GAZI UNIVERSITY FACULTY OF ENGINEERING

2021-2022 FALL SEMESTER

CHE451 CHEMICAL ENGINEERING DESIGN I

REACTOR DESIGN FOR STYRENE PRODUCTION BY

DEHYDOGENETING ETHYLBENZE

GROUP D:

171142007 BANU ARSLAN (EDITOR)

171142015 BEGÜM ÇALI

171142040 SEVİLAY SELİN ÖZÇELİK (LEADER)

161142038 SERCAN TANSU

PROF. DR. SENA YAŞYERLİ

DUE DATE: 10.12.2021

 ABSTRACT

The aim of this report is to design a reactor that will produce styrene from ethylbenzene by
dehydrogenation. The reactor is designed according to the most economical and reliable way,
taking into account the operational conditions of other side reactions that may occur during the
ethylbenzene dehydrogenation reaction. While the reactions are taking place, steam and catalyst
(Fe2O3) are used. The volume of the catalyst used and the volume of the reactors are calculated
by making the necessary calculations and drawing the adiabatic lines to design the reactor. The
volume of the catalyst is 119 m3 and the volumes of the reactors are 80 m 3 and 95 m3
respectively. In line with these volumes found, the cost of the reactors is found as $ 2 712 739
The cost per kilogram of the catalyst is given as $ 27 996

A heat exchanger is used between the reactors so that the inlet temperature of the second reactor
reaches the desired temperature. This heat exchanger is shell and tube and its area is 11.65 m 2.
The total purchased cost of this heat exchanger is 6130.9 dollars, and its installed cost is 12261.8
dollars.

The total cost of the system, designed as two reactors and a heat exchanger, is in 2 776 603
dollars. An acceptable result is reached in the calculations made by taking into account the safety
conditions and wanting to realize the most efficient production at the most appropriate costs.

i
 TABLE OF CONTENTS

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

2. METHOD OF ATTACK & CALCULATIONS......................................................................3

2.1. Literature Research About The Reactions Procedure...........................................................3

2.2. Raw Materials And Products Of The Reactions...............................................................4

2.3. Reaction Kinetics..............................................................................................................7

2.4. Material And Energy Balance...........................................................................................7

2.4.1. Specific Heat Capacities................................................................................................8

2.4.2. Enthaply and Gibb’s Free Energy.................................................................................8

2.4.3. Equilibrium Constant....................................................................................................9

2.4.4. XA – T Graph...............................................................................................................10

2.5. Reactor’s Sizes................................................................................................................15

2.5.1. Cost of Reactor Purchased Cost..................................................................................18

2.5.2. Cost of Catalyst...........................................................................................................18

2.5.3. Cost of Heat Exchanger...............................................................................................19

2.5.4. Cost of Utility..............................................................................................................19

3. RISK ASSESSMENT............................................................................................................20

4. RESULTS AND DISCUSSIONS..........................................................................................21

5. CONCLUSION......................................................................................................................25

6. REFERENCES..........................................................................................................................26

7. NOMENCLATURE...............................................................................................................28

8. APPENDIX A...........................................................................................................................29

ii
 LIST OF TABLES

Table 2-1. Steps to be followed during the reactor design ……………………………………2

Table 2.2- 1 Physical and chemical properties of ethylbenzene ……………………………...3

Table 2.2- 2 Physical and chemical properties of styrene ……………………………………3

Table 2.2- 3 Physical and chemical properties of benzene …………………………………...4

Table 2.2- 4 Physical and chemical properties of ethylene …………………………………..4

Table 2.2- 5 Physical and chemical properties of toluene ……………………………………5

Table 2.2- 6 Physical and chemical properties of methane …………………………………..5

Table 2.2-7. Enthalpy and Gibbs Energy of Formation ……………………………………..6

Table 2.3-1. Reaction Kinetics ………………………………………………………………6

Table 2.4.1-1. Heat capacity values of gases ………………………………………………..7

Table 2.4.2-1. Enthalpy of formation and Gibbs free energy of formation …………………7

Table 2.4.3-1. Value of equilibrium constants against changing temperatures ……………..9

Table 2.4.4-1. Molar fractions of components ……………………………………………...9

Table 2.4.4-2. Conversion values corresponding to changing temperatures at 1.4 atm …...10

Table 2.4.4-3. Molarflow rates of components …………………………………………….11

Table 2.4.4-4. XA values according to different temperature for 1st reactor ……………….12

Table 2.4.4-5. XA values according to different temperature for 2nd reactor ………………14

Table 2.7.1-1. Cost indexes by year ………………………………………………………..17

Table 4-1. Flow summary table for process shown in Figure 4-1 …………………………20

iii
 LIST OF FIGURES

Figure 2.4.4-1. Conversion graph versus changing temperatures ……………………………..10

Figure 2.5-1. 1/-r A versus x A graph for the first reactor ………………………………………14

Figure 2.5-2. 1/-r A versus x A graph for the second reactor …………………………………...15

Figure 4-1. Flow sheet of reactor design ……………………………………………………...20

Figure 4-2. Pie chart of cost of reactors ………………………………………………………21

Figure 4-3. Pie chart of cost of heat exchanger ………………………………………………23

Figure 4-4. Pie chart of whole system cost …………………………………………………..23

iv
 1. INTRODUCTION

The complex problem of this design is production of styrene from ethylbenzene by

dehydrogenation, taking into account safety conditions and minimum cost. In line with this
complex problem, the aim of the design is to design a reactor that enables the production of
styrene at the highest conversion at a safe and minimum cost, by considering the operational
conditions of the raw material ethylbenzene and the Fe 2O3 used as a catalyst, by considering the
formation conditions of side reactions. At the beginning of the design, a work plan was prepared
in order to proceed in a planned manner, and in this direction, the necessary literature research
was made and the operational conditions of the reactor were determined and calculations were
made accordingly. After the calculations, it was decided to place two reactors in order to produce
styrene from ethylbenzene safely with high efficiency, and a heat exchanger between these two
reactors in order to provide material entry to the second reactor at the desired temperature.

While starting this design, first of all, by finding out the side reactions that can take place during
the production of styrene from ethylbenzene and learning under which operational conditions
these reactions will take place at a minimum, the temperature was chosen as 853K and the
pressure as 1.4 atm for the actual production. When deciding on the building material of the
reactors, carbon steel was chosen so that the abrasive table of ethylbenzene was suitable for both
conditions and cost. In order to balance the matter and energy for the reactors, the Cp of the
components were calculated and the enthalpy and gibbs free energy of the reaction were
calculated. According to these calculated values, the equation was calculated for the K values at
298K and 853K. Then, material balance was made and Xa values corresponding to certain
temperatures were reached by using the K y equation and excel. By making energy balances in
both reactors, the output temperatures and transformations at these temperatures were reached by
calculating which output temperature and which transformation occurred from these energy
balances, and taking into account the equilibrium curve. Then, X a versus -1/ra graphs were
drawn according to the input and output temperatures determined by writing design equations.
The volumes of the catalyst and reactors used were obtained by calculating the areas of these
graphs and putting them in the design equations. In line with these volumes, the costs of the
reactors were calculated. The cost of the catalyst was calculated by considering the kilogram of
the catalyst used. Finally, the pressure drop values in the reactors were calculated using the ergun
equation.

1
In addition, since it was decided to use two reactors in styrene production to achieve maximum
conversion, paying attention to operational conditions and safety, it was decided to use a heat
exchanger to heat the exit temperature from the first reactor to the temperature suitable for the
second reactor amount and after that the cost required for the heat exchanger has been calculated.

Before this design was completed, risk assesment was made and necessary safety precautions
were taken into account. In this design, which was made by considering all the safety details and
standards required for the dehydrogenation of ethylbenzene and the production of styrene, the
most appropriate cost was found and the total cost was reached.

2
 2. METHOD OF ATTACK & CALCULATIONS

In this part of the report, the steps to be followed during the design of a reactor to produce
styrene from ethyl benzene, are given in Table 2-1 as the method of attack and the points to be
considered in reactor design such as physical-chemical properties of the raw materials and
products, the main and side reactions, the kinetics of the reactions, the choice of catalyst, the
reactor type has also been given. Then, detailed calculations were made for the reactor and the
cost of the reactor was calculated considering the safety precautions.

Table 2-1. Steps to be followed during the reactor design

Step 1 Make literature research about the reactions procedure

Step 2 Define the all raw materials and products and collect chemical-physical
properties of the all raw materials and products
Step 3 Decide what the reaction kinetics is like (simple, complex, phase etc.) and
select the catalyst
Step 4 Develop the process and make material and energy balance and pressure
drop
Step 5 Determine the reactor sizes
Step 6 Determine heat exchanger
Step 7 Safety precautions
Step 8 Economic evaluation (raw materials, product quality, equipment specs
and cost)

2.1. Literature Research About The Reactions Procedure

The production of styrene involves the dehydrogenation of ethylbenzene in a high-temperature,
low pressure gas-phase adiabatic reactor. The reaction is reversible and endothermic [1].

Main reaction: C 6 H 5 C H 2 C H 3 ↔ C 6 H 5 CH C H 2+ H 2

There are several other side reactions given below that consume ethylbenzene and produce
undesirable byproducts [1].

Side reaction 1: C 6 H 5 C H 2 C H 3 → C 6 H 6 +C 2 H 4

Side reaction 2: C 6 H 5 C H 2 C H 3 + H 2 → C 6 H 5 C H 3 +C H 4

3
At the same time, a superheated steam is used in the reaction. Superheated steam is used to
provide heat needed for the reaction, to reduce the ethylbenzene and hydrogen partial pressures
for maximising yields, and to keep the catalyst clean and active [1].

2.2. Raw Materials And Products Of The Reactions

Table 2.2- 1 Physical and chemical properties of ethylbenzene [2]

Property Information
Color Colorless
Odor Sweet, gasoline-like
Melting/Freezing Point -95 oC
Boiling Point at 1 atm 136 oC
Flash Point 23 oC
Upper Flammability Limit 6.7 % (vol)
Lower Flammability Limit 0.8 % (vol)
Vapor Pressure 9.5 mmHg (25 oC)
Auto-Ignition Temperature 430 oC
Molecular Weight 106.17 g/mol
Density at 25 oC, 1 atm 866 kg/m3

Table 2.2- 2 Physical and chemical properties of styrene [3]

Property Information
Color Colorless
Odor Sweet, gasoline-like
Melting/Freezing Point -31 oC
Boiling Point at 1 atm 146 oC
Flash Point 31 oC
Upper Flammability Limit 7.0 % (vol)
Lower Flammability Limit 1.1 % (vol)
Vapor Pressure 5.25 mmHg (25 oC)
Auto-Ignition Temperature 490 oC
Molecular Weight 104.15 g/mol
Density at 25 oC, 1 atm 909 kg/m3

4
Table 2.2- 3 Physical and chemical properties of benzene [4]

Property Information
Color Colorless
Odor Sweet, gasoline-like
Melting/Freezing Point 5.5 oC
Boiling Point at 1 atm 80.1 oC
Flash Point -11 oC
Upper Flammability Limit 7.1 % (vol)
Lower Flammability Limit 1.3 % (vol)
Vapor Pressure 75 mmHg (25 oC)
Auto-Ignition Temperature 498 oC
Molecular Weight 78.11 g/mol
Density at 25 oC, 1 atm 876 kg/m3

Table 2.2- 4 Physical and chemical properties of ethylene [5]

Property Information
Color Colorless
Odor Sweet, gasoline-like
Melting/Freezing Point -169 oC
Boiling Point at 1 atm -103.9 oC
Flash Point -136 oC
Upper Flammability Limit 36 % (vol)
Lower Flammability Limit 2.7 % (vol)
Vapor Pressure 5.21 × 104 mmHg (25 oC)
Auto-Ignition Temperature 490 oC
Molecular Weight 28.04 g/mol
Density at 25 oC, 1 atm 873.7 kg/m3

5
Table 2.2- 5 Physical and chemical properties of toluene [6]

Property Information
Color Colorless
Odor Sweet, gasoline-like
Melting/Freezing Point 95 oC
Boiling Point at 1 atm 110 oC
Flash Point 4 oC
Upper Flammability Limit 7 % (vol)
Lower Flammability Limit 1.2 % (vol)
Vapor Pressure 28.4 mmHg (25 oC)
Auto-Ignition Temperature 535 oC
Molecular Weight 92.14 g/mol
Density at 25 oC, 1 atm 867 kg/m3

Table 2.2- 6 Physical and chemical properties of methane [7]

Property Information
Color Colorless
Odor Sweet, gasoline-like
Melting/Freezing Point -187.6 oC
Boiling Point at 1 atm -161.48 oC
Flash Point -104 oC
Upper Flammability Limit 14 % (vol)
Lower Flammability Limit 5 % (vol)
Vapor Pressure 4.66 × 105 mmHg (25 oC)
Auto-Ignition Temperature 537 oC
Molecular Weight 16.05 g/mol
o
Density at 25 C, 1 atm 0.657 kg/m3

6
Table 2.2-7. Enthalpy and Gibbs Energy of Formation [8]
Component o o
∆ H f ,298 (kJ /mol) ∆ G f ,298 (kJ /mol)
C 6 H 5 C H 2 C H 3 ( ethylbenzene ) 29.81 130.28

C 6 H 5 CH C H 2( styrene) 147.46 213.80

H 2 (hydrogen) 0 0

C 6 H 6 ( benzene) 82.98 129.66

C 2 H 4 (ethylene) 52.33 68.12

C 6 H 5 C H 3 (toluene ) 50.03 122.01

C H 4 (methane) -74.86 -50.84

2.3. Reaction Kinetics

Table 2.3-1. Reaction Kinetics [1]

Reaction Concentration (Pascals) k E (kJ/kmol) Rate Equations

Number
1 (forward) P Ethylbenzene 0.044 90 981 − E1 F
RT
R1 F =P EB k 1 F e
1 (reverse) PStyrene P Hydrogen 6 ×10 -8
61 127 −E 1R
RT
R1 R =PS P H k 1 R e
2 P Ethylbenzene 27 100 207 989 −E2

R2=P EB k 2 e RT
3 P Ethylbenzene P Hydrogen 6.484 ×10-7 91 515 −E 3
RT
R3=P EB PH k 3 e
3
*Overall reaction rates have units of kmol/m . s

In this reactor design, an alkali promoted iron oxide (Fe 2O3) catalyst is preferred. Alkali
promoted iron oxide is known to be significantly better than any other catalyst with a higher
activity than uninitiated oxide and is preferred in the industrial process for ethylbenzene
conversion [9].

2.4. Material And Energy Balance

In this part of the report, matter and energy balances are made. The substance balance was made
to see on the graph how much the ethylbenzene conversion would be depending on the
temperatures in the reactor to be used. The energy balance was made to determine the exit
temperatures of the first and second reactors and to see how much conversion occurred at these
temperatures. In addition, these processes were made by considering the main reaction and
detailed calculations are given below.

7
 2.4.1. Specific Heat Capacities
The specific heat capacity coefficients of the components in the main reaction are given in
Appendix A.1. Specific heat capacity calculation was made using the data in Appendix A.1.

Table 2.4.1-1. Heat capacity values of gases [8]

Component a b c

C 6 H 5 C H 2 C H 3 ( ethylbenzene ) -20.53 5.96 × 10-1 -3.08× 10-4

C 6 H 5 CH C H 2( styrene) 71.20 5.47 × 10-2 6.48 × 10-4

H 2 (hydrogen) 25.39 2.02 × 10-2 -3.85 × 10-5

∆ Cp ( molK
joule
)=∆ a+∆ bT + ∆ c T 2 (2.4.1-1)

∆ Cp=∆ Cp products −∆ Cpreactants

∆ Cp=∆ CpC H 6 5 CH C H 2 + ∆ CpH −∆ CpC H

2 6 5 C H2 C H3

∆ a=∆ a products −∆ areactants

∆ a=( 71.20+25.39 )−(−20.53 )=117.12

∆ b=∆ b products −∆ b reactants

∆ b=( 5.47 × 10−2 +2.02 ×10−2 ) −( 5.96 ×10−1 )=−0.521

∆ c=∆ c products −∆ c reactants

∆ c=( 6.48 ×10−4−3.85 × 10−5 )− (−3.08 ×10−4 )=9.175 ×10−4

−4 2
∆ Cp=117.12−0.521T +9.175 ×10 T

2.4.2. Enthaply and Gibb’s Free Energy

Table 2.4.2-1. Enthalpy of formation and Gibbs free energy of formation [8]

o o
Component ∆ H f ,298 (kJ /mol) ∆ G f ,298 (kJ /mol)
C 6 H 5 C H 2 C H 3 ( ethylbenzene ) 29.81 130.28
C 6 H 5 CH C H 2( styrene) 147.46 213.80
H 2 (hydrogen) 0 0

8
 o o o
∆ H r ,298 =∆ H f , products −∆ H f , reactants
(2.4.1-2)
o o o o
∆H r ,298 =∆ H f ,C 6 H 5 CH C H 2 +∆ H f , H2 −∆ H f , C6 H 5 C H 2 C H 3

o kJ kJ kJ
∆ H r ,298 =147.46 −29.81 =117.65
mol mol mol

o o
∆ Gr ,298 =∆ G f , products −∆G f , reactants
o (2.4.1-3)

o o o o
∆ Gr ,298 =∆ G f ,C 6
H 5 CH C H 2 +∆ G f , H −∆ G f ,C
2 6
H5C H2C H3

o kJ kJ kJ
∆ Gr ,298 =213.80 −130.28 =83.52
mol mol mol

2.4.3. Equilibrium Constant

T
∆H
o
=∆ H
o
+ ∫ ∆ CpdT (2.4.3-1)
r ,T r ,298
298

T
=117 650 J /mol + ∫ (117.12−0.521 T + 9.175× 10 T )dT
o −4 2
∆H r ,T
298

o 2 −4 3
∆ H r ,T =82824.44+ 117.12 T −0.256 T +3.06 × 10 T

−∆ Gr ,298
o (2.4.3-2)
ln K 298 =
RT
−83.52 kJ /mol
ln K 298 = =−33.7
( 8.314
J
molK
(298 K ) )
−15
K 298 =2.30 ×10

T o
1 ∆ H r ,T (2.4.3-3)
ln K T =ln K 298 + ∫
R 298 T 2
dT

T
1
ln K T =(−33.7)+ ∫ 82824.44 +
117.12 −4
−0.256+ 3.06 ×10 T dT
(8.314 molK )
2
J 298 T T

9962 −5 2
ln K T =−139.836− +14.08 lnT −0.0312T +1.84 ×10 T
T
9
Table 2.4.3-1. Value of equilibrium constants against changing temperatures

T LnK K
300 -33.43 3.03E-15
350 -26.6289 2.72E-12
400 -21.4269 4.95E-10
450 -17.2885 3.1E-08
500 -13.8867 9.31E-07
550 -11.0098 1.65E-05
600 -8.51436 0.000201
650 -6.29931 0.001838
700 -4.29133 0.013687
750 -2.43578 0.08753
800 -0.69102 0.501066
850 0.975275 2.651896
900 2.588629 13.31151
950 4.169506 64.68348
1000 5.734514 309.3627
1050 7.297298 1476.305
1100 8.86918 7109.448
1150 10.45965 34879.23
1200 12.07672 175732
1250 13.72721 915487.1
1300 15.41699 4960370
1350 17.15111 28095156
1400 18.93395 1.67E+08
1450 20.76936 1.05E+09

2.4.4. XA – T Graph
Table 2.4.4-1. Molar fractions of components

Component Feed Flow Rate (mol/s) Equilibrium Conversion Molar Fraction

C6 H5 C H2 C H3 32.74 mol/s 32.74−32.74 x A 32.74−32.74 x A
452.62+32.74 x A
C 6 H 5 CH C H 2 - 32.74 x A 32.74 x A
452.62+32.74 x A

10
 H2 - 32.74 x A 32.74 x A
452.62+32.74 x A
Steam 392.88 mol/s 392.88 mol/s 392.88
452.62+32.74 x A

Material Balance:

F EB=F EB ,0−F EB ,0 x A =32.74−32.74 x A

F ST =F ST ,0 + F A 0 x A =32.74 x A
F TOTAL=452.62+32.74 x A
F H 2=F H 2 ,0 + F A 0 x A=32.74 x A

F I =392.88 kmol/ s

K P=K y K f P
Δn
(2.4.3-4)

K f =1

Δn 2−1
P =(1.4 ) =1.4 atm

32.74 x A 32.74 x A
× (2.4.3-5)
yC H5 CH C H 2 × yH 452.62+ 32.74 x A 452.62+ 32.74 x A
K y= 6
=¿
2

yC 6 H5C H2 CH3
32.74−32.74 x A
452.62+32.74 x A

Table 2.4.4-2. Conversion values corresponding to changing temperatures at 1.4 atm

T Xa
300 0
350 0
400 0
450 0
500 0
550 0 XA-T
600 0
1
650 0.11
0.9
700 0.31
0.8
750 0.586536
0.7
800 0.851578
0.6
850 0.964344
0.5
900 0.99249
0.4
950 0.998437
0.3
11
0.2
0.1
0
0 200 400 600 800 1000 1200 1400
 1000 0.999672
1050 0.999931
1100 0.999986
1150 0.999997
1200 0.999999
1250 1
1300 1
1350 1
1400 1
1450 1

Energy Balance:

TR T 1 ,f
F i ,0
∫ ∑ F i C p i ⅆT +∫ ∑ Fi C pi ⅆT +Q R=−( Δ H rxn ) γi A
X (2.4.3-6)
T0 İ TR İ

T 0=853 K

T R =298 K

Table 2.4.4-3. Molarflow rates of components

Component Inlet Outlet of the first reactor Outler of the second reactor
C6 H5 C H2 C H3 F EB , 0 F EB , 1 F EB , 2
C 6 H 5 CH C H 2 F ST , 0 F ST , 1 F ST , 2
H2 F H 2 ,0 F H 2 ,1 F H 2 ,2
Steam FI ,0 FI FI

For 1st Reactor

TR TR T1 ,f T1 ,f T 1, f T 1, f

∫ F EB ,0 C p EB ⅆT + ¿∫ F I 0 C p I ⅆT + ∫ F EB ,1 C p EB ⅆT + ∫ F ST ,1 C p ST ⅆT + ∫ F H 2 ,1 C p H 2 ⅆT + ∫ F I C p I ⅆT
T0 T0 TR TR TR TR

TR TR T1 ,f T 1, f T1 ,f T 1, f

∫ F EB ,0 C p EB ⅆT + ¿∫ F I 0 C p I ⅆT + ∫ F EB ,0 C p EB ⅆT − ∫ F EB , 0 x A C p EB ⅆT + ∫ F ST , 0 C p ST ⅆT +¿+ ∫ F EB
T0 T0 TR TR TR TR

12
298 298

∫ 32.74(−20.53+0.596 T −3.08 ×10 −4

T ) ⅆT +¿ ∫ 392.88(32.24+ 0.1923× 10−2 T +1.055 × 10−5 T 2 ) ⅆT +
2

853 853

Table 2.4.4-4. XA values according to different temperature for 1st reactor

T XA
813 0.3044
818 0.2682
823 0.2317
828 0.1950
833 0.1580
838 0.1208
843 0.0833
848 0.0455
853 0.0076

For 2nd Reactor

TR TR TR TR T 1, f T 1, f

∫ F EB ,1 C p EB ⅆT +∫ F ST , 1 C p ST ⅆT +∫ F H 2 ,1 C p H 2 ⅆT +¿ ∫ F I 0 C pI ⅆT + ∫ F EB ,2 C p EB ⅆT + ∫ F ST , 2 C p ST
T0 T0 T0 T0 TR TR

TR TR TR

∫ (F ¿ ¿ EB , 0−0.3044 F EB , 0)C p EB ⅆT + ¿∫ (F ¿ ¿ ST ,0+ 0.3044 F EB , 0)C pST ⅆT +∫ ( F ¿ ¿ H 2 , 0+0.3044 F E

T0 T0 T0

298 298

∫ (32.74−0.3044 ×32.74)(−20.53+0.596 T −3.08 ×10 −4

T ) ⅆT + ¿ ∫ (0.3044 × 32.74)(71.20+5.47 ×10−
2

853 853

Table 2.4.4-5. XA values according to different temperature for 2nd reactor

T XA
818 0.5370
823 0.5025
828 0.4684
13
833 0.4348
838 0.4015
843 0.3687
848 0.3363
853 0.3044

2.5. Reactor’s Sizes

A graph of 1/- A versus x A was drawn from the conversion values found in both reactors. The
r
area under this graph gives the volume of the catalyst. The area under the graph was calculated
using the trapezedual rule. Then, the volume of the catalyst was multiplied by the void fraction
of the catalyst and the reactor volume was calculated.

Design equation of the Plug Flow Reactor;

xA
V cat d xA (2.5-1)
=∫
F A 0 0 −r A

For 1st Reactor

60 1st reactor
50

40
-1/RA

30

20

10

0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35
XA

Figure 2.5-1. 1/-r A versus x A graph for the first reactor

From Trapezedual rule;

0.05
2
[ 56.74+ 2 ( 56.64 +52.58+50.55+ 48.35+46.34 ) +44.26 ]=15.164

V cat
=15.164 → V cat =49.59m3
3.27 mol /s

Void fraction (ε ¿ of catalyst is 0.4.

14 (2.5-2)
V reactor =V cat × ( 1−ε )+V cat

3 3 3
V reactor =49.59 m +29.75 m ≅ 80 m

For 2nd Reactor

2nd reactor
82

80

78

76
1/ra

74

72

70
0.3044 0.3544 0.4044 0.4544 0.5044
xa

Figure 2.5-2. 1/-r A versus x A graph for the second reactor

From Trapezedual rule;

0.05
2
[ 82.27+ 2 ( 80.37 +78.26+76.16+74.05 )+ 71.94 ]=18.297

V cat
=18.297 → V cat =59.60 m3
3.27 mol /s

Void fraction (ε ¿ of catalyst is 0.4.

V reactor =V cat × ( 1−ε )+V cat

3 3 3
V reactor =59.60 m + 35.78 m ≅ 95 m

As a result of the literature research, the L/D ratio for the adiabatic plug flow reactor was found
to be 2 [10]. Considering this ratio, the reactor length was calculated as 8.16 m and the radius
was 2.04 m from the reactor volume found.

3
80 m =π r L
2 r =2.04 m

3
80 m =4 π r
3 L=8.16 m

Pressure Drop:

(2.5-3)
15
 2 2
∆P μ (1−ε ) u 0 (1−ε ) ρu0
=150 3 2
+1.75 3
L ε dp ε dp

Where, ∆ P is the pressure drop, L is the length of the bed, μ is the fluid viscosity, ε is the void
fraction of the packing, u0 is the fluid superficial velocity, d p is the particle diameter and ρ is the
density of the fluid.

2
π (d reactor ) π ( 4.08 m)2 2
Sreactor = = =13.07 m
4 4

(12507.4 kgs )
Mass flow rate m
u0 =
Cross sectional area of the reactor
=
( 866
kg
m
3 ) =¿
1.105
s
2
13.07 m

−4
μ=6.5× 10 Pa . s

d p=0.025 m

3
ρ=866 kg /m

For 1st Reactor

( ) ( )
2
( 6.5 ×10−4 Pa. s ) ( 1−0.4 )2 1.105 m ( 1−0.4 ) ( 2.0823 kg /m 3 ) 1.105 m
∆P s s
=150 3 2
+1.75 3
8.16 m (0.4) (0.025 m) ( 0.4 ) (0.025 m)

∆ P=0.21 atm

For 2nd Reactor

( ) ( )
2
( 6.5 ×10−4 Pa. s ) ( 1−0.4 )2 0.76 m ( 1−0.4 ) ( 2.0823 kg /m3 ) 0.76 m
∆P s s
=150 3 2
+1.75 3
8.16 m (0.4) ( 0.025 m) ( 0.4 ) (0.025 m)

∆ P=0.26 atm

16
 2.5.1. Cost of Reactor Purchased Cost
In Appendix X, there is a graph of the purchased cost according to the capacity of the reactor.
According to this graph, the purchased cost of the 80 m3 first reactor is read as $ 800 000 and for
second reactor cost of the 95 m3 is read as $1 000 000. Since Appendix X graphic values belong
to 2002, CEPCI method was applied to reach up-to-date data.

IndexValue at Present (2.5.1-1)

Present Cost =Original Cost ×
Index Value at Original Cost was obtained

Table 2.7.1-1. Cost indexes by year

Year CEPCI Index

2002 395.6

2020 596.2

596.2
Present Cost of 1 st reactor=$ 800 000× =$ 1 205 662.285
395.6

596.2
Present Cost of 2 nd reactor = $1 000 000 × =$ 1 507 077.856
395.6

Total Purchased Equipment Cost of Reactors=$ 2 712740.141

InstallationCost =25 % × Purchased Equipment Cost =$ 678 185.04

Safety Precautions∧Equipments =8 % × Purchased Equipment Cost=$ 217 019.2

Total Cost of Reactors=$ 3 607 944.39

2.5.2. Cost of Catalyst

3 3 3
Total Catalyst Volume=V cat 1 +V cat 2=49.59 m + 59.60 m =109.19 m

3 1282 kg
Catalyst Weight=109.19 m × 3
=139 981.58 kg catalyst
m

Cost of catalyst per tone = 200$/ton []

$ 200
Cost of Catalyst =139.981 tons× =$ 27 996.316
tons

17
 2.5.3. Cost of Heat Exchanger
The heat exchanger to be used between the two reactors is designed over ChemCAD simulation.
The area of the heat exchanger was calculated and the cost of the heat exchanger was calculated
after the necessary data were entered in ChemCAD. Detailed ChemCAD results are given in
Appendix x.

J
Q=377 777 (¿ ChemCAD)
s
(2.5.3-1)
Q=U × A ×∆ T LM

J
s
W
( )
377 777 = 500 2 × A ×(64.87 K )
m K

2
A=11.64m

2.5.4. Cost of Utility

According to the ChemCAD results, the heat duty of the heat exchanger was found as 377 777
J/s.
(2.5.4-1)
Q
m steam =
∆H

377.77 kJ /s
msteam = =2.22 kg /s
( 3817.5−3705.6 ) kJ / s

18
 3. RISK ASSESSMENT

Risk assessment is the process of identifying potential hazards and analyzing what might
happen if a hazard occurs. Considering the possible risks for the reactor used in this design,
the precautions to be taken against these risks are given in below.

Operational Risks Precaution

Extreme
1 Designing a cooling jacket outside the reactor
temperature rise

To monitor all parameters such as temperature and pressure in the

2 Explosion reactor instantly from computers and to allow the operator to
intervene instantly in case of a possible change.

Keeping coolant and fire extinguishing equipment around the

3 Fire
reactor

19
 4. RESULTS AND DISCUSSIONS

The aim of this task is to design the reactor that will convert ethylbenzene to styrene by
dehydrogenetion. For this task, first of all, the complex problem was discussed and a work plan
was prepared and the necessary division of labor was made among the group members.
According to the study plan, a literature search was conducted for all items for the desired
conditions at the beginning of the design. The thermodynamic information obtained as a result of
the literature review was used to determine the reactor type and operating conditions.
Considering all the findings obtained, the type of reactor was chosen as adiabatic plug flow
reactor. Fe2O3 catalyst was chosen to be used in the system. The inlet temperature of the reactor
was determined by taking into account the temperature operating range of the catalyst used, and
the operating conditions of the reactor were determined considering the operating temperature
range of the catalyst being 580-650 °C. The flow sheet of the designed system is given in figure
4-1. Flow summary table, table 4-1. made from the flow sheet of design as figure 4-1. Necessary
calculations were made considering the operating conditions of the reactor, side reactions, the
effect of the catalyst and operating conditions, safety and cost parameters.

Figure 4-1. Flow sheet of reactor design

Table 4-1. Flow summary table for process shown in Figure 4-1

Stream 1 2 3 4
Component EB + Steam EB+STY+H2+STEAM EB+STY+H2+STEAM EB+STY+H2+STEAM
Temperature 853 K 813 K 853 K 818 K
Pressure 1.4 atm 1.19 atm 1.19 atm 0.93
Phase Vapor Vapor Vapor Vapor

20
The calculations were started by calculating the formation enthalpies and gibbs free energies of
the substances, and the equilibrium constants for different temperatures were found by using the
Van't Hoff equation. As a result of the calculations made on the equilibrium constants found, the
conversion values corresponding to the changing temperatures were calculated and the
equilibrium curve was formed with the calculated values. Since the reaction is endothermic, the
conversion values increase as the temperature increases. However, high temperatures to reach
high conversion values are difficult and expensive to apply, and also increase the rate of
occurrence of side reactions. High conversion is normally desirable, but in this particular process
it is more feasible and cheaper to operate at low conversion and therefore at low temperature.
Also, Research tells us that low pressure and high ethylbenzene concentrations will support
styrene production. The production of unwanted by-products that waste the reactant
ethylbenzene can be reduced by keeping the temperature low. Therefore, there is an inverse
relationship between conversion and selectivity. For this reason, low conversion, high selectivity
was chosen in this report. Low pressure also slows down these undesirable reactions.

Two reactors were chosen to be used in this design. The reason for this is that a single reactor is
not enough to achieve the desired transformation. In order to calculate the reactor volumes
according to the selected operating conditions, first of all, matter and energy balances were
made. The outlet temperatures of the reactors were calculated according to the equations made.
A heat exchanger was placed between the two reactors to bring the 813 kelvin feed from the first
reactor back to 853 kelvin, which is the inlet temperature of the second reactor. The required
heat duty was calculated via ChemCad, and the steam flow rate to be used was calculated from
the calculated heat duty. The cost of the heat exchanger, determined according to the heat
transfer area, was determined as approximately 26 thousand dollars. Adiabatic lines were created
by using the temperature values against the transformation from the energy balance. The lines
created must remain below the equilibrium curve, because when it reaches the equilibrium curve,
the reaction comes to equilibrium, that is, it stops. The calculated conversion versus temperature
values were written in the rate expression, and the reaction rates were calculated for different
temperature-transformation values.

The area under the 1/rA - XA graph created with the calculated velocities and conversion values
gives the ratio of the catalyst volume to the inlet flow rate. It was calculated using the trapezoidal
rule, which is one of the numerical calculation methods under the graph, and the catalyst volume
was calculated from the value found. From the calculated catalyst volume to the reactor volume,
21
the void fraction was used, and the initial reactor volume was calculated as approximately 80 m 3.
The same operations were performed for the second reactor and its volume was calculated as
approximately 95 m3.

The ratio of reactor length to diameter was determined as 2. The length and diameter of the
reactors were calculated from the volumes of the reactors calculated using this ratio. Pressure
drops were calculated as a result of the Ergun equation using different flow rates for the two
reactors. The pressure drops are in the expected dimensions and do not pose a problem for the
system.

The cost was calculated by moving from the volume of the catalyst to the mass of the catalyst.
The purchasing costs of the reactors were read from the graph and brought to today's values
using the Cepci method. Security measures costs of 8 percent of the purchase cost and
installation costs of 25 percent are foreseen. As a result, the total cost of the reactors is about 3
million dollars. A risk assessment table has been created for the risks foreseen for this system
and the measures developed against the risks. The following pie charts were created over all the
calculated cost values.

Cost of Reactors
Installation
19%

Safety
6%

Purchased Equipment
75%

Purchased Equipment Safety Installation

Figure 4-2. Pie chart of cost of reactors

A large part of the cost of reactors is the purchase cost. Since the dehydrogenation of
ethylbenzene is a difficult process, the reactor volume must be large and therefore the reactor
cost increases at the same rate.

22
 Cost of Heat Exchanger
Basic Cost
Installation 9%
15%

Purchased Equipment
76%

Basic Cost Purchased Equipment Installation

Figure 4-3. Pie chart of cost of heat exchanger

The cost of the heat exchanger was not high because a multidimensional and complicated heater
design is not required. The biggest part of 76 percent is the purchasing cost.

Total Cost of Design

Reactor 1
Reactor 2 44%
54%

Catalyst
Heat Exchanger 1%
1%

Reactor 1 Heat Exchanger Catalyst Reactor 2

Figure 4-4. Pie chart of whole system cost

When the cost of the whole system was examined, it was seen that the second reactor was the
equipment with the highest cost. The reason for this is the high volume, and the heat exchanger
and catalyst costs are very low compared to reactors.

23
 5. CONCLUSION

In this report, reactors that convert ethylbenzene to styrene by dehydrogenetion are designed.
The important results obtained as a result of the calculations made for this purpose are given in
this section of the report.

First, a literature review was conducted. As a result of this scanning, the formation enthalpies
and gibbs free energies of all substances are specified. Based on the findings obtained from the
literature, the inlet temperature of the first reactor was determined as 853 kelvin, and the
reference temperature was 298 kelvin. Equilibrium constants were calculated and an equilibrium
curve was obtained. As a result of the material and energy balances made for the reactor
according to the determined temperatures, it was calculated that the outlet temperature of the first
reactor was 813 kelvin in 0.3044 conversion. The same process was carried out for the second
reactor, and the exit temperature was calculated as 818 kelvin at 0.53 conversion. The heat
transfer area required for the heat exchanger designed to make the supply suitable for the second
reactor was calculated as 11.64 m2 and the cost of the heat exchanger to provide the required heat
in this area was calculated as $ 25 867. Adiabatic lines were drawn according to the temperatures
obtained from the energy balance. The velocity values were calculated by substituting the
temperature and transformation rate found in the energy balance in the rate expression. The area
under the graph created by plotting the calculated rate values against the conversion values gives
the catalyst volume. The total catalyst volume was calculated as 109.19 m 3. When the cost in
kilograms is calculated, the cost of the catalyst is calculated as $27 996. The pressure drop in the
reactors is 0.21 atm and 0.26 atm, respectively. Reactor volumes were calculated from the
catalyst volume. The first reactor is 80 m3, the second 95 m3, respectively. Purchasing costs were
read from the chart according to their volumes. The total cost of the reactors was calculated by
adding 8 percent safety and 25 percent installation costs to the purchase cost. The total cost of
the first reactor is $1 205 662 and the second reactor is $1 507 077. The entire system costs $2
766 603.

24
 6. REFERENCES

[1] Luyben, L., W. (2011). Design and Control of the Styrene Process. Pennsylvania:
Department of Chemical Engineering, Lehigh University

Web: Retrieved December 2, 2021, from https://pubs.acs.org/doi/full/10.1021/ie100023s

[2] Safety Data Sheet For Ethylbenzene. (2017). Safe Work Australia.

Web: Retrieved December 2, 2021, from https://www.carlroth.com/medias/SDB-0272-AU-

EN.pdf?
context=bWFzdGVyfHNlY3VyaXR5RGF0YXNoZWV0c3wyNjkyNTV8YXBwbGljYXRp
b24vcGRmfHNlY3VyaXR5RGF0YXNoZWV0cy9oYmQvaGNhLzkwNDk5OTE0NzkzMj
YucGRmfGNmMzlmZmNjNWZiM2E0M2FhMjI0YjQ1MjQzZjRiNjY2OGNlN2QzYmM2
ZjhhYjBjOWVlODRiNjFjYTdiNmJmNzk

[3] Safety Data Sheet For Styrene. (2018). ThermoFischer Sceintific.

Web: Retrieved December 2, 2021, from https://www.fishersci.com/store/msds?

partNumber=AC132790010&productDescription=STYRENE+99%25%2C+STABILIZED+
1LT&vendorId=VN00032119&countryCode=US&language=en

[4] Safety Data Sheet For Benzene. (2018). ThermoFischer Sceintific.

Web: Retrieved December 2, 2021, from https://fscimage.fishersci.com/msds/02610.htm

[5] Safety Data Sheet For Ethylene. (2018).Chevron Philips Chemical Company.

Web: Retrieved December 2, 2021, from https://www.cpchem.com/sites/default/files/2020-

05/01542791_6.pdf

[6] Safety Data Sheet For Toluene. (2015).Global Safety Managment.

Web: Retrieved December 2, 2021, from

https://beta-static.fishersci.com/content/dam/fishersci/en_US/documents/programs/
education/regulatory-documents/sds/chemicals/chemicals-t/S25611.pdf

[7] Safety Data Sheet For Methane. (2020).Airgas.

Web: Retrieved December 2, 2021, from https://www.airgas.com/msds/001033.pdf

[8] Appendix C-Physical Properties Of Liquids And Gases.

25
Web: Retrieved December 2, 2021, from
https://booksite.elsevier.com/9780750683661/Appendix_C.pdf

[9] Sayyed, B., A., Gupta, M., P., Date, S., K., Kamble, K., R., Sonsale, A., Y., Chatterjee,
A., K., (1985). Structural and catalytic studies of promoted iron oxide catalysts used in the
dehydrogenation of ethylbenzene to styrene. India: Proc. Indian Acad. Sci.

Web: Retrieved December 8, 2021, from

https://www.ias.ac.in/public/Volumes/jcsc/095/03/0285-0290.pdf

[10] Kumar, B., G.(2015). Steady state simulation of Plug Flow Reactor (PFR) in Aspen
plus. India: Department of Chemical Engineering National Institute of Technology Rourkela

Web: Retrieved December 9, 2021, from http://ethesis.nitrkl.ac.in/7116/

[11] Fe2O3 demir oksit katalizör/demir oksit kükürt giderme/demir oksit kükürt fiyat.
Alibaba

Web: Retrieved December 9, 2021, from https://turkish.alibaba.com/product-detail/fe2o3-

iron-oxide-catalyst-iron-oxide-desulfurization-ferric-oxide-desulfurizer-price-
60632906610.html

26
 7. NOMENCLATURE

ρ : Density, kg/m3 ∆ P : Pressure Drop, atm

MW : Molacular Weight, g/mol µ : Viscosity, kg/m.s

d : Diameter, m q : Volumetric Flow Rate, m3/s
ṁ : Mass Flow Rate, kg/h W : Work, kW
V : Volume, m3 ή : Efficiency
h : Height, m U : Overall Heat Transfer Coefficient,
D : Diameter, m W/m2.°C
L : Length, m k : Thermal Conductivity, W/m.°C
r : Radius, m T : Temperature, °C
P : Pressure, kPa or atm A0 : Heat transfer area, m2
g : Gravity, m/s2 ∆ T LM : Log Mean Temperature
Difference , °C
M : Mass, kg
Cp : Specific Heat, kJ/kg
CC ,: Corrosion Allowance , m
Q : Energy, kJ/h
A : Area, m2
t : Thickness, m

ε : Void Fraction

RA : Rate equation,

F : Flow rate, mol/s

K : Equilibrium constant

y : Yield

XA : Conversion

E : Activation Energy, kj/kg

°G : Gibss Free Energy, kj/kg

°H : Entalphy

27
 8. APPENDIX A.

A.1. Heat Capacity of Gases [8]

28
A.1. Cont’d [8]

A.2. Enthalpy of Formation [8]

29
A.2. Cont’d [8]

30
A.3. Gibb’s Free Energy [8]

31
A.3. Cont’d [8]

32
A.4. ChemCAD Results For The Heat Exchanger

A.4. Cont’d
33
A.5. Purchased Cost of Reactor for Their Capacity Values

34
 A.6. Work Plan of Design

Complex Problem : Production of styrene by dehydrogenetion of Ethylbenzene.

Table 1. Project Management and Risk Assessment

Assingment : 2

Duty Designing a reactor to produce styrene

Team Leader Selin Özçelik

Task # Description Time Interval Responsible

Major Task 1 Reaction Reasearch

Minor Task 1 To investigate all the physical and chemical properties of desired product.
5 days Begüm Çalı
Minor Task 2 Investigating reaction properties.

Minor Task 3 To investigate side reactions and catalysts.

Major Task 2 Reactor Design

Minor Task 1 Pressure and tempature requirements

7 days Banu Arslan
Minor Task 2 Study on Reaction Kinetics

Minor Task 3 Make material and energy balances.

Major Task 3 Estimation

3 days Sercan Tansu
Minor Task 1 Cost Estimation

A.7. Assignment 2

35
36