CHE 231 : Introduction To Chemical

Engineering Plant Design

PREPARED FOR : MADAM NURUL ‘UYUN BINTI AHMAD

GROUP : EH 110 5C

COMPANY’S NAME : FKK CHEMICAL COMPANY

PREPARED BY :

NAME STUDENT ID POSITION

MOHD. AMIR HILMI BIN IBRAHIM 2015847578 PROJECT
MANAGER
MOHD AIRIE FAZUWA BIN MOHD RAFI 2015865928 SAFETY
ENGINEER
AMIRUL FAHD BIN YESSERI 2015848158 PROCESS
ENGINEER
WAN NOR FADILAH BINTI WAN MAT TAHIR 2015847546 DESIGN
ENGINEER
TABLE OF CONTENTS
CONTENTS PAGE
1.0 ABSTRACT 2

2.0 INTRODUCTION 3-4

3.0 PROBLEM STATEMENT AND OBJECTIVES 5

4.0 PROCESS BACKGROUND 6

4.1 CHOLOROHYDRIN PROCESS 7
4.2 IMMADIATE OXIDATION PROCESS 8
4.3 AIR-BASED DIRECT OXIDATION PROCESS 10
4.4 OXYGEN-BASED DIRECT OXIDATION PROCESS 10

5.0 PROCESS SELECTION

5.1 DIRECT OXIDATION PROCESS ANALYSIS 12
5.2 AIR-BASED VS OXYGEN-BASED PROCESS 12
5.3 PROCESS DETAILS
5.3.1 REACTOR HEAT PREHEAT/EFFLUENT COOLER 13
5.3.2 REACTOR 14
5.3.3 CATALYST 15
5.3.4 DESIGN DETAILS 17
5.3.5 COOLING WATER 20
5.3.6 MATERIALS OF CONSTRUCTION 20

6.0 SITE SELECTION 23

7.0 SAFETY CONCERNS

7.1 SAFETY OF THE PLANT 25
7.2 SAFETY ISSUES (EO) 29

8.0 CONCLUSION 35

REFERENCES 36

APPENDICES 37

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1.0 ABSTRACT

With the advance of modern technology, it is becoming increasingly feasible economically to

synthesize and produce on a large scale those chemical products, for example plastics, synthetic
fibers, dye stuffs and paints, which are so much a part of our present day life. Ethylene Oxide is
an important ethylene based intermediary compound as the main use for ethylene oxide is the
manufacture of derivatives such as ethylene glycol and surfactants. In the production of ethylene
oxide, element oxygen and ethylene react over a silver catalyst surface. There are two reactions
occur, which are partial oxidation of ethylene to ethylene oxide and the other one is the total
oxidation of ethylene to carbon dioxide and water. The largest cost in production of ethylene
oxide is ethylene so, it is important to optimize the selectivity towards ethylene oxide and thus
reduce the consumption of ethylene. Multiple studies have been done to discover the kinetics of
the oxidation reactions of ethylene over a silver catalyst however there has been no general
agreement among the kinetics equation and mechanism described. It is agreed that silver can
adsorb oxygen in a number of ways and this phenomenon is the basis of silver’s efficiency in
catalyzing the oxidation of ethylene to ethylene oxide. nearly all the world's EO capacity is based
on direct oxidation, with oxygen generally preferred over the air route in larger plants due to
higher yields and less downtime. Ethylene, compressed oxygen and recycle gas are mixed and
fed to a multi-tubular catalytic reactor. The mixture is passed over a silver oxide catalyst
supported on a porous carrier at 200-300˚C and 10-30 bar. The reaction is highly exothermic and
the heat removed can be used to generate steam. The gases from the reactor are first cooled and
passed through a scrubber where the ethylene oxide is absorbed as a dilute aqueous solution. The
EO can then go straight to glycol manufacture or purified by fractionation for use in other
ethylene oxide derivatives.

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2.0 INTRODUCTION

The foundation about FKK Chemical Company and the goals of this report will be displayed in
this section. Ethylene oxide is a critical ethylene based middle person compound. The essential
use for ethylene oxide is in the fabricate of subordinates, for example, ethylene glycol,
surfactants and ethanolamine's. FKK Chemical Company is one of the world's driving industrials
organizations and is dynamic in the territories Decorative Paint, Performance coatings and
Specialty Chemicals. FKK Chemical's headquarter is situated in Amsterdam, the Netherlands.
They work in 80 nations with 47 000 representatives and are reliably positioned as one of the
pioneers on the Dow Jones maintainability file. FKK Chemical has 3200 workers in Sweden and
work at roughly 15 places. The historical backdrop of FKK Chemical in Stenungsund can be
followed back to the start of the 1900s century.

The crude materials in the generation of ethylene oxide at FKK Chemical are ethylene and
oxygen where ethylene is the biggest piece of the cost, around 70% of the crude material.
Accordingly, it is of extraordinary enthusiasm to streamline and keep up a high selectivity
towards ethylene oxide in the reactors and along these lines lessen the utilization of ethylene.
This is conceivable by supplanting the current impetus to an impetus with better selectivity
towards ethylene oxide. A trade of impetus for a superior impetus regularly implies a change in
working parameters. The point is to create more ethylene oxide with an impetus that can work
inside existing plan temperature, outline weight and to work inside a sheltered edge to
combustibility. A vital goal is to expand the life cycle while enhancing the impetus execution.
The point with this task is to make a procedure reproduction demonstrate for the reactor
framework which is reliable with the present impetus execution. This reactor reproduction can
likewise be a device for future impetus assessments.

To have the capacity to make a recreation demonstrate which compares to reality the
accompanying imperative issues will be examined:

• Find a thermodynamic model that associate with the framework and a depiction of the
advantages of the decision of model.

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• Build a static model in Aspen Plus and run it at three different working conditions.

• Create a reactor active model for the reactor framework and blade tune it so it will relate with
the current impetus. Key parameters are temperature, selectivity and warmth development

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3.0 PROBLEM STATEMENT AND OBJECTIVES

The raw materials in the production of ethylene oxide at FKK Chemical Company are ethylene
and oxygen where ethylene is the largest part of the cost, approximately 70% of the raw material
so it is of great interest to optimize and maintain a high selectivity towards ethylene oxide in the
reactors. This is highly possible by replacing the existing catalyst to a catalyst with better
selectivity towards ethylene oxide. An exchange of catalyst for a better catalyst often can be
means with a change in operating parameters. The purpose is to produce more ethylene oxide
with a catalyst that can operate within existing design temperature, design pressure and to
operate with a safe margin to flammability. Another significant objective is to extend the life
cycle while improving the catalyst performance.

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4.0 PROCESS BACKGROUND

Ethylene oxide was first arranged in 1859 by Wurtz utilizing potassium hydroxide answer for
take out hydrochloric corrosive from ethylene chlorohydrin. This prompted a modern creation of
EO (Ethylene Oxide) which started in 1914. The direct reactant oxidation of ethylene, found in
1931 by Leffort, was step by step supplanted by the chlorohydrin procedure. Today EO is
delivered by coordinate oxidation of ethylene with air or oxygen. It is these two fundamental
sorts of procedures which have been huge in the business assembling of ethylene oxide. The
chlorohydrin procedure is the most seasoned and has by the mid 1960s quickly being eliminated
and is never again being used.

The immediate oxidation process is more prudent and has been an imperative factor in the
gigantic development of the EO market.Ethylene oxide is an item that is devoured everywhere
throughout the world. The Middle East, China and United States remains for most of the market.
Of the aggregate worldwide ethylene oxide limit in 2012, 25% is in Middle East, 16% is in
China and 12% is in the United States. Whatever remains of Asia represents 25% of the world's
ability. These locales cover 79% of the aggregate world limit. In 2012 the significant ethylene
oxide finished results were monoethylene glycol (MEG), diethylene glycol (DEG), and
triethylene glycols (TEG). They spoke to over 75% of aggregate utilization. MEG is utilized as a
part of fiber produce and for liquid catalyst. DEG is utilized as a part of fiber industry for
generation of textures and as a tobacco humectant. TEG and DEG are both utilized for gas
treatment. TEG is likewise utilized as a part of the assembling of cellophane for nourishment.

The design models a process based on a four-part system developed by the conventional Shell
direct oxidation technology. This basic design contains the following parts: the reaction system,
absorption system, CO2 Removal Section, and EO purification system. This proposal focuses on
developing and optimizing the reactor system.

The reaction system involves four shell-and-tube packed plug flow reactors, which contain
silver/alumina catalyst. The feed flows are high-purity grade oxygen and ethylene. The catalyst
eases the partial oxidation of ethylene to ethylene oxide and the complete combustion of ethylene
to carbon dioxide and water. The selectivity of the ethylene oxide formation is around 81%,

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while the ethylene conversion to EO is around 10%. Since the reactions are exothermic, water is
used as a cooling medium on the shell side of the reactor and is later used to produce large
quantities of low-pressure steam.

In the design, the absorption system and CO2 Removal section is included with the reaction
system in order to produce a realistic model of the recycle stream feed for the reactor. Since
these areas were not within the scope of the project, the absorption of EO and water and the
removal of CO2 were assumed to be ideal, with 100% removal of EO, and 100% removal of the
total amount of CO2 flowing through the CO2 removal section.

The simplified and detailed design can be seen in the Figures 2 and 3 on the following pages.
Additionally, the detailed process information can be found in the Appendix. It contains all
stream data and information for a typical reactor.

4.1 Chlorohydrin process

As specified in the past section the chlorohydrin procedure is never again being used yet has a
recorded esteem and along these lines it will be portrayed in this part. One of the two major
responses that are associated with the generation of ethylene oxide by the chlorohydrin
procedure is the response of ethylene with hypochlorous corrosive to shape chlorohydrin:

CH2CH2 + HOCl →HOCH2 CH2Cl (1)

The second response is that of the chlorohydrin with a base, ordinarily calcium hydroxide, to
frame ethylene oxide.

HOCH2CH2Cl + ½ Ca(OH)2 → CH2CH2O + ½ CaCl2 + 2 H2O (2)

The chlorohydrin procedure is done in stuffed towers at 27-43°C and 2-3 atm weight at a yield of
85-90%. To keep away from arrangement of side-effects (ethylene dichloride, dichlorodiethyle
ether and so forth.) the centralization of chlorohydrin in the chlorohydration response
arrangement is kept up beneath 7 wt.%.

The second step of the procedure, dehydrochlorination, is proficient by including 10 wt.% watery
slurry of lime to the chlorohydrin arrangement. The blend is then warmed to recently under

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100°C in the hydrolyzer, a round and hollow vessel with a reflux condenser working at basically
environmental weight. As the chlorohydrin responds with the disintegrated lime ethylene oxide,
results and some water is framed. The ethylene oxide is expelled as a vapor from the incomplete
condenser. The vapor stream from the hydrolyzer is gone through a cooler and mostly
consolidated and after that bolstered to the fractionated segment. The refinement of the unrefined
ethylene oxide is troublesome and requires various refining towers. As said in the past section
MoDo delivered ethylene oxide from ethanol. In this procedure, drying out of ethanol produces
ethylene and water.

C2H5OH → C2H4 + H2O (3)

The consequent procedure steps are like the chlorohydrin procedure portrayed previously.

4.2 The immediate oxidation process

The primary business EO process utilizing direct oxidation was created in the United States via
Carbide and Carbon Chemicals Corp. (today Union Carbide Corp.) which began its initially plant
in 1937 in light of the utilization of air. In 1953 the Scientific Design (SD) air based process was
marketed and by the late 1950s the immediate oxidation process began to supplant the
chlorohydrin procedure. In 1958 Shell Development presented the primary oxygen based process
for coordinate oxidation of ethylene. In ensuing years the oxygen based process was marketed by
SD/Halcon (1969), Nippon Shokubai (1976), and Union Carbide (1976).

The principle motivation behind why chlorohydrin process is never again being used is the
efficient factor. It is 3-4 times more costly to create ethylene oxide by chlorohydrin process than
by coordinate oxidation process. Another burden of the chlorohydrin procedure is the issue of
treating the expansive waste stream containing calcium chloride and measures of chlorinated
hydrocarbons and glycols. The fundamental burden and wastefulness of the immediate oxidation
process is the lower selectivity of ethylene oxide per unit of encourage ethylene devoured, comes
about because of the loss of 20-25% of the ethylene to carbon dioxide and water.

All ethylene oxide coordinate oxidation plants depend on the first procedure science found by
Lefort in 1931. The immediate vapor-stage oxidation of ethylene to ethylene oxide over a silver

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impetus at 220-300°C and 10-30 bar weight produces few bi-items other than carbon dioxide and
water.The imperative responses that happen are:

Ethylene is oxidized with oxygen over a silver alumina impetus to shape ethylene oxide.

CH2=CH2 + ½ O2 → CH2-CH2O (ΔH = - 106,7 kJ/mol) [8] (4)

Ethylene is completely oxidized to frame carbon dioxide and water.

CH2CH2 + 3 O2 → 2 CO2 + 2H2O (ΔH = - 1323 kJ/mol) [8] (5)

Ethylene oxide is additionally oxidized to frame carbon dioxide and water.

CH2CH2O +5/2 O2→ 2CO2 + 2H2O (ΔH = - 1323 kJ/mol)[8] (6)

To avert assist oxidation of ethylene oxide, the ethylene change of the business procedure is
commonly between 10-20% bringing about a recycled gas circle that is clarified promote in
resulting part. In coordinate oxidation forms a couple of ppm of ethyl chloride (2,5-3,0 ppm) or
vinyl chloride (4-6 ppm) is added to the vaporous encourage to hinder the total oxidation
response and increment selectivity to ethylene oxide. [9] Although little hints of bi-items,
normally under 0,1 % of acetaldehyde and considerably littler measure of formaldehyde are
additionally created.

CH2CH2O → CH3-CHO (Acetaldehyde) (7)

CH3-CHO + 2 1/2 O → 2CO2 + 2H2O (8)

CH2=CH2 + O2 → 2CH2O (Formaldehyde) (9)

The immediate oxidation (EO) process can be partitioned into air-and oxygen based procedures.

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4.3 Air-Based Direct Oxidation Process

Compacted air is first cleansed to expel contaminants and after that blended with reused gas and
crisp ethylene. Vapor stage oxidation inhibitors, for example, ethylene dichloride or vinyl
chloride or other halogenated mixes are included the bay of the reactor to impede carbon dioxide
arrangement. The gas is encouraged to a multitubed synergist reactor in which the reactor
temperature is controlled with bubbling water or flowed non-bubbling natural oil on the shell
side. In the event that oil is utilized, it is cooled in a steam generator, creating high weight steam
which is utilized as a part of the procedure.

The gushing gas from the primary power source, which now contains ethylene oxide, is cooled in
a shelland-tube warm exchanger with frosty reactor encourage gas. The cooled gas is then
bolstered in to the principle safeguard where the ethylene oxide is caught up in water, create a
weaken fluid arrangement. The scoured gas from the safeguard is then compacted and the real
segment of the gas is reused to the central power source. A piece of the gas stream is sent to
auxiliary (or cleanse) reactor framework to cleanse both the nitrogen presented noticeable all
around encourage and furthermore the carbon dioxide created in the reactor.

4.4 Oxygen-Based Direct Oxidation Process

High immaculateness oxygen is blended with reused gas and new ethylene and the consolidated
gasses are the fed into a multitube reactor like the one noticeable all around based process. The
emanating gas, containing ethylene oxide is warm traded with icy reactor bolstered gas before it
enters the safeguard. In the safeguard the ethylene oxide is disintegrated in the safeguard water to
create a weaken watery arrangement. The scoured gas is then compacted and reused to the
reactor. A piece of the reuse gas is first sent to a CO2 safeguard where carbon dioxide delivered
in the reactor is synthetically invested in a recycled arrangement of hot potassium carbonate. The
CO2 lean gas is then come back to the reused gas and back to the reactor. The CO2-rich
carbonate arrangement is recovered in the CO2 stripper utilizing steam and the desorbed carbon
dioxide is vented out in the highest point of the segment. To stay away from gathering of other
idle, for example, argon which is a pollution in the oxygen supply a little cleanse of cycle gas is
vented to environment or incinerator. In the event that argon isn't vented out it can develop to 30-

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40% in the cycle gas. As a result of the lower warm limit of the argon, the cycle gas may enter
the combustible locale, and because of that the oxygen focus should be diminished in the cycle
gas.

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5.0 PROCESS SELECTION

Ethylene oxide production is an old process that has gone through one major change throughout
its life. The basic goal is still the same, to react ethylene and oxygen either directly or indirectly
to produce ethylene oxide and several undesirable by-products. Initially, this was accomplished
by the World War I era chlorohydrin process. In modern times, EO is produced by the direct
oxidation of ethylene.

5.1 Direct Oxidation Process

Lefort was the first to synthesize ethylene oxide through the direct oxidation of oxygen and
ethylene in the early 1930’s. This process became popular commercially, and still is the most
common method of making ethylene oxide.

The main byproducts of the reactions are carbon dioxide and water. Two other side reactions also
occur in the reactor, which are the isomerization of acetaldehyde and production of
formaldehyde. This initial proposal does not account for the amounts of these two products,
typically less than 0.1% acetaldehyde and even less formaldehyde in the total amount of reaction
products (12). This design process uses the direct oxidation process to synthesize ethylene oxide.

5.2 Air-based vs. Oxygen-based Process

Different industries use either air or oxygen as feed streams to obtain an oxygen source to react
ethylene with oxygen. The company need to consider whether to use air or oxygen for its source
of oxygen feed. The oxygen-based process is chosen due to its many advantages. For all plant
capacities and a given type of catalyst, the oxygen-based reactor yields a higher selectivity and
requires less catalyst (10). Although the air-based process may cost lower to run (for small to
medium-sized plants), the initial building costs of the air-based plant is much more than the
oxygen-based plant (10). While the oxygen-based process requires a carbon dioxide removal
section, more stainless steel, and some expensive instrumentation, the air-based process requires
more catalyst, more reactors (to achieve a comparable selectivity), a multi-stage compressor, air
purification units, a vent gas treating system, and two to three reactor train in series (12).

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In spite of the extra equipment for the air-based process, the production level of ethylene oxide
for an air-based process is still less than the oxygen-based process. The average selectivity
ranges from 65-75% compared to 70-80% for the oxygen-based process. Furthermore, the
oxygen-based plants can have a yield of up to 0.1 kg ethylene oxide per kg ethylene more than
the air-based plants (12). Due to this reason, the oxygen-based process is a more attractive
choice.

The air-based process has the gas purge stream, which contains ethylene that requires extra
treatment before it can be vented to the atmosphere. This extra air pollution is not part of the
oxygen-based process (5). The cycle gas purge stream of the oxygen-based process is usually
small enough to be burned without too many pollution problems (8). The pure oxygen process
poses less potential problem for the air.

Since the silver catalyst is expensive, the length of catalyst life is an important consideration. For
the oxygen oxidation, the catalyst lasts longer and less is required for the catalyst charge (12).
The air-based oxidation generally needs 1.5 times the catalyst charge of the other process. The
required amount of catalyst and length of catalyst life also makes the oxygen-based process a
more economically viable choice. Therefore, we decide to went for Oxygen-based Oxidation
Process.

5.3 Process Details

5.3.1 Reactor Feed Preheat/ Effluent Cooler

The Pre-heat exchanger’s main purpose is to pre-heat the inlet feed from 181oF to 266 oF. This is
accomplished efficiently by pre-heating the feed in the tube side while simultaneously cooling
the reactor effluent from 482oF to 408oF. The pre-heat temperature is selected based on previous
research performed by a previous engineering team of FKK Chemical Company, studying
ethylene oxide production. Although a high reactor inlet temperature is desired, FKK Chemical
Company concluded that the heat exchanger surface area needed for any higher temperature
required the use of an excessive amount of large and costly heat exchangers. The heat exchanger
pressures are determined by the optimal reactor pressures. The tube side inlet pressure is 261

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psia, and the shell side inlet pressure is 243 psia. The pressures are determined by the reactor
pressure requirements.

Stainless steel is chosen for both the tube and shell sides because there is a large amount of EO
flowing through the shell and possible trace amounts of EO in the tube side. EO is very reactive
with rust and thus the use of stainless steel is critical to avoid a hazardous situation.

5.3.2 Reactor

Reaction Chemistry and Kinetics

Two reactions for ethylene oxide production were considered for the reactor system, which can
be seen in Table 1. The main reaction is the formation of ethylene oxide from ethylene, with
approximately 81% selectivity towards this reaction. The second reaction is the combustion of
ethylene to carbon dioxide. The specifications for the system were to obtain approximately 10%
conversion of ethylene and a 30-50% conversion of oxygen within the selectivity range stated.

Table 1: Reactions of the System

Primary Reaction: C2H4 + O2 --> C2H4O

Ethylene Oxide Formation

Secondary Reaction: C2H4 + O2--> CO2 +

H2O
Ethylene Combustion

The kinetics of the system are determined in order to begin the design of the reactor. Through the
use of Arrhenius kinetics, the reactions are modeled based on given activation energies from
literature (7). Pre-exponential factors need to be obtained in order to complete the kinetic design.
The pre-exponential factors are determined using an iterative method. First, a base case is built in
HYSYS in order to calibrate the reactor design. The Soave-Redlich-Kwong equations of state are
selected since they are commonly used, and all simulated components are compatible in this set

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for HYSYS. Literature values are needed to obtain an idea of the total reactor tube volume to
reactor inlet flow rate ratio. These figures are necessary to obtain an estimate for the residence
time associated with typical literature values for conversion and selectivity. Since literature
usually provides product flow rate to reactor volume correlation, a conversion reactor is used to
solve for the inlet flow rate to reactor volume ratio. This type of reactor simply performs a mass
and energy balance given the individual conversions for each reaction. With a residence time,
inlet flow to reactor volume ratio and kinetic data obtained from Kenson (7), the pre-exponential
terms are solved for a typical industrial reactor. These values are used to develop a plug flow
kinetic model to replace the conversion model. The following table shows the kinetic data for the
reactor:

Table 2: Reactor Kinetics

Activation Energy Pre-exponential

Factor

Ethylene Oxide 3.8e4 Btu/lbmol 1.1e12 hr -1

Formation

Ethylene 5.2e4 Btu/lbmol 4.8e14 hr -1

Combustion

These values allow for the selectivity and conversion to stay within range, allowing selectivity of
the ethylene oxide formation to be high, while obtaining a relatively low conversion per pass.
The selectivity of the synthesis reaction is maintained at around 81%. Approximately 12% of the
ethylene is converted per pass, while 40% of the oxygen is converted.

5.3.3 Catalyst

The catalyst is an important part of the reaction mechanism because it determines the
heterogeneous kinetics. Silver/alumina catalyst is the type of catalyst used, which drives the
selectivity of the reactions towards ethylene oxidation. The silver allows for oxygen adsorption

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on its surface, which forms an ionized superoxide. The ethylene is reactive with this superoxide,
resulting in the formation of ethylene oxide (4).

Although there are several variations of silver/alumina catalyst available, average values
provided in the literature are used. Unfortunately, data on specific catalysts is proprietary and
very difficult to obtain. This situation did not allow for any reliable or supportable comparisons
between catalysts. The company, therefore models the catalyst in a manner to produce
conservative results and uses catalyst properties consistent with the literature values for the
classic Shell direct oxidation catalyst. This catalyst is capable of producing the 12% conversion
and 81% selectivity desired. The change out time for this catalyst is approximately three years.
One catalyst that the company feels should be studied in the future is a fairly new catalyst that is
capable of 86-87% selectivity with a reduced change out time of one year. Due to time and data
constraints, the company is not able to provide a satisfactory evaluation of this option.

Catalyst physical properties are modeled since they play a significant role in reactor performance
and pressure drop. A higher catalyst density leads to an increased reaction rate, but unfortunately
produces a higher pressure drop. Therefore an accurate representation of the catalyst properties
in the model is crucial to obtaining accurate results.

The following table shows the details of the catalyst sizing that are used in the reactor:

Table 3: Catalyst Details

Volume 352 ft3

Diameter 0.026 ft

Length 38 ft

Solid Density 48.7 lb/ft3

The results obtained with these catalyst properties are in line with the literature values. The
pressure drop in it model is 14.2 psia. Industry correspondance states that a typical pressure drop

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across a reactor should be between 10-20 psia (13). Therefore, the model appears to be
reasonable in regards to yet a third parameter in addition to conversion and selectivity.

5.3.4 Design Details

Vertical plug flow shell-and-tube reactors are used for the system. Plug flow reactors are the
most common reactors currently being used in industry for ethylene oxide production (13), since
they allow for high velocities to be used and require less volume than other types of reactors.
Since the reactions are exothermic, a shell-and-tube reactor design is ideal because it allows for
coolant to be run through the shell side for heat exchange. This is critical in reducing hot spot
formation, and more importantly in preventing the reactor temperature from running away (4).
Hot spots cause severe catalyst degredation, and runaway temperatures can lead to catastrophic
process failures. Therefore, the process feed flows through the tube side, while the cooling
medium flows through the shell side. The reactors are vertical in order to provide back pressure
for the system. This helps to keep the catalyst in place.

The parameters of the reactors are determined based on achieving the objectives of
approximately 10% ethylene conversion and 81% selectivity. These values are typical in the
literature and have been proven to yield an efficient consumption of the reactants. Using the
developed kinetic model for the dominant reactions, the reactor parameters are optimized. The
company’s design includes a total of four reactors that are run in parallel. This design is superior
to one large reactor because smaller reactors are less expensive to construct. Furthermore, this
design allows for a smaller and less expensive spare which is crucial to reduce the threat of
unexpected business interruptions. Each of these reactors contain 1712 tubes, which are 38 ft
long and have a 0.13 ft inner diameter and a wall thickness of 0.017 ft. The tube diameters are
consistent with the industry standard, and the number and length of the tubes are determined by
rigorous simulation in HYSYS. These two parameters are selected in order to obtain the desired
conversion and selectivity while maintaining an acceptable pressure drop.

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It is determined that the inlet temperature should be 268 oF (based on preheat exchanger
limitations—see Reactor Feed Preheat/Effluent Cooler section) with an outlet temperature of
482 oF. The reactor operates at 231 psia. Literature sources indicate that typical reactor
conditions are with temperatures of 230-260 oC and pressure at around 147-367 psia (12) The
feed contains ethylene at 99.5% purity and oxygen at 99.5% purity. The inlet is 33% ethylene
and 8% oxygen.

The following table gives the reactor inlet and outlet conditions and compositions:

Table 4: Reactor Feed and Effluent Data

Ethylene Oxygen Feed Reactor Reactor

Feed Recycle Effluent

86 oF 86 oF 162 oF 482 oF

Temperature

261 psia 261 psia 231 psia 241 psia

Pressure

1051 1023 24064 25577

lbmol/hr lbmol/hr lbmol/hr lbmol/hr
Total Molar
Flow

Component

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Flows
(lbmol/hr):

1050 0 7532 7533

Ethylene

0 1023 1039 1039

Oxygen

0 0 1483 1881

Carbon Dioxide

0 0 0 850

Ethylene Oxide

1.36 0 12549 12550

Methane

.0607 0 690 552

Ethane

.0145 0 127 127

Nitrogen

0 .0420 366 366

Argon

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 0 0 278 679

Water

5.3.5 Cooling Water

The highly exothermic reactions require an effective cooling medium in the shell side of the
reactor to prevent runaway reactions and hot spot formations. The chosen cooling medium
chosen is water, which enters the reactor at 187 oF and leaves at 366 oF in the form of steam.
According to JChem, this method of cooling provides the best heat transfer (4).

The cooling water requires a pump system to propel the water into the shell side of the reactor.
This pump system provides the necessary cooling water to each of the four parallel reactors to
remove the heat generated by the very exothermic reaction. Four separate pumps (one for each
reactor) transport a total of 75,189 lb/hr of cooling water. This arrangement delivers an equal
amount of cooling water to each reactor and reduces the risk of complete failure associated with
the use of a single large and very expensive pump. It is unlikely that four pumps should fail or
simultaneously need replacements. Therefore, a less expensive, smaller pump can be used as a
universal spare. Additionally, repair expenses are not as high for smaller pumps.

5.3.6 Materials of Construction

Stainless steel is chosen the tube side and carbon steel is chosen for the shell side. There is a
large amount of EO flowing through the tube side. Since EO is very reactive with rust, the use of
stainless steel is critical to avoid a hazardous situation. Cooling water is flowing through the
shell, therefore carbon steel is suitable.

Absorber Section

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The reactor effluent leaves the reactor train and moves into the absorber area, with a great deal of
inert gases and unreacted ethylene. From the reactor, the process flow enters the EO absorber,
where water removes the EO from the stream. The EO exits through the bottom of the absorber
and enters further separation and purification steps. These further steps are not within the scope
of this proposal. The remaining components leave through the overhead of the absorber. A
portion of this overhead stream enters the CO2 removal system. This stream serves as the recycle
at the beginning of the process. Part of the overhead from the EO absorber completely bypasses
the CO2 removal system and joins the recycle stream. The vent purges a small fraction of the
inerts in the EO absorber overhead (to prevent build up of inerts in the stream).

Compressor Train

The compressor train increases the pressure of the recycle stream returning to the reactor inlet, in
order to achieve the reactor inlet pressure conditions. The compressor train increases the pressure
of the stream from 223 psia to the reactor inlet condition at 261 psia. A two-stage compression
train consisting of rotary compressors accomplishes this goal. When compared to other units
such as axial, reciprocating, and centrifugal compressors, this type of compressor is a suitable
and very economical choice. Additionally, two-stage compression is more economical as the use
of a single, much larger compressor is very expensive due to the large pressure increase it must
produce. The process requires compressors that are sized to achieve approximately 75%
adiabatic efficiency and 75% polytropic efficiency.

Utilities

The reactor inlet preheater warms the reactor inlet from 181oF to 266oF, which requires a duty of
2.33e7 Btu/hr. This heat exchanger also serves to remove approximately 2.33e7 Btu/hr of heat
from the reactor effluent stream, which cools the stream from 482oF to 408oF.

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The cooling water system around the reactor serves to remove heat released by the reaction. This
heat removal decreases the reactor effluent temperature to 482oF. The heat removal required is a
duty of 8.66e7 Btu/hr. This extra heat vaporizes the cooling water from 187oF to 365oF. The heat
duty requires a cooling water flow of 75,200 lb/hr. The water comes from an external source.
This amount of water requires 4.72e4 Btu/hr (13.8 kW), which is provided by electricity.

The compressor performs work on the recycle stream to increase the pressure of the stream from
223 psia to 261 psia. Two-stage compression, which uses electricity, provides the work. The first
stage involves a compression from 223 psia to 242 psia. This requires 3.15e6 Btu/hr (920 kW).
The second stage of compression increases the pressure from 242 psia to 261 psia. This requires
2.97e6 Btu/hr (872 kW).

Table 5 lists the total utilities used:

Table 5: Total Utilities

Total Electrical Consumption 1,800 kW

Total Cooling Water Consumption 75,200 lb/hr

Internal Heat Exchanger Duties 8.66e7 Btu/hr

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6.0 SITE SELECTION

There are many things need to be considered in making a decision of site selection. This is due to
the geographical location of any industrial plant has strong influence on the success of the
project. Considering the evolvement of EO production in Malaysia, we all agreed that Kerteh,
Terengganu is a right choice for the production of ethylene oxide industry in this country.

Raw material availability

 It is near to the source(Petronas petrochemical)

 Ethylene is produced in the petrochemical industry

Market

 Near to the port

 Ease the process of import and export

Climate condition

 Located near the equator, Malaysia’s climate is categorised as equatorial. Being hot and
humid throughout the year.
 One out of five countries with the lowest risk of having natural disaster

Transportation facilities

 The cost can be saved a lot due to the direct transportation of ethylene from Petronas
through the underground pipe line system

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Water supply

 Syarikat bekalan air KIPC Sdn Bhd

 Recycle the end product (water)

Waste disposal

 The end products of the process are ethylene oxide and water
 Water can be used as water supply in the industry

Labour supply

 Tones of fresh graduates which are still unemployed in Malaysia

Site characteristics

 Close to mountainous area which also might help in order to protect the factory from any
natural disaster such as flash flood
 Near to the sea also is a benefit of fire protection

Community factors

 Its located far from the residential area in which it will not affect them in case of any
disaster strike

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7.0 SAFETY CONCERN

7.1 SAFETY OF THE PLANT

Piping

Pipelines are specifically dedicated to transportation of ethylene oxide, due to the potential
hazards of servicing the system for multiple substances. Since carbon steel can potentially rust
(which leads to other reactions of ethylene oxide), the pipelines are constructed of austenitic
stainless steel (Type 304). Copper, silver, magnesium, mercury and cast irons are not
recommended for equipment servicing ethylene oxide due to low ductility, acetylenic materials,
or high corrosion rates (3). The design of the piping system minimizes low points and stagnate
dead spots, to also avoid the polymerization reaction (6). Furthermore, the surface area of the
pipe sizes will be limited by keeping the diameter and length relatively short. High surface areas
tend to lead to more polymerization of the product. Pipelines are kept short by utilizing a gravity
drainage system where the line can be purged with nitrogen.

Flanges, O-rings, and Packing

The piping system is designed with very few flanges. At each flange, there is a potentially
hazardous leak, which could lead to dangerous reactions in the atmosphere. The gasket material
of flanges are spiral wound stainless steel with either Teflon filler or Grafoil GTB filler. The
exact filler material of each flange are chosen according to the temperature of the substance
passing through, since teflon is only chemically resistant to ethylene oxide up to 400-500 degrees
Farenheit. For the same reason, o-rings are made of Kalrez 2035, virgin Teflon, or Chemrez 505.
Only Teflon or Grafoil GTB are for the packing material (3).

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Pumps

Only carbon steel, stainless steel, or ductile iron pumps are used in the process. Based on past
experience, centrifugal pumps with double mechanical seals are used. The seal fluid is a 50%
aqueous solution of ethylene glycol, due to its low reactivity when in contact with ethylene
oxide. The pumps are strategically placed in curbed spots, isolated from direct process or storage
units. This decreases the risk of potential overheating, leading to ignition of ethylene oxide
vapors (3).

Valves

Valves are selected to avoid stagnate ethylene oxide in any valve openings. As in the pipelines,
these dead areas can lead to polymerization of the chemical. For this reason, ball valves and plug
valves are not recommended for ethylene oxide service. Furthermore, possible emissions of
specific valve designs should also be considered (3). Gate valves, globe valves, and butterfly
valves are installed at the necessary locations in the pipelines.

Insulation

The external walls of pipelines and vessels should be protected against excessive heat, due to the
possibility of ethylene oxide decomposition. Insulation materials should be selected based on
low corrosion rates, resistance to exothermic reactions of ethylene oxide, and durability under
fire flames. In consideration of these issues, cellular foamglass are used as insulation since it is a
closed cell material (decreasing the risk of trapping water, which leads to exothermic reactions).

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Relief Systems

The pressure relief system are designed to tie into an overall system, which feeds to a flare. This
reduces the risk for potential exposure to people in the surrounding area. A careful analysis of
the system is performed, and relief mechanisms are designed for storage units and piping (where
stagnant liquid can gather). The relief system is designed to avoid any possible plugging due to
polymerization. The following factors are considered (3):

 Stainless steel piping

 Installation of rupture disks underneath relief valves
 Decrease the distance between relief valves and equipment units
 Adding nitrogen to the relief valve system periodically

Storage and Transportation

Upon production of ethylene oxide, it is transported by a railcar to a storage area. From the
railcar, the substance is pressurized with an inert gas, such as nitrogen, and pumped into the
temporary storage tank before it is used for further chemical processing (4). The storage vessels
are designed according to ASME specifications and constructed of stainless steel (Type 304).
The tanks are externally coated to avoid the possibility of long-term stress corrosion due to
exposure to atmospheric chlorides. The railcars and storage units are exclusively used for
ethylene oxide to reduce the risk of contamination. The vessels are refrigerated (in the range of
20-80 oF) to decrease the possibility of polymerization and control the heat of any other
reactions, which might occur (3). The ethylene oxide can also be stored longer with refrigeration.
The storage tanks are electrically grounded, placed in an area free from possible fires, and
equipped with pressure relief valves (12).

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Vent Gas Scrubber

Vent gas scrubber systems are commonly used to remove ethylene oxide from the stream. The
scrubber column will be filled with pall ring packings. The ethylene oxide is absorbed by a
strong acidic stream running countercurrent to the vent gas. Although a base can also be used, it
is not as effective as the acid (3). The scrubbed gas is then released atmospherically and the
absorbed ethylene oxide disposed of according to environmental regulations.

Prevention of Backflow

In order to prevent the possibility of backflow from downstream processes using ethylene oxide
to the storage units, a detailed analysis is made of the piping system and vessels. Based on the
distance between units and other structures, check valves are placed along the pipelines,
particularly at the discharge site of pumps. In the event of an incident, the system can be shut off
completely at specific spots, so as to avoid further backflow into the storage units, which could
lead to exothermic reactions and possible vessel explosions.

Operability

With all of the above safety considerations in mind during the design phase, the process is easily
operable. There are provisions for the system in the case of shutdown, plugs in the piping
system, long-term breakdown of hardware, safer storage options, and a viable transportation
plan. In the case of a spill or leak, the possible harmful effects are evaluated and determined to
be relatively acceptable, in consideration of the societal benefits of ethylene oxide.

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7.2 SAFETY ISSUES (Ethylene Oxide)

Although ethylene oxide is a hazardous material in terms of flammability, reactivity and toxicity,
it can be distributed and handled safely provided that appropriate precautions are observed.

Flammability
Ethylene oxide is highly flammable and has a flash point below -18°C. It is flammable in air at
all concentrations above 2.6 % (by volume). There is no upper flammable limit as normally
conceived in that exothermic decomposition replaces combustion at the higher ranges up to 100
% ethylene oxide vapour. Due to its low boiling point and flammability, ethylene oxide is, in
some respects, similar to LPG. However, an essential difference is that ethylene oxide is fully
miscible with water. Another important difference is that ethylene oxide has an
unusually low minimum ignition energy for mixtures in air. The lowest value at about 10.4 %
ethylene oxide by volume is 0.06mJ and this fgure is similar to the ignition energy of about
0.02mJ required by hydrogen/air mixtures. Any leaks of ethylene oxide, for example from
flanges, must therefore be avoided because of the high risk of ignition. Appearance of frost can
be observed in case of liquid EO leaking. The auto-ignition temperature (AIT) of ethylene oxide
in air at atmospheric pressure is 429°C. However, any contaminants present, such as rust can
signifcantly reduce the AIT. Solutions of ethylene oxide in water may give rise to flammable
vapour. Even a 1 % solution of ethylene oxide in water has a closed cup flashpoint of 22°C. As
much water as possible should always be used for dilution. If insuffciently diluted solutions enter
sewers there may still be a flammability risk. If ethylene oxide comes into contact with certain
insulation materials it can self heat. Temperatures up to 700°C have
been recorded. Insulation fres can raise vessel wall temperatures above the auto decomposition
temperature and cause explosive decompositions.

Chemical Reactivity

Ethylene oxide is a highly reactive chemical which reacts exothermically, especially in the
presence of a catalyst, with impurities/compounds such as water, alcohols, ammonia, amines,
acids/bases and rust. These reactions can be selfaccelerating and strongly exothermic, even with
only traces of the compound present.

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Decomposition
Pure ethylene oxide vapour decomposes explosively if ignited even in the absence of air.
Ethylene oxide decomposition is initiated if the chemical is heated to about 560°C, the auto-
decomposition temperature (ADT). Decomposition is catalysed by metal acetyl ides as well as
the metals copper, silver, mercury, and their alloys. Increasing pressure lowers the ADT. The
presence of rust may also initiate decomposition at a lower temperature due to the
formation of a hot spot caused by polymerisation.

Polymerisation
Ethylene oxide is stable at room temperature in the absence of catalysts/contaminants. Purely
thermal initiation of polymerisation begins at around 100°C. Polymerisation of ethylene oxide is
highly exothermic and, if the temperature is not controlled by removal of heat at a suffcient rate,
the polymerisation is self-accelerating. This can lead to vaporisation of unreacted ethylene oxide
and also possibly to explosive decomposition of the vapour. This polymerisation can be
promoted by impurities or contamination which act as catalysts, for example by acids, bases,
metal oxides and anhydrous chlorides of iron, aluminium and tin. Therefore it is most important
to maintain clean equipment when handling ethylene oxide, and to ensure inadvertent mixing
with other chemicals does not occur. Rust is also a moderate initiator of the polymerisation
reaction of ethylene oxide. It must be thoroughly removed from any equipment containing
ethylene oxide. At ambient temperature, the polymerisation of ethylene oxide in the presence of
rust is slow. The polymer is a thermally stable viscous liquid which is soluble in the monomer. If
exposed to water at temperatures higher than 50°C the polymer will react to produce
polyethylene glycol which is sticky and diffcult to remove from equipment.

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Health hazards

Since ethylene oxide boils at 10.5°C it vaporises rapidly at ambient temperatures and
atmospheric pressure.

1. Acute Toxicity

Acute toxicity data by inhalation route indicates that Ethylene Oxide is hazardous. A study for
the inhalation route performed in rats concluded an LC50 of 3.8 mg/l for males and 3.0 mg/l for
females (Snellings et al., 2011). Thus, Ethylene Oxide is classifed as acutely toxic via inhalation,
Cat 3. Acute toxicity data by oral and dermal routes are not applicable as the test substance is a
gas on normal conditions (classifed toxic by inhalation) and no acute dermal toxicity data are
available respectively. However, in vitro studies (Wester et al., 1997 and Von Baumbach et al.,
1987) have indicated that Ethylene Oxide can be absorbed via the skin. Under normal operating
conditions, this dermal uptake is negligable, due to stringent exposure controls in place. In case
of an accidental spill, high concentrations of Ethylene Oxide and subsequent exposure may
occur. During clean-up, personnel are often well protected against exposure to Ethylene Oxide
via the inhalatory route. It is also crucial to avoid dermal exposure in such cases.

2. Aspiration Hazard

Ethylene Oxide is not known to be an aspiration hazard based on expert judgment of several
physicochemical properties of Ethylene Oxide. Its viscosity is low (0.254 mPa.s at 10 °C);
however, high water solubility and no reported cases in humans support that Ethylene Oxide is
not an aspiration hazard.

3. Irritation / Corrosion

Ethylene Oxide was tested in rabbit skin in vivo where it was found to be both irritating and
corrosive. Hyperemia and oedema resulted when the duration of skin contact was greater than 6
minutes. It can also lead to scar formation and serious burns. Ethylene Oxide was also tested in
rabbit eyes in vivo. Again, it was found to be irritating with the maximum non-damaging

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concentration of 0.1% ethylene oxide. Based on these fndings,Ethylene Oxide is classifed as an
eye and skin irritant.

4. Sensitisation

There is no valid animal study data or reliable human study data available for sensitisation in
skin or respiratory tract. Since it rapidly evaporates from the skin, ethylene oxide would not be
expected to be a skin sensitiser.

Environmental hazards

1. Acute (short-term) aquatic toxicity

The acute aquatic toxicity of Ethylene Oxide has been assessed at two different trophic levels:
fsh and invertebrates. Fish were the most sensitive trophic level tested with a 96h LC50 of 84
mg/L; daphnia were somewhat less sensitive with a 48h LC50 of between 137-300 mg/L. No
acute toxicity studies were carried out on aquatic algae, however, the toxicity of Propylene Oxide
and Ethylene Oxide are similar for fsh and daphnia, therefore, it can be assumed that the algal
toxicity is also comparable. The EC50 (96h) for Propylene Oxide on the growth rate of the green
alga Selenastrum capricornutum was measured to be 240 mg/L. Based on these data,Ethylene
Oxide may potentially be acutely harmful to aquatic organisms.

2. Chronic (long-term) aquatic toxicity

There are no studies available which assess the chronic aquatic toxicity of Ethylene Oxide.

3. Environmental fate

Ethylene Oxide achieved 96% degradation (TOC removal) after 28 days during an OECD 301C
test as well as 69% degradation after 20 days in an OECD 301D equivalent test. Ethylene Oxide
is therefore considered readily biodegradable. The calculated log Kow value of Ethylene Oxide
is low (-0.3) suggesting a low tendency to partition to organic phases and therefore a low
potential for bioaccumulationn in aquatic organisms.

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Personal safety equipment

In all situations where exposure to ethylene oxide liquid and/or vapour is possible, adequate
personal protection should be worn. As a minimum, the following should be used:

a) Eye protection: use chemical resistance safety goggles.

b) Gloves suitable for ethylene oxide

c) Suitable respiratory protective device (Compressed air/Oxygen apparatus or AX-flter)

Protective suits and boots may also need to be considered depending upon the
circumstances.Review your supplier eSDS for more information. Clothing for spill and fre:

• wear full protective clothing EO resistant gloves under gauntlet type Butyl rubber gloves/

• safety boots and approved positive pressure breathing apparatus

• remove contaminated clothing immediately, preferably under safety shower / fre hose spray

• destroy contaminated clothes, shoes and leather items

It should be noted that many materials in common use are permeable to or are attacked by
ethylene oxide. Butyl rubber has been found to give the best degree of protection. Neoprene or
natural rubber may also be considered for protective clothing, but may not remain vapour-tight
after prolonged use. Leather is permeated by liquid ethylene oxide and PVC and nitrile rubber
offer only very limited resistance. Consequently, these materials should not be used for
protection against ethylene oxide liquid or vapour. Leather, PVC or nitrile rubber footwear
should be avoided. Delayed skin burns may result if ethylene oxide is allowed to permeate
through these materials. Prior to the acquisition of the personal protective equipment (PPE),
formal confrmation needs to be obtained from the PPE-manufacturer that the PPE is resistant for
EO-use (including breakthrough / degradation time).Following contact with EO-liquid/vapours
all used gloves must be discarded.

If any leather wear does come into contact with ethylene oxide, it should be discarded
immediately because decontamination of leatherwear is not possible. Eyewash facilities and

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safety showers (frost-protected as necessary) should be provided in all areas where ethylene
oxide is handled.

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8.0 CONCLUSION

In conclusion, our team has determined that it is profitable to enter the EO market by constructing a
plant that will come on-line in two years. Our company, FKK Chemical Company has developed the
most profitable reactor train design possible. The process design focuses on a four-reactor train
utilizing the typical Shell direct oxidation catalyst. The process produces 150,000 tons of EO per
year. Considering mainly the reactor section of the process, the capital cost involved is $9.3 million,
the yearly operating cost is $92 million, and the final cumulative discounted cash flow is $350
million. These results show that construction should begin immediately in order to start-up in two
years. Several sites were not suitable for production of ethylene oxide, but are very suitable for
other economic activity such as oil palm plantation, residential area and tourism spot. However,
site-by-site study biological and archeological surveys on each of the selected sites need to be
conducted to avoid any undesirable event to occur. We also need to concern if any changes to the
selected site could affect its condition or surrounding. Soil stabilization and erosion control
should be considered during construction. Ethylene oxide industry may cause harm to the health
therefore several actions such stated above and others need to be taken. Throughout
observations, Kerteh is the most suitable spot for the production of ethylene oxide.

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REFERANCES

1. Ullman’s Encyclopedia Of Industry Chemistry

2. Hamad Alhajiri, Mohammad Alanezi, Mohammad Alrashidi and Nour Sadeqi. Design
and Optimize Ethylene Oxide Production Plant, Flourida, Flourida Of Institute
Technology
3. A. Maulijn, Jacob. Makkee, Michiel. E. Van Diepen, Annelies. Chemical Process
Technology. 2nd ed. John Wiley & Sons. Ltd. 2013. E-book.
4. Trambouze, P., Van Landeghem, H., and Wauquier, J.P. (1988) Chemical Reactors,
Design/Engineering/ Operation. Gulf Publishing Company, Houston, TX. E-book.
5. Celanese Web Site, Ethylene Oxide Users Guide 10/2/99
http://www.hcc.com/eo/contents.html
6. http://www.owlnet.rice.edu/~ceng403/gr1599/finalreport3.html
7. https://www.icis.com/resources/news/2007/11/05/9075773/ethylene-oxide-eo-
production-and-manufacturing-process/
8. http://www.tandfonline.com/doi/pdf/10.1080/03602458108068074?needAccess=true
9. https://www.lyondellbasell.com/globalassets/documents/.../ethylene-oxide-manual.pdf

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APPENDICES

Figure 1 : EO Liquid Density

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Figure 2 : EO Vapor-Pressure

Figure 3 : EO Liquid Heat Capacity

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Figure 4 : EO Liquid Viscocity

Figure 5 : Flammability Data on EO-Air Mixtures at Subatmospheric Pressure

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Table A1 : Conversion Factors

*Note that 1 means that this table only valid for EO

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