1 / FT1) * (5) ^ 2
rA2 = (225/100) * (10 ^ 11) * exp(-27900 / (R * T)) * (FA2 / FT2) * (FB2 / FT2) * (5) ^ 2

R = (1987/1000) # cal/(mole*K)

FA0 = (712575/1000) / (1 - (125 / 100) * X1)

FA1 = FA0 * (1 - (125 / 100) * X1)
FB1 = FA0 * (2079 - (4875 / 1000) * X1)
FT1 = FA0 * (9901 + (125 / 1000) * X1)
FA2 = FA0 * (1 - 5 * X2)
FB2 = FA0 * (2079 - (195 / 10) * X2)
FT2 = FA0 * (9901 + (5 / 10) * X2)

V = 48
rt = (V/((31416 / 1000) * z)) ^ (1 / 2)
n = 700 # Tube nuber
S = 2 * (314 / 100) * r * z * n
r = 1905 / 100000 # m
Sr = (314/100) * 2 * rt * z + (314 / 100) * 2 * rt ^ 2

z(0) = 0.000001
z(f) = 12

X1(0) = 0.00001
d(X1)/d(z) = S * (rA1) / FA0

X2(0) = 0.00001
d(X2)/d(z) = S * (rA2) / FA0

P=5

u = 3 / 10000 # viscosity (Pa.s)

den = 360 / 100 # density(Kg/m3)

46
v = ((113 / 100) * 99 * (2896 / 100) + (113 / 100 * 1 * 106) * (1 / den) * ((31416 / 10000) * 1 / (r ^ 2)) * (1 /
3600)) # velocity (m/s)
e = 5 / 10 # void fraction
dp = (127/10000) # particle diameter (m)
DP = z * (9869 / 1000000000) * ((150 * u * v * ((1 - e) ^ 2) / ((dp ^ 2) * (e ^ 3))) + (1.75 * (1 - e) * den * (u ^ 2)
/ (dp * (e ^ 3))))
XA = X1 + X2
Pressure = P - DP

FA = 712
FB = 1651
FC = 63
FD = 253
FE = 15
FF = 63
FB0 = 16460
FI = 61922

d(T)/d(z) = S * (Q + (-1 * rA1 * DeltaH1 - rA2 * DeltaH2)) / ((FA * CpA) + (FB * CpB) + (FC * CpC) + (FD *
CpD) + (FE * CpE) + (FF * CpF) + (FI * CpI)) # Energy Balance

T(0) = 518 # K
Ta = 518 # K
Tb = 518 # K

CpA = 182 / 1000 + 5 * 10 ^ -1 * T - 2 * 10 ^ -4 * T ^ 2

CpB = 29 - 8 * 10 ^ -3 * T + 3 * 10 ^ -5 * T ^ 2
CpC = 40 + 3 * 10 ^ -2 * T + 9 * 10 ^ -4 * T ^ 2
CpD = 33 - 8 * 10 ^ -3 * T + 2 * 10 ^ -5 * T ^ 2
CpE = -72015 + 1 * T - 1 * 10 ^ -3 * T ^ 2
CpF = 27 + 4 * 10 ^ -2 * T - 1 * 10 ^ -5 * T ^ 2
CpI = 29 - 3 * 10 ^ -3 * T + 1 * 10 ^ -5 * T ^ 2

DeltaH1 = -1118
DeltaH2 = -2982
U = 100 # W/m^2.K
Do = 1905 / 100000 # m
Q = U * (4 / Do) * (Ta - T) # W/m

47
APPENDIX E. Cost

APPENDIX E.1. Reactor cost [2, p:681]

48
APPENDIX E.2. CEPCI index

49
APPENDIX F. TEMA Standards [11]

50
APPENDIX G. MEMORANDUM

51
52