Table of Contents

CHAPTER 1........................................................................................................2
INTRODUCTION................................................................................................2
1.1 Introduction............................................................................................2
1.2 Physical properties..................................................................................2
1.3 Chemical properties................................................................................3
1.4 Supply and Demand................................................................................4
1.5 Production Technologies..........................................................................6
CHAPTER 2......................................................................................................11
MATERIAL AND ENERGY BALANCE.............................................................11
2.1 Introduction..........................................................................................11
2.2 Block Flow Diagram.............................................................................11
2.3 Material Balance...................................................................................12
2.4 Energy Balance.....................................................................................16
CHAPTER 3......................................................................................................20
REACTOR SIZING CONSIDERING MAIN REACTION....................................20
3.1 Reactor Sizing According Algorithm......................................................20
3.2 Catalyst Determination..........................................................................23
3.3 POLYMATH Result..............................................................................24
REFERENCES..................................................................................................28

CHAPTER 1

INTRODUCTION

1.1

Introduction
Ethylbenzene is an organic compound with the formula (C6H5CH2CH3) also

known as phenylethane, ethylbenzl or alpha-methyltoluene, a single ring and alkyl

aromatic compound. In petrochemical industry, the aromatic hydrocarbon is important
and almost exclusively (> 90%) as an intermediate in the production of styrene, which
is used for making polystyrene, it is a common plastic material. In styrene production,
which uses ethylbenzene as a starting raw material, consumes ca. 50% of the worlds
benzene production. Less than 1% of the ethylbenzene produced is used as paint
solvent or as an intermediate for the production of diethylbenzene and acetophenone.
(Ullmman''s, 1985)
It is used as a solvent for aluminium bromide in anhydrous electro deposition
of aluminium. Ethylbenzene is an ingredient in some paints and solvent grade xylene
is nearly always contaminated with a few per cent of ethylbenzene. (Vincent AVincent
A.Welch, 2005)
Essentially all commercial of ethylbenzene production is captive consumed for
the manufacture of styrene monomer. Styrene is used in the production of polystyrene
and a wide variety of other plastics. Of the minor uses, the most significant is in the
paint industry as a solvent, which accounts for <1% of production capacity.
Acetophenone, diethylbenzene, and ethylanthraquinone with smaller volumes also go
toward for the production. (Vincent AVincent A.Welch, 2005)

1.2

Physical properties
Under ordinary conditions, ethylbenzene is a clear, colourless liquid with a

characteristic aromatic odour which can be detected at low concentrations.

Ethylbenzene is an irritant to the skin and eyes. Moreover, it is moderately toxic by

ingestion, respiratory effects such as throat irritation and lung constriction, irritation
to the eyes and skin adsorption. The physical properties of ethylbenzene are as
follows (Ullmman''s, 1985) :
Table 1.1: Physical properties of Ethylbenzene
No.

1.3

Density

2
3

Melting Point
Boiling Point

Refractive Index

5
6
7
8

Critical Pressure
Critical Temperature
Flash Point
Auto Ignition Temperature

Flammability Limit

10

Latent Heat

11

Heating Value

12

Kinematic viscosity

13

Surface tension

14

Specific Heat Capacity

Properties
At 150C
At 200C
At 250C
At 101.3 KPa
At 200C
At 250C

lower
upper
fusion
vapour ization
gross
net
At 37.80C
At98.90C
Ideal gas,250C
Liquid,250C

0.87139 g/cm3
0.8669 g/cm3
0.86262 g/cm3
-94.9490C
136.1860C
1.49588
1.49320
3609 KPa
344.020C
150C
4600C
1.0%
86.3 J/gm
335 J/gm
429999 J/gm
40928 J/gm
0.6428x10-6 m2/s
0.390x10-6 m2/s
28.48 mN/m
1169 J kg-1 K-1
1752 J kg-1 K-1

Chemical properties
Chemically, it is a monocyclic alkylaromatic compound with a 106 of

molecular weight. It is miscible with most of the commonly used organic solvents in
any ratio, but is only sparingly soluble in water (170 ppm under ambient conditions).
Spilled ethylbenzene will float on water and partition strongly towards air. No
significant environmental hazards are expected due to its high evaporation rate.
Being rather volatile and having a flash point of 19-23 C, ethylbenzene is
classified as a highly flammable substance, which in use may form flammable or
explosive vapour-air mixtures. The most important commercial reaction of

Ethylbenzene is its dehydrogenation to styrene. The reaction is carried out at high

temperature (600-6600C) usually over an iron oxide catalyst. Steam is used as
diluents. Commercially, selectivitys to styrene range from 89 to 96% with per-pass
conversions of 65-70%.
The production by products is reduced if the temperature is gradually lowered
during the course of the reaction. The hydro peroxide is subsequently reacted with
propene in a process that yields styrene and propylene oxide as co products. With
suitable catalyst, it can be converted to xylenes. Commercially processes for
isomerising xylenes usually involve the catalytic isomerisation or dealkylkylation of
Ethylbenzene. Like toluene, it may be dealkylated catalytically or thermally to
benzene. It is also undergoes other reaction typical of alkyl aromatic compounds.
(Vincent AVincent A.Welch, 2005)

1.4

Supply and Demand

We have mentioned that ethyl benzene is a colourless liquid with a gasoline

odor and high inflammability. So that it is widely used in the petrochemical industry
in manufacturing of styrene.
Styrene is used mostly important applications of ethylbenzene that were
manufactured

in polymer production for polystryrene and

mostly in polymer

production for polystyrene, acrylonitrile-butadiene-styrene (ABS) and styreneacrylonitrile (SAN) resins, styrene-butadiene elastomers and latexes, and unsaturated
polyester resins..
It is also used as an intermediate material in the production of plastic products
and is utilized as one of the basic raw materials in the production of various
chemicals. Ethylbenzene also a good solvent which it have in different sectors like in
the rubber industry, ink industry, the major markets of the styrene ware include
packaging, electrical/electronic/appliances, construction and consumer products.
The global demand for ethyl benzene is growing wherein the Asia Pacific
region has retained more than 47% of the market. China is the largest consumer and

producer of ethyl benzene, having a market share of 28%. It is because, the value of
Ethyl Benzene were so high that will give benefit to the industry to produce more
product that were linked to Ethyl Benzene.
This shows that the Ethyl Benzene (EB) is quite an important chemical
product that has a lot of uses to the industry. Based on analysis, The Asia-Pacific is
the biggest market of benzene consuming a significant share of the total consumption
in 2012, and it is also the second fastest growing market next to ROW. The
consumption patterns of benzene and its various derivatives are continuously showing
an upward trend which is mainly due to the shift of manufacturing industry to the
Asia-Pacific on account of increasing demand and low cost of production. China is
the leading country in the region in terms of both, production as well as consumption
of benzene and its derivatives, while the Indian market, despite being small in size, is
expected to be a market with high potential (PRNewswire , New York, June 19,
2014).

Figure 1. 1: The consumption of Ethyl benzene in the world in 2013

Figure 1.1 shows the consumption of Ethyl benzene in the world in 2013. The
world consume the EB about 99% to produce a lot of variety product that will
generate economy and about 1% consumed of ethylbenzene is used for other
applications.

For instance, global demand for ethyl benzene amounted to 28,567,852 tons
in 2014 (BGI research, 2012). The global EB market was dominated by the AsiaPacific region, with the domestic markets in developing economies expanding
exponentially (Global Chemical Price, 2013). The increasing standard of living and
increased styrene capacities across the globe increased the usage of EB in a number of
countries. With demand recovery expected in developed markets and increasing
demand expected from developing economies, overall global EB demand is expected
to have reached 34,667,874 tons by 2020 (GBI Research, 2012). Figure 1.2 shows
global demand trends for EB in volume terms from 2000 to 2020.

Figure 1. 2: Global Demand Trends for EB in volume terms from 2000 to 2020 by
GBI Research (2012)

1.5

Production Technologies
Currently, almost all ethylbenzene is produced commercially by alkylating

benzene with ethylene. There are different manufacturing processes available for
ethylbenzene .Some these are listed below:

1)
2)
3)
4)

1.5.1

Liquid phase aluminum chloride catalyst process

Vapour-phase zeolite catalyst process
Liquid phase zeolite catalyst process
Mixed Liquid-Vapour Phase zeolite Catalyst process

Liquid Phase Aluminium Chloride Catalyst Process

This is the first process used in producing of ethylbenzene since 1930s.

Alkylation of benzene with in the presence of an aluminum chloride catalyst complex

is exothermic (_H-114 kJ/mol); the reaction is very fast and produces almost
stoichiometric yields of Mthyl benzene. In addition to AlCl3, a wide range of Lewis
acid catalysts, including AlBr3, FeCl3, and BF3, have been used. Aluminum chloride
processes generally use ethyl chloride or hydrogen chloride as a catalyst promoter.
These halide promoters reduce the amount of AlCl3 required.

1.5.2

Vapour-Phase Zeolite Catalyst Process

Vapour-phase alkylation has been practiced since the early 1940s, but at that

time processes were unable to compete with liquid-phase aluminum chloride based
technology. The alkar process developed by UOP, based on boron trifluoride catalyst,
had modest success in the 1960s, but fell from favour because of high maintenance
costs resulting from the severe corrosion caused by small quantities of water.
Nevertheless, some Ethylbenzene units continue to use this process. The Mobil
badger Ethylbenzene process represents the latest and most successful vapour phase
technology to be introduced. The process was developed in the 1970s around.

1.5.3

Liquid Phase Zeolite Catalyst Process

The EBMax process offered by Mobil/badger is a liquid phase alkylation

reaction using a catalyst based on the MCM-22. A commercial plant based on the
EBMax technology was commissioned in 1955 at Chiba Styrene Monomer Company.
1.5.4

Mixed Liquid-Vapour Phase zeolite Catalyst process

The CDTECH process is based on mixed liquid-vapour phase alkylation

reactor section. The design of commercial plant is similar to the liquid phase
technologies except for the design of the alkylation reactor which combines catalytic
reaction with distillation into a single operation.
Table 1.2: The Comparison for Production Technology of Ethylbenzene.
(Shenglin Liu, March 2009)

Proper
ties

Liquid Phase
Aluminium
Chloride
Alkylation

Operat
ing
Tempe
rature
Operat
ing
Pressur
e
Conver
99%
sion
Three phase
are present ;
Aromatic
liquid,
Phase
ethylene gas,
and a liquid
catalyst
complex
phase
Aluminium
Catalys Chloride
t
catalyst
complex
Advant i.
The
ages
aluminium
chloride
present in
alkylation
reactor
effluent
catalyst trans

Vapour-phase
Zeolite
Alkylation

Liquid phase
Zeolite
Alkylation

400-450 C

450 to 600 C.

Mixed Liquidvapour phase

Zeolite
Alkylation

2-3 MPa (20-30

bars).
100%

100%

100%

The high-activity
catalyst allows
transalkylation
and alkylation to
occur
simultaneously in
a single reactor

The alkylation
reactor is
maintained in
liquid phase

Mixed liquidvapour phase

Zeolite Catalyst

Zeolite Catalyst

Zeolite Catalyst

i.
Use of
zeolite catalyst
that eliminated
issues associated
with corrosion
and waste
disposal of
aluminium

i.
The
liquid phase
zeolite catalyst
process
operates at
substantially
lower
temperature

i.
Combines
catalyst reaction
with distillation
into single
operation
ii.
The

alkylation
reaction.
ii.
Reaction is
very fast in
presence of
Aluminum
chloride
&produces
almost
stoichiometric
yields of
Ethylbenzene.
iii.
Essentially
100% of
ethylene is
converted

Disadv i.
antages
Handling and
disposal of
aluminium
chloride
catalyst and
waste has
become
increasingly
more costly
and
complicated
because of

decreased side
exothermic heat
reactions
of reaction
dramatically
creates
resulting in
chloride
vaporisation
ultra-high
ii.
The
necessary to
purity EB
original vapour
effect distillation
product
phase design
iii.
Capable
ii.
The
accomplished the
of using dilute
plant achieve
alkylation and
ethylene feed
high on stream
trans alkylation
e.g. Off gas
efficiency often
reactions in single
from a fluid
greater than
reactor
catalytic
99% which
iii.
The third
cracking plant or
results in low
generation
dilute ethylene
turnaround &
technology is
from steam
maintenance
capable of
cracker
cost
achieving EB
iv.
In
iii.
EBZyield greater than
general ethylene
500 catalyst has
99%
feed streams
operating length
iv.
The third
containing
of more than
generation
significant
8year without
technology
amounts of
catalyst
offered significant
hydrogen,
regeneration
benefits in
methane or
iv.
The
purity ,capital
ethane do not
regeneration is
cost
require some
mild carbon
pre-treatment.
burn procedure
(David Netzer,
that is relatively
1999)
inexpensive
i.
The
Do not have disadvantage
significant extent
of isomerisation
reactions and
catalyst
deactivation by
deposition of
carbonaceous
material are most
important
problems
associated with
high temperature
ii.
The length

environmental
considerations
ii.
Equipment
and piping
corrosion and
fouling along
with related
environmental
issues led to
development
of EB process
based on solid
acid
heterogeneous
catalysts
iii.
Major
equipment
pieces needed
to replace on
regular
schedule
because of
corrosion
which results
in extensive
turnarounds
poor plant onstream
efficiency and
thus are
primary
contributors to
the high
operating
costs
associated
with
aluminium
chloride

of time between
regeneration can
vary from as little
as 2 months to
slightly more than
1 year depending
on specific plant
design and
operating
conditions
iii.
Because
the reactors must
be taken off line
for
regeneration ,onstream efficiency
can be low
resulting in high
operating costs
for vapour phase
plant
iv.
Additional
equipment may be
required for
regeneration
procedure
depending on
specific plant
design which adds
capital cost to
plant

From above advantages & disadvantages for different processes we select

Vapour Phase Zeolite Catalyst process (UOP). Since it has more advantages over
other existing manufacturing process for Ethylbenzene. Not only that, it also have
long catalyst run-length with excellent stability which can minimizes plant downtime,
and It has highly selective reaction that are insignificant amount of xylenes are
produced, providing a highest product quality. Also it requires less pure benzene &
ethylene. Less harm full to environment also. (technology, 2012)

CHAPTER 2

MATERIAL AND ENERGY BALANCE

2.1

Introduction
This chapter will focus on calculation of material and energy balance for

production of 40,000 MT of Ethylbenzene. The reaction kinetics of EB production is

as follows. The production of ethylbenzene (C6H5C2H5) takes place with the direct
addition reaction between ethylene (C2H4) and benzene (C6H6).
C6H6 + C2H4 C6H5C2H5

----- (1)

However, there is another inevitable reaction takes place at the same time as
reaction (1) which is to produce diethylbenzene (C6H4(C2H5)2), an unwanted product.
C6H5C2H5 + C2H4 C6H4(C2H5)2

2.2

----- (2)

Block Flow Diagram

To roughly interpret the process of the Ethylbenzene production, an input-

output structure of reactor is illustrated as shown in Figure 2.1. In stream 1, there is

pure feed of Benzene, n1, and in stream 2, a pure feed of Ethylene, n2. Stream 3
consists of unconverted ethylene n3 and benzene n4, ethylbenzene n5, as well as
diethylbenzene n6.

Figure 2. 1: Input-output structure of reactor of Ethylbenzene plan

2.3

Material Balance
As this is mini project for Chemical Reaction Engineering II, we will consider

the material balance in the reactor only. Analysis of material balance follows the
extent of reaction method. The symbols 1 and 2 are used to denote the extents of
reaction for the first and second reaction, Equation (1) and Equation (2) respectively.
The material balances of all chemical species are generally computed using
the correlation as follows:
Mi = M0 + vi 1 -----(3)
where Mi is molar flow rate of the species i and v i is the stoichiometric coefficient.
The summary of using extent of reaction is as in Table 2.1.
Table 2.1: Material Balance Summary
Species
Benzene
Ethylene
Ethylbenzene
Diethylbenzene

Inlet
FB
FE
0
0

Change
- 1
- 1- 2
1- 2
2

Outlet
0
0
PEB
PDEB

The capacity of the plant producing commercial grade ethylbenzene is 40,000

metric tonne per year and it has been assumed that the plant operates 8000 hours per
year with about 32 days for shutdown, maintenance and troubleshooting. The basis of
production of ethylbenzene per day will be used.
40,000 MT 1000 kg
1 year
x
x
=5000 kg /hours
year
1 MT 8000 hours

----- (4)

From Equation (4), 5000 kg of Ethylbenzene will be produced per hour. The
assumption of calculation are listed as follows;

Pure benzene and ethylene

All gases behave ideally
Yield is 99.99%
90% conversion of ethylene (limiting reactant) to ethylbenzene &
diethylbenzene

Molecular mass for each species is summarized in Table 2.2

Table 2.2: Molecular Mass of Species Involved in the Process
Species
Ethylene
Benzene
Ethylbenzene
Diethylbenzene

Ethylene
Ethylene inlet into the reactor, FE = FFE + (1 - X)
= FFE/X
= PEB/YX
= 47.09/0.99 (0.9)
n2

= 52.85 kmol/hour

Molecular Mass (kg/kmol)

28.05
78.11
106.17
134.22

Ethylene outlet from the reactor, FE = FFE + (1-X)

= PEB/YX * (1-X)
= 47.09/0.99 (0.9) * (1-0.9)
n3

= 5.29 kmol/hour

Benzene
For PEB,

n5

==

5000 kg
1 kmol
x
hour
106.17 kg

= 47.09 kmol/hour

For benzene inlet into the reactor,

= PEB/Y+FE (3 X)
= 47.09/0.99 + 52.85 (3-0.90)
n1

= 158.55 kmol/hour

Benzene outlet from the reactor,

= PEB/YX (3-X)
= 47.09/0.99(0.9) * (3-0.90)
n4

= 110.99 kmol/hour

Diethylbenzene
Diethylbenzene outlet from the reactor, PDEB=PEB/YX * (1-0.99)
= 47.09/0.99 (0.9) * (0.01)
n6

= 0.53 kmol/hour

The results of calculations are tabulated as in Table 2.3. It is shown from total
of mass balance, the calculation is considered balanced.
Table 2.3: Summary of Mass Balance.
Species
Benzene
Ethylene
Ethylbenzene
Diethylbenzene
Total

Inlet
(kmol/hour)
158.55
52.85
0
0
211.4

Outlet
(kmol/hour)
110.99
5.29
47.09
0.53
163.9

Inlet
(kg/hour)
12384.3405
1482.4425
0
0
13866.783

Outlet
(kg/hour)
8669.4289
148.3845
4999.5453
71.1366
13888.4953

2.4

Energy Balance
In this part, only energy balance in the packed bed reactor will be calculated

accordingly. Figure 2.2 shows input-output structure of temperature in the said reactor, where
temperature feed is at 298K, while the temperature outlet is 573K. The reactor operates at
573K and 5000 kPa.

Figure 2. 2: Input-output structure of temperature in reactor

The assumptions for energy balance calculation are as follows;

The process follow the law of conservation of energy where:

Energy out = Energy in + Generation Consumption Accumulation
Steady-state condition in all equipment.
Kinetic energy, potential energy and shaft work change for these streams will be
neglected and only enthalpy changes take place. Hence the energy balance equation

equal to Q = H
Ideal properties for evaluating the energy balances of the process streams. This means

the pressure effect can be neglected.

No heat of mixing and pressure effect on H.
Reference temperature for all the calculation is 1 atm and 25C.

Figure 2.3 shows structure of enthalpy path of reaction from 298K to 573K, where H
is enthalpy change of the reaction, Hrxn is heat of reaction of benzene and ethylene to

ethylbenzene at 298K and HP, 1 denotes enthalpy change of ethylbenzene from 298K to
573K.

Figure 2. 3: Enthalpy structure for energy balance

As both ethylene and benzene enter in gas phase at 298K (Smith, 1925), no heat of
vaporization is required. To aid the calculation, thermodynamic properties is tabulated as in
Table 2.4.
Table 2.4: Thermodynamic Properties of the Species Involved (Smith, 1925)
Species
C2H4 (Ethylene)
C6H6 (Benzene)
C6H5C2H5 (Ethylbenzene)

2.4.1

A
1.424
-0.206
1.124

B (103)
14.394
39.064
55.380

C (106)
-4.392
-13.301
-18.476

Heat of Reaction, Hrxn at 298 K:

According to Smith (1925), the heat of reaction of ethylene, benzene, and

ethylbenzene are as follows;

Hf 298C Ethylene (gas)

: 52510 J/mol

Hf 298C Benzene (gas)

: 82930 J/mol

Hf 298C Ethylbenzene (gas)

: 29920 J/mol

H rxn= H rxn PRODUCT H rxn REACTANT

From equation above,

Hrxn = 29920 82930 52510
Hrxn = -105520 J/mol

The heat of reaction is calculated by using formula;

298 K

H R =R

( A+ BT + C T 2 + D T 3 ) dT T [ ] K

773 K

The heat of reaction of Benzene from 298 K to 573 K

H R , C H = 3904.97 J/mol
6 6

The heat of reaction of Ethylene from 298 K to 573 K

H R , C H = 1878.78 J/mol
2 4

The heat of reaction of Ethylbenzene from 298 K to 573 K

H R , C H C H = 5945.88 J/mol
6 5 2 5

The total heat of reaction of benzene, ethylene, ethylbenzene from 298 K to 573 K
HP,1 =

H R ,

C6H6 +

H R ,

= 3904.97 +1878.78 + 5945.88

= 11729.63 J/mol

C2H4 +

H R ,

C6H5C2H5

To find the total heat of reaction

Total, H

= Hrxn + HP,1
= -105520 +11729.63
= - 93, 790.37 J/mol

Since alkalynation of ethylbenzene is exothermic reaction, the heat of reaction

calculated have negative value indicated it is in exothermic reaction.

CHAPTER 3
REACTOR SIZING CONSIDERING MAIN REACTION

3.1

Reactor Sizing According Algorithm

The reactor is determined to packed bed reactor. Manually, calculation is done by

following the algorithm as studied.

Recall the reaction,
C6 H 6 +C 2 H 4 C8 H 10
A + B C

Mechanism,
Adsorption:

A +S A .S

B+ S B. S
Surface area:
Desorption:

A . S+ B . S C . S + S

C . S C+ S

Rate law,
Adsorption:

Surface area:

Desorption:

[
[

r A 1=k 'A P A C v

C A. S
KA

r A 2=k 'B PB C v

C B .S
KB

r S=k 'S C A . S C B .S

r D =k 'D C A . S

]
]

CC . SCv
KS

PC C v
1
,assume
=K C
KD
KD

And it is assumed that the limiting step is surface reaction,

r A 1
0
k 'A
C A .S =P A C v K A ..(1)
r A 2
0
k 'B
C B . S=PB C v K B ..(2)
r D
0
k 'D
CC . S=P C C v K C ..(3)

r S=k 'S C A . S C B .S

CC . SCv
.(4 )
KS

Site balance,
CT

C v +C A . S +C B . S +C C. S
C v + P A C v K A + PB C v K B + PC C v K C
C v [ 1+ P A K A + P B K B + PC K C ]

Cv

CT
..(5)
[ 1+ P A K A + PB K B + PC K C ]

substitute (1),(2),(3)and (5) into (4)

r S

k ' S P A C v K A P B C v K B

PC Cv K C C v
KS

PC C2v
k 'S P A PB K A KB C
KS K D
2
v

k ' S P A P B K A K B C 2v
r S

k ' S K A K B C2v P A P B

PC
K eq

PC C v K A K B
KS K D K A KB

assuming K eq=K S K D K A K B

PC
K eq

1+ P A K A + PB K B + PC K C
k ' S K A K B C 2T P A PB

r S

r S

k P A PB

[ 1+ P A K A + PB K B + PC K C ]

, assuming k=k ' S K A K B C 2T

Stoichiometry
A

Species
Benzene

Ethylene

Inlet
FA 0

C Ethylbenzene

Change
F A 0 X

Outlet
F A =F A 0 (1 X )

Concentration
1X T 0
C A =C A 0
y
1+X T

)( )

FA 0B

F A 0 X

F B=F A 0 ( B+ X )

C B=C A 0

FA 0C

FA 0 X

FC =F A 0 ( C+ X)

CC =C A 0

BX
1+X
C

Pressure
1X
P A =P A 0
y
1+ X

P B P A 0 BX
=
RT R T 0 1+X

T0
y
T

PB =P A 0

T0
y
T

PC =P A 0

P C P A 0 C + X
=
RT R T 0 1+X

)( )

)( )
)( )

B X
y
1+X

C+ X
y
1+X

Where

6.344 X 10

k1 [kmol/m cat/h/atm ] 0.69 10 exp

3

RT

)( )

( 1++XX )( TT ) y

Rearranging
P A P A 0 1X T 0
=
y
RT R T 0 1+X T

T0
y
T

 162,730

RT

K A [atm -1 ] 1.2328 10 17 exp

35,368

RT

K B [atm -1 ] 2.0850 10 4 exp

3.933 X 10

K A [atm ] 1.5202 10 exp

Design Equation
dX
=r ' A
dW

dy
=
( 1+ X )
dW 2 y

Rate law
k PA PB

[ 1+ P A K A + P B K B + PC K C ]

Stoichiometry
PA=

P AO (1X )
1+ X

PB =

P AO (5X )
1+X

RT

r S=

-1

FA 0

PC =

P AO X
1+X

Combine

FA 0

k P A PB
dX
=
dW [ 1+ P A K A + P B K B + PC K C ]2

FAO = 158.55 kmol/hr

PAO = 5000 kPa
Temperature reactor = 573 K

3.2

Catalyst Determination
It is chosen that zeolite is the catalyst for this Ethylbenzene production. And its

properties is evaluated as below;

Dp

= 0.0005 m

Void fraction

= 0.45

P=

P AO
5000
=
y AO 0.16667

= 1.6404 x 10-3 ft

= 30 000 kPa = 297 atm

= 2200 kg/m3 = 62.99 kg/ft3

Bulk density of catalyst

Ac

= 0.0144 ft2 = 0.0013378 m2

= 1.2928 m3/s

= Ac x Q = 1.2928 x 0.0013378 = 1.7295 x 10-3 kg/m2.s

gc

= 32.174 lbm.ft/s2.lbf = 4.17 x 108 lbm.ft/h2.lbf

= 2.71 x 10-5 Pa.s = 0.06556 lbm/ft.h

= 0.7 kg/m3 = 0.0437 lbm/ft3

=

u = 1.21067 kg/m2.s = 0.8927 lbm / ft2.h

Therefore,

0=

G (1 ) 150 ( 1 )
+1.75 G
3
DP
0 g c D P

( 0.81986 )( 10.45 )
8

( 0.0437 ) ( 4.17 X 10 ) ( 1.6404 X 10 ) ( 0.45 )

0=0.54605

(150 )( 10.45 )( 0.06556 )

( 1.6404 X 103 )

+1.75 ( 0.81986 )

lbf
atm
=2.5796 X 104
2
ft
ft

2 0
c (1) A c P0

(2)(2.5796 X 104)

(0.0144)(62.99)(10.45)(297)

=3.482 X 106 kg1

3.3

POLYMATH Result
In order to find the weight of catalyst, the simulation is ran by using Polymath

software as shown below,

POLYMATH Report

No Title
30-Dec-2014

Ordinary Differential Equations

Calculated values of DEQ variables

Variable

Initial value

Minimal value

Maximal value

Final value

3.482E-06

3.482E-06

3.482E-06

3.482E-06

-0.1666667

-0.1666667

-0.1666667

-0.1666667

Fao

158.55

158.55

158.55

158.55

k1

1.136199

1.136199

1.136199

1.136199

Ka

0.0084311

0.0084311

0.0084311

0.0084311

Kb

0.3494354

0.3494354

0.3494354

0.3494354

Kc

-3.949E-06

-3.949E-06

-3.949E-06

-3.949E-06

Pa

5000.

5000.

Pao

5000.

5000.

5000.

5000.

10 Pb

2.5E+04

2.372E+04

2.5E+04

2.372E+04

11 Pc

5993.528

5928.934

12 R

8.314

8.314

8.314

8.314

13 r1

-1.842766

-1.842766

14 rT

-1.842766

-1.842766

15 T

573.

573.

573.

573.

16 W

8100.

8100.

17 X

1.

1.

18 y

1.

0.9881557

1.

0.9881557

Differential equations
1
d(X)/d(W) = -rT/Fao
design equation for packed bed reactor

d(y)/d(W) = - A * (1+(E*X))/(2*y)

Explicit equations
1
Fao = 158.55
2
Pao = 5000
3
E = -1/6
4
R = 8.314
5
T = 573
6
k1 = 0.69 *10^(6)* exp(-6.344*10^4/(R*T))
7
Ka = 1.2328 *10^(-17) * exp (162730/(R*T))
8
Kb = 2.085*10^(-4) * exp(35368/(R*T))
9
Kc = -1.5202 *10^(-2) * exp(-3.933*10^4/(R*T))
10 Pa = Pao * y*(1-X) /(1+E*X)
11 Pb = Pao *y* (5 - X)/(1+E*X)
12 Pc = Pao *y* (X)/(1+E*X)
13 r1 = -k1 * Pa * Pb / (1 + Ka * Pa + Kb * Pb + Kc * Pc)^2
14 A = 3.482*10^(-6)

alpha

15

rT = r1

General
Total number of equations

17

Number of differential equations

Number of explicit equations

15

Elapsed time

0.000 sec

Solution method

RKF_45

Step size guess. h

0.000001

Truncation error tolerance. eps

0.000001

Figure 3. 1: Graph obtained from Polymath simulation

W
0
22.95491
40.55491
49.35491
58.15491
66.95491
84.55491
93.35491
102.1549
110.9549
128.5549
137.3549
146.1549
154.9549
172.5549
181.3549
190.1549
198.9549
216.5549
225.3549
234.1549
242.9549
260.5549
269.3549
278.1549
286.9549
304.5549
313.3549

X
0
0.2396088
0.3891483
0.4539301
0.5126204
0.565648
0.656403
0.6949469
0.7294536
0.7602877
0.8122901
0.8340773
0.8534292
0.8705981
0.8992874
0.9112068
0.9217439
0.9310528
0.9465244
0.9529215
0.9585615
0.9635323
0.9717691
0.9751658
0.9781561
0.9807882
0.9851426
0.9869357

X calc
0.767278907
0.774224554
0.779549923
0.782212608
0.784875292
0.787537977
0.792863346
0.795526031
0.798188713
0.800851397
0.806176767
0.808839451
0.811502136
0.814164821
0.81949019
0.822152875
0.82481556
0.827478244
0.832803614
0.835466298
0.838128983
0.840791668
0.846117037
0.848779722
0.851442406
0.854105091
0.859430461
0.862093145

X residual
0.767278907
0.534615754
0.390401623
0.328282508
0.272254892
0.221889977
0.136460346
0.100579131
0.068735113
0.040563697
-0.006113333
-0.025237849
-0.041927064
-0.056433279
-0.07979721
-0.089053925
-0.09692834
-0.103574556
-0.113720786
-0.117455202
-0.120432517
-0.122740632
-0.125652063
-0.126386078
-0.126713694
-0.126683109
-0.125712139
-0.124842555

X residual ^2
0.588716922
0.285814004
0.152413427
0.107769405
0.074122726
0.049235162
0.018621426
0.010116162
0.004724516
0.001645414
3.73728E-05
0.000636949
0.001757879
0.003184715
0.006367595
0.007930602
0.009395103
0.010727689
0.012932417
0.013795724
0.014503991
0.015065263
0.015788441
0.015973441
0.01605636
0.01604861
0.015803542
0.015585663

Table 3. 1: Result of simulation

From Table 3.1, at approximately 90% conversion the weight of catalyst required is
172.55 kg. Hence, analyzing the reactor sizing,
AC = 0.0144 ft2 = 0.0013378 m2
b=2200 ( 10.45 )=1210
L=

kg
m3

W
A C b

172.55
(0.0013378)(1210)
= 106.60 m

D=

L
6

= 17.76 m
It is determined that the length of the reactor is 106.6 m while its diameter is 17.76 m

REFERENCES

David Netzer, 1. H. (1999). "Mixed Phase Ethylene Process for Manufacturing Ethylbenene".
U.S.Patent, 977,423.
ICIS. (2011, August). Retrieved from Ethylbenzene (EB) Prices and Pricing Information:
http://www.icis.com/resources/news/2007/11/02/9075692/ethylbenzene-eb-pricesand-pricing-information/
iHS Chemical. (2012, October). Retrieved from
http://www.ihs.com/products/chemical/planning/ceh/ethylbenzene.aspx
Klaewkla, R., Arend, M., & Hoelderich, W. F. (2011). A Review of Mass Transfer Controlling
the Reaction Rate in Heterogeneous Catalytic Systems. InTech.
Petronas. (2014). Retrieved from http://www.petronas.com.my/ourbusiness/downstream/petro-chemicals/Pages/other-petro-chemical-plants.aspx
Polimeri Europa. (n.d.). Retrieved from
http://www.eni.com/it_IT/attachments/azienda/attivitastrategie/petrolchimica/licensing/Ethylbenzene-fl-lug09.pdf
Scorecard. (n.d.). Retrieved from http://scorecard.goodguide.com/chemical-profiles/uses.tcl?
edf_substance_id=100-41-4
Shenglin Liu, F. C. (March 2009). "Highly selective ethylbenzene production through
alkylation of dilute ethylene with gas phase-liquid phase benzene and transalkylation
feed". Journal of Natural Gas Chemistry, 21-24.
Smith, J. M., Van Ness, H. C., & Abbott, M. M. (2005). Introduction to Chemical
Engineering Thermodynamics. New York: Mc Graw Hill Education.
technology, w. (2012, - -). Ethylbenzene/Styrene Monomer. Retrieved oktober 14, 2014, from
Ethylbenzene/Styrene Monomer.
Turton, R., Bailie, R. C., Whiting, W. B., Shaeiwitz, J. A., & Bhattacharya, D. (2013).
Analysis, Synthesis, and Design of Chemical Processes (Fourth ed.). United States:
Pearson Education.
Ullmman''s. (1985). Ethylbenzene. Encyclopedia of Industrial Chemistry, vol. 12 pp-519-530.
Vincent A.Welch, K. J. (2005). Ullman's Encyclopedia of Industrial Chemistry. Weinhem:
Wiley-VCH.

Vincent AVincent A.Welch, K. J.-P. (2005). Ethylbenzene. Wiley-VCH, Weinheim: Ullmans

Encyclopedia of Industrial Chemistry.