PROJECT REPORT

On

SIMULATION AND OPTIMIZATION OF AN EXISTING

ETHYLBENZENE DEHYDROGENATION REACTOR

Submitted by

N.ILAKKIYA (AC15UCH031)

BACHELOR OF TECHNOLOGY

IN

CHEMICAL ENGINEERING

Under guidance of

Shri Shekhar Kumar

Head, Reprocessing Operation Division (RpOD)

Reprocessing Group

Indira Gandhi Centre for Atomic Research

Kalpakkam, Tamil Nadu - 603102.

1
 DECLARATION

This is to certify the project entitled “SIMULATION AND OPTIMIZATION OF AN EXISTING

ETHYLBENZENE DEHYDROGENATION REACTOR.” submitted by N.ILAKKIYA
(AC15UCH031) to ADHIYAMAAN COLLAGE OF ENGINEERING, Hosur as inplant training
of Bachelor of Technology in Chemical Engineering, is done by us under the guidance of Shri
Shekhar Kumar, Head, Reprocessing Operation Division (RpOD), Reprocessing Group Indira
Gandhi Centre for Atomic Research, Kalpakkam, Tamil Nadu-603102 is an original work and has
not been submitted for the award of any other degree or fellowship or any similar titles at this
university or elsewhere.

2
 ACKNOWLEDGEMENT

I would like to thank the Almighty and my parents for the successful completion of this
project. I would like to express my sincere gratitude to my Project Guide Shri Shekhar Kumar,
Head, Reprocessing Operation Division (RpOD), Reprocessing Group Indira Gandhi Centre for
Atomic Research, Kalpakkam, Tamil Nadu-603102, for his constant support and guidance
throughout the project.

3
Abstract:

The production of styrene is a 28 billion dollar industry worldwide. There is a significant

demand for it and cutting costs even a few cents per pound will yield large savings. These savings
can then be passed to the consumer and will ultimately make styrene products (like polystyrenes
and ABS polymers) available to more people worldwide. It is believed it is feasible to simulate a
process for producing styrene that will make this possible. The idea is to use cheaper raw
materials, namely ethane instead of ethylene, and utilize the fundamentals of the process, such as a
dehydrogenation unit, to convert the ethane to ethylene in the process. An advantage to the new
process is that it starts with a less expensive raw material, ethane, instead of ethylene. The project
has been guided by Shri Shekhar Kumar, Head, Reprocessing Operation Division (RpOD),
Reprocessing Group Indira Gandhi Centre for Atomic Research, Kalpakkam, Tamil Nadu-603102.
The process flow sheet for the production of 1000 TPD was developed. Material and energy
balance over the full plant was done. Design of fixed-bed reactor (ideal adiabatic reactor operation)
with process steam as diluents was done. The reactor was thus, optimized and required catalyst
weight was found, which was done using MATLAB. Mechanical design of the reactor was made
using AutoCAD. Process control and P&ID charts for the reactor made using Microsoft Visio. A
detailed layout of the styrene plant was developed. HAZOP analysis on the entire plant and other
general safety analysis were made and pollution control measures were noted. MSDS was
documented for the chemicals involved in the process. The basic data applicable to this design will
be derived from J.M.Smith (1987).

Keywords: AspenHysys, DWSIM, Ethylbenzene, Styrene, J.M.Smith, Fixed bed catalytic reactor,
Mathematical modeling.

N.ILAKKIYA
(AC15UCH031)

4
 Chapter 1: Introduction

Styrene is one of the most important monomers and is the precursor to polystyrene and many
other copolymers. The IUPAC name for styrene are Vinyl benzene, is an organic compound with
the chemical formula C6H5CH=CH2. This derivative of benzene is a colorless oily liquid that
evaporates easily and has a sweet smell, although high concentrations have a less pleasant odor.
The chemical structure of the styrene is shown in the figure 1.1

Figure 1.1 - Styrene Molecular Structure.

1.1 Major Producers in the World:

The styrene process was developed in the 1930s independently and simultaneously by BASF in
Germany and by DOW Chemical in the USA.

Some of the leading producers of styrene in the world:

 Americas Styrenics

 Carville Styrenics Complex

 Pars Petrochemical Co

 Shell Chemicals Canada Ltd

5
  Integrated Refinery and Petrochemical Co

 Siam Styrene Monomer Co

 Saudi Petrochemical Co

 Samsung Total Petrochemicals Co Ltd,

 Mitsubishi Chemical Corp,

 Sinopec Beijing Yanshan Petrochemical Co Ltd,

 Daqing Petrochemical Co

The US is a producer and net exporter of styrene to the rest of the world. There has been little
styrene imported to the US. Canada has usually been the only source of US styrene imports. This is
because of the proximity of plants in nearby Canada that ship through the US. In India there is no
producer of styrene and the demand is being met by imports.

Figure 1.2 – Global Styrene Demand by Region

6
 Figure 1.3 - Distribution of the forecasted global demand for styrene in 2020, by region.

This statistic shows the distribution of the forecasted demand for styrene worldwide in 2020, by
region. It is forecasted that in 2020, North America will account for a 14 percent share of the
global demand for styrene.

7
 Chapter 2: Literature Survey

2.1 Chemistry of Ethylbenzene Dehydrogenation:

The main reaction produces styrene and hydrogen.

Ethylbenzene ↔ Styrene + H 2 , ΔHr (620°C) = 124.83 kJ/mol
The dehydrogenation reaction is usually conducted at temperatures above 600°C with an excess
of steam. The ethylbenzene dehydrogenation is an endothermic and reversible reaction with an
increase in the number of mole due to reaction. High equilibrium conversion can be achieved by
a high temperature and a low ethylbenzene partial pressure. The main byproducts are benzene
and toluene.

Ethylbenzene →Benzene + C2 H 4 , ΔHr (620°C) = 101.50 kJ/mol

Ethylbenzene + H 2 →Toluene + CH 4 , ΔHr (620°C) = -65.06kJ/mol

2.2 Role of Promoter in Ethylbenzene Dehydrogenation:

Potassium is the main promoter of Fe 2O3. It increases the activity by more than one order
of magnitude, and also slightly increases the selectivity to styrene and the stability of the
catalyst. The effect of the potassium promotion on the activation energy has been reported in
numerous publications. A recent improvement to the manufacture of the catalysts is to
incorporate small amounts of vanadium and other modifiers, which can beneficially affect the
pore structure of the catalysts. Cr and Al are considered to be structural promoters, as they can
enter in the Fe3+ compounds. Ce oxide increases the activity and Mo the selectivity.

2.3 Role of Steam in Ethylbenzene Dehydrogenation:

Steam is present in excess in the ethylbenzene dehydrogenation process. In the last

decades, great efforts were invested to decrease the steam/hydrocarbon ratio to molar values
lower than 6, essentially through modifications in catalyst compositions. The overall effects of
the increase of the steam/hydrocarbon ratio are to increase the selectivity for styrene at the same
level of conversion and the lifetime and stability of the catalyst.

8
Advantages of using steam are:

 Steam can provide the heat to maintain the reaction temperature.

 Steam acts as a diluent to shift the equilibrium conversion to higher value through a
decrease of the partial pressures of ethylbenzene and hydrogen.

 Steam removes the carbonaceous deposition by the gasification reaction.

The effect of steam on the catalyst activity was studied from various other papers and they
showed that surface carbon level decreased with increasing H2O/EB molar ratio and that a
H2O/EB molar ratio of three is optimum to minimize the carbon content on the surface while
maximizing the activity of the catalyst.

2.4 Deactivation Phenomena in Ethylbenzene Dehydrogenation:

Both the catalyst and the process have been improved during the last 70 years. However, the
migration of potassium promoter and its loss from the catalyst still remain as major problems.
For adiabatic operation the potassium compounds are slightly volatile, so potassium migrates in
the direction of the fluid flow in the catalyst bed. On the microscale, it moves from the exterior
to the core of each catalyst pellet due to the temperature gradient resulting from the
endothermicity of the reaction. This migration and loss of potassium result in a serious loss of
activity, selectivity to styrene, and mechanical strength. It was indicated that hydrogen formed as
product of the reaction can reduce the active catalysts to magnetite, Fe3O4. Once these phases
are formed, segregation of the phases occurs, leading to a potassium-rich core and a potassium
depleted shell in the catalyst.

9
 Chapter 3: Safety Analysis and Pollution control

3.1 Public Health Statement

This problem statement is the summary chapter from the Toxicological Profile for Styrene
and the effects of exposure of it.
The Environmental Protection Agency (EPA) identifies the most serious hazardous waste
sites in the nation. These sites are then places on the National Priorities List (NPL) and are
targeted for long-term federal clean-up activities. Styrene has been found in at least 251 of the
1,699 current or former NPL sites.
When a substance is released either from a large area, such as an industrial plant, or from a
container, such as a drum or bottle, it enters the environment. Such a release does not always lead
to exposure.
3.2 Safety Analysis of Styrene

1.1 Chemical Identification

S.No Property Value

1 physical state Liquid(clear viscous liquid)
2 Molecular weight 104 g/mol
3 color Colorless
4 Boiling point 145.2 ° C
5 Melting point -30 ° C
6 Specific gravity 0.906 (water=1)
7 Vapor density 3.59(air=1)
8 Vapor pressure 4.5 mm of Hg (@20 ° C)
9 solubility Very slightly soluble in cold water

10
1.3 First Aid
Eye Contact:
 Check for and remove any contact lenses.

 Immediately flush eyes with running water for at least 15 minutes, keeping eyelids open.
Cold water may be used.

 Do not use an eye ointment. Seek medical attention.

Skin Contact:
 After contact with skin, wash immediately with plenty of water. Gently and thoroughly
wash the contaminated skin with running water and non-abrasive soap. Be particularly
careful to clean folds, crevices, creases and groin. Cover the irritated skin with an
emollient. If irritation persists, seek medical attention. Wash contaminated clothing
before reusing.

Serious Skin Contact:

 Wash with a disinfectant soap and cover the contaminated skin with an anti-bacterial
cream.

 Seek immediate medical attention.

Inhalation:
 Allow the victim to rest in a well ventilated area.

 Seek immediate medical attention.

Ingestion:
 Do not induce vomiting.

 Examine the lips and mouth to ascertain whether the tissues are damaged, a possible
indication that the toxic material was ingested; the absence of such signs, however, is not
conclusive.
11
  Loosen tight clothing such as a collar, tie, belt or waistband.

 If the victim is not breathing, perform mouth-to-mouth resuscitation.

 Seek immediate medical attention.

1.4 Fire and Explosion Data

 Flammability of the Product: Flammable

 Auto-Ignition Temperature: 490°C

 Flash Points: CLOSED CUP-31.1°C

 Flammable Limits: LOWER-1.1% UPPER- 6.1%

 Products of combustion: Oxides of Carbon( CO2 ,CO)

Flammable in presence of open flames and sparks. Slightly flammable to flammable in presence
of heat.

 In case of small fire: Use DRY chemical powder.

 In case of large fire: Use alcohol foam, water spray or fog. Cool containing vessels with
water jet in order to prevent pressure build-up, auto ignition or explosion.

1.5 Handling and Storage

Precautions:

Keep locked up and away from heat. Keep away from sources of ignition. Ground all
equipment containing material. Do not ingest. Do not breathe gas/fumes/ vapor/spray.
In case of insufficient ventilation, wear suitable respiratory equipment if ingested, seek medical
advice immediately and show the container or the label. Avoid contact with skin and eyes.

12
Storage:

Flammable materials should be stored in a separate safety storage cabinet or room. Keep
away from heat. Keep away from sources of ignition. Keep container tightly closed. Keep in a
cool, well-ventilated place. Ground all equipment containing material. A refrigerated room would
be preferable for materials with a flash point lower than 37.8°C (100°F)

1.6 Personal Protection

Engineering Controls:

Provide exhaust ventilation or other engineering controls to keep the airborne

concentrations of vapors below their respective threshold limit value. Ensure that eyewash
stations and safety showers are proximal to the work-station location.

Personal Protection:

Splash goggles, Lab coat, Vapor respirator, are sure to use an approved/certified respirator
or equivalent, Gloves.

Personal Protection in Case of a Large Spill:

Splash goggles, Full suit, Vapor respirator, Boots, Gloves. A self-contained breathing
apparatus should be used to avoid inhalation of the product. Suggested protective clothing might
not be sufficient. Consult a specialist BEFORE handling this product.

3.3 HAZOP Analysis for Styrene manufacturing plant

HAZOP study is a systematic technique for identifying all plant or equipment hazard and
operability problems.

13
In this section, we argued that basis of safety according to
 Equipment

 Material Properties

 Risk Tolerability

Table 3.1: HAZOP for the Styrene plant

S. Equipment Cause/Type of Risk Factor Precautions
No Risk
1 Storage *At styrene storage *Combustion with * Usage of flow,
Tanks(Styrene and tank, air level, pressure and
Ethylbenzene) polymerization risk temperature for all
may occur. *Explosion occurs tanks
due to flammable
*EB and Styrene gas *More fire
are flammable equipment storage
chemical, fire and *polymerization of
explosion risk may styrene. *More control
occur. equipment
*Tank is colored
paint which is
Reflected sunlight.

*Insulation shall be
increased

*Storage tanks must

be placed away from
the main plant.
2 Distillation column *Vacuum in the *Explosion * Settling far enough
column from plant which
*Pressure increase increases land factor.
due to more
component *More pressure,
entrance to system temperature control
equipment should be
*heating system used.
failed

*polymerization

3 Three phase *Flow rate changes *inlet temperature *Material of

14
 separator decrease construction must be
*Flow temperature selected suitably.
changes *inlet flow rate
decrease or * Valves should be
increase placed before and
after heat exchangers

*Maintenance and
Repair cost shall be
increased.

*More temperature
control
equipment should be
used
4 Heat exchangers *Flow temperature *inlet temperature *Material of
change decrease construction must be
*Flow rate change *inlet flow rate selected suitably.
decrease or
increase * Valves should be
placed before and
after heat exchangers

*Maintenance and
Repair cost shall be
increased.

*More temperature
control
equipment should be
used

15
 Chapter 4: Optimization of reactor configuration

4.1 Process Description:

In styrene monomer reactor fresh ethyl benzene mixed with recycled ethyl benzene and
steam is preheated using the product stream from the reactor, and then mixed with the
superheated steam to reactor inlet temperature of over 875 K before injecting into the fixed bed
catalytic reactor. Super-heated steam provides the necessary heat of reaction and pre-vents coke
formation reduces partial pressure of styrene and hydrogen to shift the thermodynamic
equilibrium in favor of the styrene production. The reactor effluent is cooled to quench all
reactions in several heat exchangers, and then directed to the separator to recover styrene. Six
main reactions occur in styrene reactor. Rate equations and frequency factors and activation
energy of those reactions are listed. The kinetic constants of the reactions are expressed by
Arrhenius equation. Dehydrogenation of ethyl benzene is an endothermic reversible reaction, and
proceeds thermally with low yield but catalytically with high yield. As it is an endothermic
reaction producing two moles of product with one mole of reactant, low pressure and high
temperature favor forward reaction producing styrene. The competing reactions, degrade ethyl
benzene to by-products such as benzene and toluene, thus reduce styrene yield. As the rate of
formation of by-products increases with temperature, an optimal operating temperature is
necessary to compromise between conversion of ethyl benzene to the styrene and by-product
formation. Moreover, a selective catalyst is desirable to achieve high styrene yield at the low
temperature and to minimize side reactions.

4.2 Development of model:

The pseudo-homogeneous model of styrene monomer production reactor was formulated

and numerically was integrated with Runge-Kutta-Verner fourth and fifth order method using
MATLAB. The profile of effects of some important parameters in the reactor was found by
pseudo-homogeneous mathematical model. The results of the proposed model compared to an
industrial reactor that was very similar. The proposed mathematical model was used for

16
 calculation of the output of the reactor against variation in S/E and inlet temperature. Accor ding
to the results of the proposed model, with increasing of S/E, the conversion of ethyl benzene
increases but the selectivity of styrene decreases. The selectivity of styrene has an optimal value
in S/E =13.5-14.5 and inlet temperature between 850 °C to 950 °C is the best temperature to get
the highest con- version and selectivity.
Table 4.1: Kinetic Equation and Frequency Factors and Activation Energy of Ethylbenzene
Dehydrogenation
Ei (kJ/
S.NO Reaction Reaction express Ai mol
−1
)
R1=K 1 (
1 C6 H 5 CH 2 CH 3 ↔C 6 H 5 CHCH 2 + H 2 -0.0854 90981.4
peb −p eb p H 2 / K eb )

2 C6 H 5 CH 2 CH 3 →C 6 H 6 +C2 H 4 R2=K 2 peb 13.2392 207989.2

3 C6 H 5 CH 2 CH 3 + H 2 →C 6 H 5 CH 3+ CH 4 R3=K 3 peb p H 2 0.2961 91515.3

0.5
4 2 H 2 O+C2 H 4 → 2CO+ 4 H 2 R4 =K 4 psteam p ef h -0.0724 103996.7

5 H 2 O+CH 4 →CO +3 H 2 R5=K 5 psteam pmet h -2.9344 65723.3

R6=K 6 (P/ T 3 )
6 H 2 O+CO → CO 2+ H 2 21.2402 73628.4
psteam p CO

Table 4.2: Industrial Reactor Specifications, Catalyst Properties and Feed Condition.
Quantity Numerical value
Reactor tube diameter 1.22m
Exit conversion 45%
Feed rate per reactor tube(ethyl benzene) 13.5 lb mol/h (1.70* 10−3 kg mol/s)
Feed rate per reactor tube(steam) 270 lb mol/h (34.0* 10−3 kg mol/s)
Bulk density of catalyst as packed 90 lb/ ft 3 (1440 kg/ m3 )
Average pressure in reactor tube 1.2 atm (121 K Pa)
Heat of reaction ∆H 60,000 Btu/lb mol(1.39* 103 KJ/(kg mol))
Inlet temperature 625ْ c (898K)
Surrounding temperature 70ْ F (294 K)

17
 0.45

0.4

0.35

0.3
conversion x

0.25

0.2

0.15

0.1

0.05

0
0 0.2 0.4 0.6 0.8 1 1.2 1.4
Reactor length m

630

620

610
Temperature oC

600

590

580

570

560
0 0.2 0.4 0.6 0.8 1 1.2 1.4
Reactor length m

Chapter 5: Detailed Layout of Styrene Plant

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5.1 Plant Layout:
The economic construction and efficient operation of a process unit will depend on how well the
plant and equipment specified on the process flowsheet is laid out.

Meaning:

Plant layout is the most effective physical arrangement, either existing or in plans of industrial
facilities i.e. arrangement of machines, processing equipment and service departments to achieve
greatest co-ordination and efficiency of 4 M’s (Men, Materials, Machines and Methods) in a
plant.

The possibility of attaining the best possible layout is directly proportional to following factors:

 The Weight, Volume or Mobility of the Product

 Complexity of the Final Product
 The Length of the Process in relation to Handling Time
 The Extent to which the Process Tends towards Mass Production.

The principal factors to be considered are:

 Economic considerations: construction and operating costs

 The process requirements
 Convenience of operation
 Convenience of maintenance
 Safety
 Future expansion.

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5.2 Standards to Be Followed In the Plant Layout:

 In process layout study, firstly the process equipment was placed according to inside
battery limit. Minimum spacing of equipment were argued with safety considerations.

 The auxiliary unit, as the second step, is placed. The control room and the laboratory
should be close to the process but at a safe distance from the moment of danger.

 Fire stations are placed in fire hazard areas.

 Social areas and offices should be remote from the process.

 Safety and minimum pollution of any kind should be given importance

 Green surroundings are important; this reduces the pollution.

5.3 Detailed Plant Layout (Bock-Diagram):

Figure 6.1: Detailed Layout of Plant

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5.4 Site Selection:

Based on the market survey and preliminary feasibility study, there are few places have
been considered for the site selection. The location for the plant must be chosen for the existing
infrastructure, close proximity to road, rail and sea transport and thus minimizing the overall
transportation costs. Government assistance is anticipated in order to encourage the development
of the state. The plant layout is design based on specified safety considerations, costs and ease of
access and flexibility.

Factors affecting the site to be selected are:

Raw material availability:

 The source of raw material is one of the most important factors in selection of a plant site.
If large volume of raw material is consumed, it is the best to choose the place for the
plant site near the raw materials sources. This is because it will reduce the transportation
cost and storage sites facilities.
Market:

 It is necessary that a plant is situated in a site which is located in the place near where the
demand is high, else exporting should be followed which will lead to increase in the
prices of product.
 Energy Availability:
 All the state government supplies electrical supplies to the industrial sector. However, for
the company that generates their own electricity by using turbine concepts or other means
of generation electricity allowing the reducing of the utilities cost.

Climate Conditions:

21
  Adverse climatic conditions at a site will increase costs. Abnormally low temperatures
will require the provision of additional insulation and special heating for equipment and
pipe runs. Stronger structures will be needed at locations subject to high winds
(cyclone/hurricane) or earthquakes.
Transportation facilities:

 Transportation is another factor that must be considered for site selection because with
transportation is the way for connection. The plant should have better transportation
facilities to ease the transportation of the product to the customer and for the utilities.

Water supply:

 Nearby areas with high water tables are highly advantageous for a plant site.

Waste Disposal:

 All industrial processes produce waste products, and full consideration must be given to
the difficulties and cost of their disposal.

Labor supply:

Labor will be needed for construction of the plant and its operation. Skilled construction
workers will usually be brought in from outside the site area, but there should be an adequate
pool of unskilled labour availability locally and labour suitable for training to operate the plant.
Skilled tradesmen will be needed for plant maintenance. Local trade union customs and
restrictive practices will have to be considered when assessing the availability and suitability of
the local labour for recruitment and training.

22
Taxation and legal restrictions:

 Capital grants, tax concessions, and other inducements are often given by governments to
direct new investment to preferred locations such as areas of high unemployment. The
overriding of such grants can be the overriding considerations in site selection

Site characteristics:

 Sufficient suitable land must be available for the proposed plant and for future expansion.
The land should ideally be flat, well drained and have suitable load-bearing
characteristics. A full site evaluation would be made to determine the need for piling or
other special foundations.
 Flood and fire protection:

 The location should be located nearer the port location. However, the protection such as
flood protection should be considered. The plant must build at the place that has low
chances to be flooding. It can be measure by studies the topography of the site location.
For the fire protection, the plant should have many protections for the fire such as fire
extinguisher, and etc. The location of the fire extinguisher must be easy for the people to
see. It is because the fire extinguisher can be used easily whenever getting emergency
situation.
Community factors:

 The proposed plant must be fit in with and be acceptable to the local community. Full
consideration must be given to the safe location of the plant so that it does not impose a
significant additional risk to the community. On a new site, the local community must be
able to provide adequate facilities for the plant personnel: schools, banks, housing, and
recreational and cultural facilities. All of the state or site chosen for the potential site of
the styrene plant has considerably enough and complete facilities of their own
community.

23
 Conclusion

Styrene is the precursor for polystyrene, which is used in plastics, protective coatings,
polyesters, resins, and chemical intermediates. . The demands for styrene are indeed very
high. The most common method for styrene production is catalytic dehydrogenation, thus
the team proceed with the method. Since the raw material availability and the demands
for styrene are easily available for that process. The teams successfully construct Block
Flow Diagram (BFD), Process Flow Diagram (PFD) and Piping and Instrumentation
Diagram (P&ID) for the production of styrene. Coming to the results of optimization.
The pseudo-homogeneous model of styrene monomer production reactor was formulated
and numerically was integrated with Runge-Kutta-Verner fourth and fifth order method
using MATLAB. The profile of effects of some important parameters in the reactor was
found by pseudo-homogeneous mathematical model. The results of the proposed model
compared to an industrial reactor that was very similar. A safety analysis was made on the
entire plant and cost estimation was made for the full plant.

24