CHAPTER 1

INTRODUCTION

1.1 INTRODUCTION OF ETHYLBENZENE

Ethylbenzene is an organic compound with the formula C 6H5CH2CH3.
Ethylbenzene is a clear, colorless liquid, flammable liquid that smells like
gasoline. The aromatic hydrocarbon is important in the petrochemical
industry and as an intermediate in the production of styrene, which is
used for making polystyrene that is common plastic material. It is the
primary feedstock for the synthesis of styrene that is subsequently
polymerised into polystyrenes [Hancock, (1975)].

Ethylbenzene also

present in small amounts in crude oil. It also is naturally found in coal tar
and petroleum and it is in manufactured products such as inks, pesticides,
paints, tobacco products, and automotive products [R. Manuel (2010)].

Figure 1: Structural Formula of Ethylbenzene

Many improvements in the technology for the production of ethylbenzene have been
made over the past few decades. Recent process design innovations have been
commercialized that remains the process of choice for the production of ethylbenzene. All of
this effort is to improve yield, process costs, and process safety for the preparation of
ethylbenzene as a key intermediate for the growing need of ethylbenzene in industries.

1.1.1

PHYSICAL AND CHEMICAL PROPERTIES OF ETHYLBENZENE

Ethylbenzene is a colorless liquid with an aromatic odor. Information regarding the

physical and chemical properties of ethylbenzene is located in Table 1.1. Ethylbenzene is a
flammable and combustible liquid. Vapors are heavier than air and may travel to a source of
ignition and flash back. Liquid ethylbenzene floats on water and may travel to a source of
ignition and spread fire. Combustion may produce irritants and toxic. Ethylbenzene may
accumulate static electricity and will react with oxidizing materials.
Table 1.1 Physical and Chemical Properties of Ethylbenzene

Property

Information

Molecular weight

106.17 g/mol

Color

Colourless liquid

Physical state

Liquid

Melting point

-94.975 C

Boiling point
Density
at 20 C/4 C :
at 25 C/25 C :
Odor
Odor threshold:
Water:
Air

136.19 C
0.8670
0.8671
Sweet, gasoline-like

0.029 mg/L , 0.140 mg/L

2.3 ppm, 22.6 mg/m3

Solubility:
Water at 0 C
at 15 C
at 20 C
at 25 C
Partition coefficients:
Log Kow
Log Koc

197
140
152
160 mg/L, 177

mg/L
mg/L
mg/L
mg/L, 208 mg/L

4.34, 3.13, 3.15

2.22(calculated), 2.38(measured),
2.40(calculated)

-Ethylbenzene undergo dehydrogenation

to styrene, flammable, combustable, may
accumulate static electricity, may travel
towards a point of ignition , evaporates at
room temperature
-Miscible with usual organic solvents,
Soluble in alcohol and ether.

Chemical properties :

Organic solvents :

1.2

APPLICATION OF ETHYLBENZENE

Ethylbenzene is an organic compound with the formula C 6H5CH2CH3,

Ethylbenzene is almost exclusively or more than 99 percent used as an
intermediate for the manufacture of styrene monomer [CAS RN: 100-425], C6H5CH=CH2, one of the most important large-volume commodity
chemicals, or in the co-production of styrene monomer with propylene
oxide. Less than 1 % of the ethylbenzene produced is used as an
intermediate for the production of acetophenone, diethylbenzene and
ethylanthraquinone, as a constituent of asphalt and naphtha, and as an
anti-knock additive in fuels and gasolines. Of the minor uses, the most
significant is in the coatings industry as a solvent (mixed xylenes) for
paints, lacquers, and varnishes. Ethylbenzene also used in the chemical
industry

in

the

manufacture

of

acetophenone,

cellulose

acetate,

diethylbenzene (DEB), ethyl anthraquinone, ethylbenzene sulfonic acids,

propylene oxide, and methylbenzyl alcohol. A mixture of ethylbenzene
and xylene is used as a solvent in the paint industry and for producing
pesticides in agriculture.

1.3. MARKET SURVEY

Market surveys are an important part of market research that
measure the feelings and preferences of customers in a given market.
Varying greatly in size, design, and purpose, market surveys are one of
the main pieces of data that companies and organizations use in
determining what products and services to offer and how to market them.

Market Research Report on Global and Chinese Ethylbenzene Industry,

2009-2019 is a professional and

in-depth market survey on Global

and Chinese Ethylbenzene industry). It was reported that in 2001 the

world annual production capacity of EB was estimated to be 23 million
metric ton per year, with an average annual growth rate of approximately
4% from 2001 to 2006, and over 90% of the production of EB is used in
the manufacture of styrene (Degnan et al., 2001).
The report firstly reviews the basic information of Ethylbenzene
including its classification, application and manufacturing technology. The
report

then

explores

global

and

Chinas

top

manufacturers

of

Ethylbenzene listing their product specification, capacity, production

value, and market share and others.

1.3.1 Current and Project Demand

Demand until 2010

1999: 13,193 million pounds
2000: 13,444 million pounds
2004: 14,552 million pounds
2010: 17,075 million pounds

Growth
Historical (2004-2010) : 2.7 percent per year

Strength
Ethylbenzene demands run parallel to that of styrene. Styrene
is a mature and stable commodity, used in many homopolymer, copolymer and ter-polymer applications. These
applications cover a wide scope in industrial, consumer and
medical products.

Weakness
Ethylbenzenes major shortcoming is that is essentially a one
market segment product which is styrene. Moreover, as the
styrene is produced with captive Ethylbenzene there is not
much noticeable market activity.

1.3.2 Price and Price Variations

Price
Historical (1995-2000):
a. High, $0.25 per pound, ($ 0.5511/Kg) by Friday 8 August,
2010
b. Ethylbenzene was valued at $1,554- $1570/ tonne ($1.5541.570/Kg) price

Variations:
The US unit sales value Ethylbenzene in $/KG from 1960-1986:

Year
1960
1965
1970
1973
1974
1975
1978
1979
1980
1983
1986

Sales ($/Kg)
0.13
0.09
0.09
0.11
0.37
0.20
0.24
0.35
0.50
0.51
0.48-0.51

1.3.3 Simple Economic Potential Calculation for production of ethylbenzene using

benzene and ethylene

C6H6 + C2H4

C6H5CH2CH3

Benzene + Ethylene

Ethylbenzene

EP 1 = Profit Price of raw materials

$ 2 .00
gal

Benzene price :

Ethylene price:

$ 0.88
gal

Ethylbenzene price :

EP 1= [

RM 3.65
Kg

RM 3.32
$1

RM 3.32
$1

$ 1.10
Kg

RM 1.75
Kg

1 gal
3.7854118 kg

1 gal
3.7854118 kg

RM 3.32
$1

RM 0.77
Kg

]=

RM 1.75
Kg
RM 0.77
Kg

RM 3.65
Kg

RM 1.13
Kg

1.3.4 Equipments cost

For economic reasons, carbon steel was selected for equipment construction. Carbom
steel has suitable corrosion resistance for the chemicals used in the production of
ethylbenzene.

Equipment
CSTR (R-1)
CSTR (R-2)
Separator
Heat Exchanger
Distillation column (1)
Distillation column (2)

Purchase cost, US $
121,800
2,600
33,400
8,279
1,051,200
977,300

Install cost, US $
54,800
1,200
15,000
3,312
788,400
733,000

1.4. SCREENING OF SYNTHESIS ROUTE

There are altogether 3 routes for the synthesis of ethylbenzene ,namely :

Production by liquid phase alkylation .

Production by vapor phase alkylation.
Mobil-Badger Process.

1.4.1. Production by liquid phase alkylation:

Alkylation of benzene with in the presence of an aluminum chloride
catalyst complex is
exothermic ; the reaction is very fast and produces almost stoichiometric
yields of ethylbenzene. In addition to AlCl3, a wide range of Lewis acid
catalysts, 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 and essentially 100
percent of the ethylene is converted. Low ethylene: Benzene ratios are
used to give optimum overall yield of ethylbenzene. The process is also
capable of operating with low concentration ethylene feed.
1.4.2. Production by vapor phase alkylation:
This process produces a high purity ethylbenzene product and can
use dilute ethylene feed stock. If the entry of water into the process is
strictly prevented, the corrosion problems associated with aluminum
chloride processors are avoided. However, even small amounts of water
(<1mg/kg) hy6drolze the BF, catalyst. where ethylbenzene of more than
99.9 percent purity is produced. However, purification of these streams is
necessary to remove components that poison the BF3 catalyst, such as
trace amounts of water sulfur compound, and oxygenates.
1.4.3 Mobil-Badger Process:
The fixed bed ZSM-5 catalyst is used in this process .The
advantages is that the catalyst is

noncorrosive and nonpolluting. The

catalyst is essentially silica alumina, which is environmentally inert.

Because no aqueous waste streams are produced by the process,
the equipment for waste treatment and for catalyst recovery is eliminated.

Availability of feed stocks:

Figure 1.4.1 : Production of Petrochemical feedstocks in

Malaysia.

According to the figure 1.4.1 there are 1.63 million and 775
thousands metric tonnes per annual of ethylene and benzene produced
respectively which is sufficient for the annual production of 50000 metric
tonnes of ethyl benzene for our project .

Availability of catalyst :

Figure 1.4.2: Global zeolites Mine Production 2013

China is the main producer with 74% of world production share. It is
followed by South Korea, USA, Turkey and Jordan with a combined share of
13.7%.The worldwide zeolites production is predicted to see poor growth

in the years ahead. In 2017, the world zeolites production volume is

forecast to be around 2.9 million. The highest growth in the demand for
zeolites is expected to be witnessed in APAC and the Middle East.
Route of choice for ethyl benzene production:
Although both the alkylation process , liquid phase and vapor phase are
of equal use commercially . Yet there are some differences :

In vapor phase alkylation , the reactor operates at higher

temperatures ( 400- 4500 C ) which causes catalytic deactivation by

fouling as a result catalyst required periodic generation .

In vapor phase alkylation 2 reactors will be required so that
processing and regeneration can proceed alternatively without

interrupting production.
All the ethylene feedstock is reacted completely in the liquid

benzene, thus eliminating off gas recovery equipment.

Ethyl benzene yield is 99.7 % in liquid phase alkylation process

while in vapour phase alkylation it is around 98 %.

Zeolite as a catalyst can be used in any of the process.
Up to 99.95 wt % product purity in the with no xylene formation , in
liquid phase alkylation process.

So after considerations, the route of choice is production of liquid phase

alkylation due to higher percentage of product purity , lower operating
temperature

,complete

conversion

of

ethylene

and

the

above

mentioned advantages compared to the other methods of production.

Environmental Issues

The environmental issues and regulations have been magnified in

the public, political and economic world over the last fifteen years
(Hoeldrich, 2000). In addition to catalysts upgrading, the development of
the environmentally friendly chemical processes concentrate on the
process optimisation and equipment improvement (Nexant, 2004). The
process optimisation and equipment improvement such as minimising the

energy consumption of the chemical processes would lead to the

commercial

and

environmental

benefits.

The

reduction

of

energy

consumption would decrease the emission of greenhouse gases, namely

carbon dioxide (CO2), and reduces the operation cost of the process
(Yoon, et al., 2007).

CHAPTER 2
PROCESS SYNTHESIS AND FLOW SHEETING

2.1

Process Description

2.1.1

Background
A feasibility on the production of 99 wt% of the ethylbenzene (EB) is to be

performed. The plant is capable of producing 50,000 metric tons of EB per year via the liquid
phase alkylation of benzene and ethylene. EB is the aromatic hydrocarbon which is important
in the petrochemical industry and as an intermediate in the production of styrene, which is
used for making polystyrene. It also present in in small amounts of crude oil as ingredient in
some paints.

2
3

Figure 2.1: The process flow diagram for production of ethylbenzene (EB)

2.2 Process Flow Diagram Process

From figure 2.1, we used two reactors in series (CSTR 1 and CSTR 2), two
distillation columns (RADF1 RADF2) and two liquid recycle streams. Firstly, fresh ethylene
at temperature 46.85 C is fed as a liquid in ETHYFEED stream and combines with total
benzene, temperature 46.85 C from fresh benzene and benzene recycle at TOTBENZENE
stream. The ethylbenzene process involves gaseous ethylene into the liquid phase of the first
two CSTR reactors in series. Then at CSTOUT1 stream with temperature 162.85 C, pressure
20.265 bar gives out the productions of ethylbenzene as main product while ethylene,
benzene and diethybenzene such as a side products. Next, it goes into CSTOUT2 stream at
temperature 158.85 C and pressure 19.2518 bar. Both reactors operate at high pressure to
maintain liquid in the reactor at high temperature required for reasonable reaction rates. The
reactor effluent is cooled and then throttled to 0.303975 bar at RADF1 at the bottom. The
bottom product, at BOT1 stream goes to RADF2 where the ethylbenzene and diethylbenzene
mixture are separated. The benzene will separate from the other components and recycled
back to DST1 stream. It will mix with stream BENFEED with mixer in TOTBENZE stream
and goes into CSTR1 back. At RADF2, ethylbenzene as the main product will be distillate at
the upper part at DIST2 stream while the diethylbenzene exits at BOT2 and recycle back to
CSTOUT1 stream at CSTR2. In this process we used two CSTR reactors which is labelling
number 1 and 2. CSTR is used because we had the kinetics value, K and is better than using
RStoic with conversion unit. For distillation columns we choose two Rad Frac columns

labelling number 3 and 4. Rad frac is more accurate than DSTWU column. Last but not least,
the mixer labelling number 5 is using to mix of recycle benzene and benzene feed before
enter at TOTBENZE stream.

2.2 Reaction Mechanism and kinetics

Production of ethylbenzene involves the liquid-phase reaction of ethylene with benzene

C2H4 + C6H6

C8H10

K = 1.528 106
E (Cal/mole) = 17,000
Concentration terms (kmol/m3)= CECB

Undesirable reaction occurred by the formation of Di-ethyl benzene from reaction of

ethylbenzene with ethylene.
C8H10 + C2H4

C10H14

K = 2.778 107
E (Cal/mole) = 20,000
Concentration terms (kmol/m3) = CECEB

A third reaction also occurs, in which Di-ethyl benzene reacts with benzene to form
ethylbenzene.
C10H14 + C6H6

2C8H10

K = 1000
E (Cal/mole) = 15,000

Concentration terms (kmol/m3) = CBCDEB