VIET NAM NATIONAL UNIVERSITY HCMC

HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY

FACCULTY OF CHEMICAL ENGINEERING

--------o0o--------

REPORT OF EXTRA WORK

APPLICATION OF CHEMICAL REACTION

ENGINEERING IN PETROCHEMICALS
STYRENE PRODUCTION
Lecturer: Assoc. Prof. Mai Thanh Phong

Phan Nguyễn Thiên Sơn 1813860

Nguyễn Đình Sáng 1810762

Hồ Xuân Thiện 1814130

Huỳnh Văn Thành 1814006

Hồ Gia Quỳnh 1813770

Phạm Phú Thanh Cường 1810849

Lâm Thuận An 1813792

Ho Chi Minh City, December 2020

 TABLE OF CONTENTS

1. Introduction ......................................................................................................... 3

2. Chemical reactions and reaction kinetics ............................................................. 3

2.1 Chemical reactions ········································································································ 3

2.2 Reaction kinetics ············································································································ 3

3. Process description............................................................................................... 4

4. Reactor design...................................................................................................... 5

References .................................................................................................................. 7

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1. Introduction
Styrene is the monomer used to produce polystyrene and it has a variety of
uses. By dehydrogenating ethylbenzene, styrene is formed and that reaction is highly
endothermic.

C6H5C2H5 = C6H5C2H3 + H2

The Styrene process flow diagram (Figure 1) displays the process of

manufacturing styrene using Ethylbenzene and high pressure steam whereas two
packed beds are used.

2. Chemical reactions and reaction kinetics

2.1 Chemical reactions
Styrene is formed by the dehydrogenation of ethylbenzene. Here are the
actual main reaction and side reactions of this process.
C6H5C2H5  C6H5C2H3 + H2 , ΔH > 0 (rxn.1)
C6H5C2H5 → C6H6 + C2H4 (rxn.2)
C6H5C2H5 + H2 → C6H5CH3 + CH4 (rnx.3)

2.2 Reaction kinetics

The equilibrium constant of reversible reaction (rxn.1) is given(where T is
in K and P is in bar):
𝑦𝐶6 𝐻5 𝐶2 𝐻3 𝑃
𝐾=
𝑦𝐶6 𝐻5 𝐶2 𝐻5

14852.6
𝑙𝑛𝐾 = 15.5408 −
𝑇

Because the Styrene formed reaction is reversible and highly endothermic,

heating to the reactor will increased reaction speed, it also drives the equilibrium
to the right and enhances the conversion. Therefore, steam is used as inert
superheated steam in the reaction. On the other side, the styrene product can
spontaneously polymerize at higher temperatures. The experience suggests that it’s

3
 temperature should be maintained at less than 125oC, there’ll be no spontaneous
polymerization problem. The equilibrium calculation with steam added is given as

C6H5C2H5  C6H5C2H3 + H2
1 0 0
1-x x x

total = N + 1 + x includes N moles of inert steam

𝑥2𝑃
𝐾=
(1 − 𝑥)(𝑁 + 1 + 𝑥)
where P is in bar.

This equation can be used to generate data for equilibrium conversion, X,

versus P, T, and N.

The equations of reaction speed are given:

21708
𝑟1 = 10.177x108 exp (− ) 𝑝𝑒𝑏
𝑅𝑇
7804
𝑟2 = 20.965exp ( ) 𝑝𝑠𝑡𝑦 𝑝ℎ𝑦𝑑
𝑅𝑇
49675
𝑟3 = 7.206x108 exp (− ) 𝑝𝑒𝑏
𝑅𝑇
26857
𝑟4 = 1.724x103 exp (− ) 𝑝𝑒𝑏 𝑝ℎ𝑦𝑑
𝑅𝑇
where p is in bar, T is in K, R = 1.987 cal/mol K, and ri is in M/s

3. Process description
The diagram below shows a process of Styrene production in industrial
scale.

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 Figure 1: Styrene Process Flow Diagram

The reactants including ethylbenzene, recycled ethylbenzene, and high pressure

steam are sent to two adiabatic packed beds with inter heating. After that, the products
are cooled, producing steam from the high-temperature reactor effluent. The cooled
product stream is sent to a three-phase separator, in which light gases, organic liquid,
and water exit in separate streams. The hydrogen stream is further purified as a source
of hydrogen elsewhere in the plant. The benzene/toluene stream is currently returned
as a feed stream to the petrochemical facility. The organic stream consisting of styrene
is distilled twice to remove benzene and toluene and to recycle unreacted ethylbenzene.

4. Reactor design
In this system, there are two reactors in series: R401 and R402. They are
tubular reactors with packed bed (PBR) and cylindrical catalyst pellets (1.6 mm x 3.2
mm). This type of reactor has a spacious reaction area on the catalytic surface, hence
it is usually used in gas reactions. Having packed bed, the reaction happens with
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higher conversion per weight of the catalyst, so the conversion of reaction depends on
the weight of the catalyst rather than the volume of the reactor. In comparison with
stirring tank reactor, tubular reactor has a higher conversion when they are the same
volume. Tubular reactor is easy to clean and its pressure drop is also low. However,
its disadvantages are the difficulty in controlling the temperature of exothermic
reactions which may occur local hot spots. The reason for the high price of PFR is the
complication in fabrication. Two reactors in this system are both made from 316
stainless steel to avoid chemical erosion. They are 9.26 m high, 1.85 m in diameter, so
the volumes are 25 m3 with void fraction equals 0.4.

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References
[1] Analysis, Synthesis and Design of Chemical Processes – Prentice Hall

[2] Elements of Chemical Reaction Engineering - H. SCOTT FOGLER