Production of Ethylene From Ethane: King Saud University College of Engineering Chemical Engineering Department

King Saud University
College of Engineering
Chemical Engineering Department
Production of
Ethylene from
Ethane
Project Team
Abdullah Albulaihed 441102682
Ziyad Almujalli 441103042
Supervised by
Dr. Mohamed K. Hadj-Kali
Dr. Jemal A. Bessadok
First Semester
1445H- (2023-2024) G
Acknowledgment
n the name of Allah, the Gracious, the Merciful. All praise is due to Allah and his peace and
blessings be upon the Prophet (PBUH).
The success and final outcome of this project required a lot of guidance and assistance from
many people and we are extremely privileged to have got this all along the completion of our
project. All that I have done is only due to such supervision and assistance and I would not forget
to thank them. We would like to express our heartfelt gratitude to our advisors Dr. Mohamed K.
Hadj-Kali and Dr. Jemal A. Bessadok for their constant guidance, encouragement, and support
throughout our work on this project. We believe that they have positively influenced us and
helped us to become better chemical engineers. We are also indebted to the Department of
Chemical Engineering at King Saud University for educating us and giving us the opportunity to
work with the wonderful faculty.
1
Problem Statement
Ethylene is a very valuable chemical component in many industries specially the petrochemicals
as it is a building block for the one of the largest industries in our time and for the future and that
is polymer industry. The current market for production of ethylene is increasing of about 6%
annually, and the current market production is 223.86 million ton annually, and Saudi Arabia is
the third largest produce and has 9% of the global capacity of production and the demand for
ethylene is driven by industries such as plastics, textiles, and agriculture. However, the
production process faces challenges in terms of efficiency, environmental impact, and economic
viability.
2
EXECUTIVE SUMMARY
The production of ethylene is crucial for mane industries and that makes it very important for the
industry chain so the investments in the ethylene production techniques is high and attracted
increasing attention from all involved parties.
This project aims to make up with the increasing annual demand of ethylene by producing one
million metric ton annually to and to help maintain Saudi Arabia as a leading country in the
ethylene market. The introductory chapter discussed the background and history of ethylene and
its applications and uses and listed the characteristic of the main component in the project. This
chapter also included statistics on the global production of ethylene and what the future holds in
terms of supply and demand and a preliminary Feasibility Study. In chapter two various
processes for the production of ethylene were locked into and studied; some of them were
discarded due to various drawbacks such as the feedstock’s availability or the lack of maturity of
the process. Based on several criteria, the process of thermal cracking of ethane with diluted
steam was selected.
Based on the information and descriptions published in the literature on the ethane cracking, an
optimal process flowsheet was developed based on many trials using CHEMCAD software to
reduce cost and waste and increase purity. The newly developed process was described in detail
in chapter two. Material and energy balances were manually calculated and listed in chapter
three along with molar flow rates, rate of enthalpy, temperatures, and pressures for each stream
and equipment involved in the process.
Chapter four provides a summary of previous accident that have occurred at ethylene production
plant and the causes and effects of accident. are also discussed in this chapter. In addition, the
flammability, toxicological data and hazards associated with each material in the process have
been identified in this chapter. The selection of the site based on various locations and criteria
was discussed and explained in chapter five. Finally, the layout of the plant was illustrated using
a proposed diagram of the plan.
3
Contents
1. Introduction............................................................................................................................3
1.1. Background and History...................................................................................................3
1.1.1 Discovery of Ethylene....................................................................................................3
1.1.2 History of Ethylene in Petrochemical Industry..............................................................4
1.2. Applications and Uses......................................................................................................5
1.3 Properties...............................................................................................................................5
1.3.2. Safety and Toxicological Properties Related to the Project..........................................6
1.4 Initial Feasibility Study and Market Survey..........................................................................7
1.4.1 Production and Consumption: Worldwide, Regional, and National..............................7
1.4.2 Preliminary Economic Analysis.....................................................................................7
Chapter Two: Process Selection and Process Description..............................................................8
2.1 Process Selection...................................................................................................................8
2.1.1 Production of Ethylene from Methanol..........................................................................8
2.1.2 Production of Ethylene by Dehydration of Ethanol.......................................................9
2.1.3 Production of Ethylene by Oxidative coupling of Methane...........................................9
2.1.4 Production of Ethylene by Cracking of Ethane............................................................10
2.1.5 Comparison of Existing Processes................................................................................11
2.1.6 Selecting process..........................................................................................................12
2.2 Detailed Description of Selected Process............................................................................12
Chapter Three: Mass and Energy Balances...................................................................................15
References......................................................................................................................................17
4
List of Tables
Table 1: Physical and Chemical Properties Related to the Project.................................................5
Table 2: Heat Capacities Coefficients of Shomate Equation in J/mol*K........................................6
Table 3: the Antoine Equation Parameters for Finding the Vaper Pressure and the Boiling
temperature .....................................................................................................................................6
Table 4: Viscosity Coefficients.......................................................................................................6
Table 5: Safety.................................................................................................................................6
Table 6: Criteria Justification........................................................................................................11
Table 7: Evaluation Scenario 1......................................................................................................12
Table 8: Evaluation Scenario 2......................................................................................................12
Table 9: List of reactions in the cracker........................................................................................15
Table 10: List of components in each stream................................................................................15
List of Figures
Figure 1: Ethylene chemical structure ............................................................................................3
Figure 2: GCC feedstock types (mtpa)............................................................................................4
Figure 3: Ethylene breakdown by key derivatives in the GCC.......................................................5
Figure 4: Ethylene production by country, 2021...............................................................................
Figure 5: GCC Ethylene production and demand .............................................................................
Figure 6: Block flow diagram for MTO process.............................................................................8
Figure 7: Block flow diagram of the dehydration of Ethanol..........................................................9
Figure 8: Block flow diagram of production of Ethylene by oxidative coupling of Methane ......9
Figure 9: Block flow diagram of production of Ethylene by cracking of Hydrocarbons..............10
Figure 10: Production of Ethylene by Ethane cracking block diagram.........................................14
Figure 11: Production of Ethylene by Ethane cracking process flow diagram.............................14
5
1. Introduction
1.1. Background and History

Ethylene is an organic compound from the family of alkenes it’s the simplest compound
from his family and from olefins known as alkene, which contains carbon-carbon double bonds.
It’s a colorless, flammable hydrocarbon gas with sweetish odor having the formula of C 2H4,
Natural sources of Ethylene include both natural gas and petroleum, and it does not exist in large
quantities in nature. [1].
Figure 2: Ethylene chemical structure [2]

1.1.1 Discovery of Ethylene
To start we must go back in time to when the Chinese ripened the hard pears by putting
them in closed rooms with incense and then burning the incense, they were ripening the pears in
the manner of “that's what their fathers before them did so” little did the Chinese people knew
that in the smoke from the incense was a gas and that gas is now known as the organic
compound Ethylene, a compound capable of effecting the physiological process of fruits,
vegetables, flowers, flower bulbs, roots, tubers and germinating seeds, and so potent a substance
as to be able to make its presence known in some instances, when present to the extent of only
one part in sixty million part of air.
but the Chinese were not the only people who utilized the Ethylene without knowing it the
ancient Egyptians did so too, but going to beginning of the present century it was customary to
ship oranges from Florida to north and markets in railroad cars that hated with kerosene stoves to
prevent them from freezing at the time it was noted that the green-colored fruits in the car
assumed the characteristics orange color do ring transit, but this was considered merely a
ripening process caused by the heat generated by the stoves.
6
In 1912 Sievers and True, walking with lemons, show that the active agent bringing about the
color change was to be found in the products of incomplete combustion of the kerosene stove
and that heat was of secondary importance. Furthermore, the fruit could be “degreened” by the
exhaust gases over gasoline motor. However, the actual identity of the coloring agent was still
unknown. In 1923 Danny suspected that this range gas was an unsaturated hydrocarbon because
he found that the fumes of the kerosene stove were rendered ineffective as a coloring agent if
they were first filtered through bromine water. Ethylene was a well-known unsaturated gas at
that time, although its property as a coloring agent were unsuspected, but when Danny
substituted small quantity of pure Ethylene for the Kerosene fumes in the coloring of citrus
fruits, he found the Ethylene was much more effective: thus began the practice of degreening
citrus fruits with Ethylene on a commercial scale[3].
1.1.2 History of Ethylene in Petrochemical Industry

in 1942 ABB Lummus Global built the first Ethylene plant. In mid 50s’ the production of
Ethylene in the world (excluding the Soviet Union) was about 1.6 MTA. Most of the production
was in the United States. Soon the production of Ethylene grew worldwide especially in the
Middle East and East Asia. Ethylene is produced mainly by hydrocarbon thermal cracking.
Figure 1 shows different types of feedstocks used in the GCC (Gulf Cooperation Council).
Ethylene production is energy intensive, so in the 70s’ during the oil crisis plant designers
focused on reducing the operating and energy cost by introducing better heat integration process
which reduced the energy requirement by 40-50%. With the improvement in the design of
thermal cracking unit and selectivity the sitting time reduced to 150-250ms[4].
Figure 3: GCC feedstock types (mtpa)[5]
7
1.2. Applications and Uses
The main industrial uses of Ethylene include polymerization, oxidation, alkylation,
halogenation, hydration, oligomerization and hydroformylation.
The primary use of Ethylene is the Polyethylene production which consumes approximately 50%
of total Ethylene supply. Polyethylene is mainly used in film. applications for packaging, carrier
bags and trash liners. The other use of Ethylene is the Ethylene Oxide production which is an
important raw material for the intermediate raw materials in the chemical industry. Ethylene
Oxide is able to react with almost all compounds which have available hydrogen such as water,
alcohols, organic acids and amines. Ethylene glycol, which is the derivative of Ethylene is used
to produce soft drinks, food packaging and textiles. In addition, Ethanol amines are used to
produce surfactants. Styrene monomer is the alkylation product of Ethylene, and the Polystyrene
form is used for packaging and insulation. In addition, the Styrene Butadiene form is used in tire
and footwear production[6]. The figure 2 shows Ethylene breakdown by key derivatives in the
GCC.
Figure 4: Ethylene breakdown by key derivatives in the GCC[5]

1.3 Properties
1.3.1 Physical and Chemical Properties Related to the Project
Table 1: Physical and Chemical Properties Related to the Project [7], [8]
Component Molecular Mw(kg/ Tb ∆Hf Tm ∆Hvap ρ(kg/ ∆Hc
Formula kmol) ( ℃ ) kJ/mol (℃ ) kJ/mol m3 ) at kJ/mol
25℃
Ethylene C2H4 28 -103 52.5 -169 14.6 1.176 -1410.9
Ethane C2H6 30 -88 -84.68 -182 15.7 1.356 -1560.3
8
Table 2: Heat Capacities Coefficients of Shomate Equation in J/mol*K[7], [8]
Cp(T)=A+BT+CT2+DT3+E/T2
3
Component A B*10 C*106 D*105 E*103 TminK TmaxK
Ethane 27.287 12.51 3.22 -0.3 -247.4 100 1500
Heat Capacity for Gases: Cp(T)(J/mol*K)=A+BT+CT +DT3 2
Ethylene 21.208 8.984 3.66 11.43 -2772.9 100 1500
This equation used to calculate the heat capacity of gases as a function of temperature it's
important to use this equation within its applicable conditions to obtain accurate results and they
are the
temperature range and the ideal gas and stable phase and the purity of components.
Table 3: the Antoine Equation Parameters for Finding the Vaper Pressure and the Boiling
temperature [7]
B
Antoine Equation ln(Pvap)= A− P(kPa)
T ( ℃ ) +C
Component A B C
Ethylene 4.01 632.83 188.43
Ethane 3.98994 622.24 184.44
Table 4: Viscosity Coefficients’[7], [9], [10]

Component T(K) At 298K 1atm
A*106 B C
'
Ethane 1.5
Sutherlan d s Law μ ¿ )=A*(T )/(T+C)
1.55^0.5 - 305
Ethylene Andrade Equation μ ¿)=A* exp(B/(T+C))
197 959 194
The coefficients to calculate the viscosity in different temperatures within the atmospheric
pressure
1.3.2. Safety and Toxicological Properties Related to the Project

Table 5: Safety[11]–[14]
Component AIT (K) LFL (vol UFL (vol FP (K) AOT AIT Exposure
%) %) (LD50) (Rat) limit mg/m3
(Rat) (LC50) TLV-TWA
(mg/m3) (ppm )
Ethylene 720 2.7 32.2 138 N/A N/A N/A

9
Ethane 560 1.8 8.4 169 N/A N/A 1890
10
1.4 Initial Feasibility Study and Market Survey
1.4.1 Production and Consumption: Worldwide, Regional, and National
The global Ethylene capacity was 223.86 mtpa in 2022 and is expected to grow at an
average annual growth rate (AAGR) of more than 6% during 2022-2027. In 2022, China, the US,
Saudi Arabia, South Korea, and Iran were the key countries in the world accounting for over
60% of the total Ethylene capacity[15]. The GCC production capacity in 2021 was 26.5 mtpa.
Which represent 12% of the global production. GCC is the third largest production hup of
Ethylene after USA 17%, and China 15%. Ethylene generates USD 1-1.5 bn per year to GCC
economy. Saudi Arabia represent 68.8% of the GCC production (figure 3)[5], the main
production companies at the national level are SABIC, Shell Global and ExxonMobil Corp[16].
Figure 5: GCC Ethylene production Figure 6: Ethylene production by

and demand [4] country, 2021[4]
1.4.2 Potential Gross Profit

The average price of one metric ton of ethylene is 1000$ USD [17], the average price of
one metric ton of ethane in Saudia Arabia is 86.1$ USD [18], and in this project the aim is to
produce 1 million metric ton annually of ethylene, the feed required of ethane to produce this
amount is calculated to 1.528 kmol/s
days
∗kg
kmol kmol s∗24 kg year
1.528 =1.528 ∗3600 ∗30 ∗330 =1.307 ×10 6 mtpa
s s h kmol 1000 ton
To calculate the gross profit = price of selling ethylene* amount of ethylene produced - price of
buying ethane* amount of ethane consumed in the feed= profit
6 6
1 ×10 ∗1000 $−1.307 ×10 ∗86.1 $=887.5 million $ USD / year
11
For the project to be profitable the separated capital cost of equipment on the life time of the
plant and the annual operation cost must be less than 887.5 million$.
12
Chapter Two: Process Selection and Process Description
2.1 Process Selection

Ethylene is produced via many processes, such as Methanol to olefins (MTO), and the
second process is the dehydration of Ethanol, and the third process is the Production of Ethylene
by Oxidative coupling of Methane, and the fourth process is the cracking of Ethane.
2.1.1 Production of Ethylene from Methanol
Figure 7: Block flow diagram for MTO process
Methanol is used in this process as a feed stock, and Methanol also known as Methyl
alcohol, which is a chemical with the formula CH 3OH and often abbreviated as MeOH. It is the
simplest alcohol with a methyl group linked to a hydroxyl group. Methanol is an important
ingredient in low cost method especially Ethylene plant for producing Ethylene and the price of
Methanol is 400$/ton[19]. In the production of Ethylene from Methanol the process starts with
transforming the Methanol to olefin (MTO) at the reactor with the SAPO-34 as a catalyst at a
temperature about 450℃ , then the purification and the separation of the product. the MOT
process is into second separation stage where processes like C2-splitting and C3- described into
four stages which are reaction stage, conditioning stage, first separation stage, and second
separation stage. In the reaction stage and conditioning stage, the raw material – Methanol is
converted into olefins mixture, The olefin rich stream will be forward for fractionation and
convert to light olefin such as Ethylene and Propylene. According to Wahabi [20], nearly 80% of
the carbon in the Methanol feed has been converted into Ethylene and Propylene in MTO
process. Block Flow Diagram (BFD) of MTO process is illustrated and shown in Figure 6. The
proposed BFD is to be referred for equipment selection sample. With an optimized operating
condition, the production of Propylene to Ethylene can achieve a ratio of 1.5 to 0.75.
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2.1.2 Production of Ethylene by Dehydration of Ethanol
Figure 8: Block flow diagram of the dehydration of Ethanol
The dehydration reaction of Ethanol to yield Ethylene C2H5OH  H2O + C2H4 and it
is a zero-order reaction and endothermic, the process use the Ethanol as a feed stock and the it’s
also known as Ethyl alcohol, which has the chemical formula CH3CH2OH with a price in the
Middle East is about 500$/ton, the process use a high temperature reactor operating at near 400
C to shift the reaction equilibrium to the product favor to produce Ethylene with high conversion
rate. Additionally the reaction over γ-Alumina yields an overall conversion of 98% with a
selectivity to Ethylene of 98% a number of byproducts that’s needs removal through the
separation system[21]. Block Flow Diagram (BFD) of Ethanol dehydration process is illustrated
and shown in Error: Reference source not found The proposed BFD is to be referred for
equipment selection sample.
2.1.3 Production of Ethylene by Oxidative coupling of Methane
Figure 9: Block flow diagram of production of Ethylene by oxidative coupling of Methane [25]
Direct methods for converting Methane into more valuable products including olefins and
high molecular weight hydrocarbons have recently attracted great interest in the area of
14
heterogeneous catalysis. Methane, the main component of biogas and natural gas, will be a
primary source of hydrocarbons for the manufacture of useful chemicals and liquid fuels in the
future. At present, the industrial conversion of Methane into higher added value products is
possible indirectly by the synthesis gas route, but this is only commercially viable on a large
scale. However, The oxidative coupling of Methane (OCM) represents an interesting alternative
process for producing Ethylene, typically manufactured in steam-crackers from naphtha[22]. A
complete OCM process, as shown in Figure 7, consists mainly of three units: OCM reaction
that’s operate at a temperature near 800 ℃ , purification for CO2 separation and demethanizer
for CH4 recycling. The preheated natural gas and oxygen are continuously fed into the OCM
reactor, and the reacted effluent mixture is led to the separation unit where it is cooled, and its
CO2 removed. Then, the resultant CO2-purified stream is sent to a demethanizer to separate the
unreacted CH4 and simultaneously produce C2H4 and C2H6 product. Although much effort has
been made over the past 40 years on improving the Methane conversion and Ethylene selectivity
at various OCM conditions, the Ethylene yields have not yet reached a minimum level of 30%
(about 35% single-pass Methane conversion and 88% C2+ selectivity) required for
commercialization of the reaction[23].
2.1.4 Production of Ethylene by Cracking of Ethane
Figure 10: Block flow diagram of production of Ethylene by cracking of Hydrocarbons
The modern Ethylene plant usually has a yield of billions of pounds per year. The
majority of the processes are thermal pyrolysis of hydrocarbons, which is mixed with dilution
steam[24]. The whole process works in this way. The feedstocks, mixed with dilution steam,
enters the cracking section that’s operate at a temperature near to 900 ℃ and is pyrolysised by
heat into small components. The pyrolysis gas enters the quench section and is cooled there to
some controlled temperature. Finally, the pyrolysis gas goes into the separation section to be
15
separated into a variety of desired final products. Water enters the water quench tower, a part of
quench section, cooling down the high temperature pyrolysis gas and becoming steam. That
steam, called dilution steam, mixes with the feedstock before entering the pyrolysis section to
decrease the partial pressure of the cracked gases and slow coke formation. A variety of
feedstocks can be used in a thermal cracking process. The feedstock for an Ethylene plant could
be Methane, Ethane, Propane, and naphtha. The choice of feedstock is a compromise of
availability, price, and yield.
2.1.5 Comparison of Existing Processes

Studying the alternatives to any process plays a significant part in determining how the
specifications might affect our choices. Additionally, creating a practical path to meet the
process specifications has its own challenges without considering comparison of these
alternatives. Making a multi-criteria table is useful for making decisions and actions. These
criteria and arguments will be considered in our weighting and rate matrix that will provide a
clear indicator of the process that is most likely to succeed Table demonstrates the main criteria
and specifications that our process will build on.
A- Pre-Excluding Processes
The processes of Ethylene from Methanol (MTO) and of Ethanol dehydration has been excluded
from the evaluation process due to the unavailability of Methanol and Ethanol at an industrial
scale and they are the feed stocks of the processes feed stock in Saudia Arabia where the plant is
decided to be built at
B- Criteria and the Scenarios Evaluation

Table 6: Criteria Justification
Criteria Justification
High conversion Different raw materials impact the conversion
due to their reaction mechanisms
High selectivity Each raw material has different yield% of
Ethylene
Raw material cost Lower raw material price can affect
profitability
Maturity of the process The presence of the process globally due to
continues improvement in their productivity
and efficiency
Feed stock availability The rate of the feed is a major factor in
16
deciding the production capacity
Low carbon emissions Lower carbon emissions is better for the
environment and the operation cost
Low energy consumption The lower energy is consumed the cheaper the
operational cost become
Table 7: Evaluation Scenario 1
Scenari Production Capacity
o
Criteria
High High Raw Maturit Feed Energy carbon Scor
Process conversio selectivit materia y of the stock consumptio emission e
n y l cost process availabilit n s
y
Weight(W) 20 20 5 20 25 5 5 100
%
OCM Rate (R) 3 6 10 1 10 3 5 540
WxR 60 120 50 20 250 15 25
Ethane Rate (R) 7 8 8 9 9 2 2 765
crackin WxR 140 160 40 180 225 10 10
g
Table 8: Evaluation Scenario 2

Scenari Environment Friendly
o
Criteria
High High Raw Maturity Feed stock Energy carbon Score
Process conversion selectivity materia of the availability consumption emissions
l cost process
Weight(W)% 10 20 5 5 5 20 35 100
OCM Rate (R) 3 6 10 1 10 3 5 490
WxR 30 120 50 5 50 60 175
Ethane Rate (R) 7 8 8 9 9 2 2 470
crackin WxR 70 160 40 45 45 40 70
g
2.1.6 Selecting process
Based on the evaluation and we prioritized the production capacity, we concluded that the
Ethane cracking is the best process for production of Ethylene. Yet the Ethane cracking doesn’t
score high in the environment friendly scenario but there are ways to mitigate the energy
consumption by energy integration.
17
2.2 Detailed Description of Selected Process
Ethane is mixed with delution steam and enters the convection section in the cracker and
heated approximately to 600℃ . The delution steam is added to reduce coke formation. The
mixer then is briefly heated to 750-900 ℃ and the Ethane start cracking. The cracked gas is
cooled via transfare line exchenger ( TLE ) to stop further reaction. The cracked then cooled to
nearly 35℃ in quenching tower. The cracked gas leaving the quench tower is compressed to 25-
35 bar in a three stage compressors and maintaining a maximum temperature of 100 ℃ to
prevent any further reaction, Between each compression stage are condensing exchangers and
knock-out drums to separate water and condensed hydrocarbon for processing in other areas of
the plant. While the free water is removed between each stage of compression, the complete
removal of water is essential in preparation for cryogenic separation and is achieved with
adsorption over molecular sieves. Typically, the system consists of two dryers, with one in
normal operation while the other is being regenerated. The dryers are designed for an on-stream
time of 24 to 36 hours between successive regenerations. High-pressure Methane, heated with
steam to 225°C, normally is used as the regeneration medium because this stream is dry and
easily available within the Ethylene plant. The cracked gas is typically chilled with refrigerant to
reduce the saturated water amount entering the dryer, thus limiting the size and capital cost. The
chilling temperature is kept above the hydrate formation temperature, which depends on the
system pressure and charge gas composition. The cracked gas leaving the dryers is fed to the
high pressure (HP) deethanizer to separate C2 and lighter components from C3+ components.
The overhead from the HP deethanizer which contains C2 and lighter components is heated
before being fed to the Acetylene converter reactors. The converter system selectively
hydrogenates Acetylene to Ethylene and Ethane. The net overhead from the HP deethanizer,
which contains the C2 and lighter components of the charge gas, is then fed to the chilling train.
The chilling train involves the successive chilling of the charge gas at essentially constant
pressure. The stage condensates are separated and fed to the appropriate location of the
demethanizer tower. Hydrogen (typically 95 mol% purity) is withdrawn from the lowest
temperature stage separator. The overhead from the demethanizer tower essentially consists of
Methane and some Ethylene. The C2s the demethanizer bottoms are The Ethylene/Ethane
mixture in the C2 stream is fed to the Ethylene fractionator. The mixture is fractionated to
18
recover a polymer-grade Ethylene product. The Ethane, drawn from the bottom of tower goes to
recycling.
Figure 11: Production of Ethylene by Ethane cracking block diagram
19
20
M-101,102 R-101,102 E-10(1-5) C-101 D-101 T-101,102,103
Mixer Reactor Heat Compressor Dryer Fractionator

Exchanger
5
E-101 R-101 C-101 D-101
M-101
3
1 2 M-102 E-102
7
6 8 9
4
10
T-102 T-103
T-101 18 19 21
E-103 13 E-104 R-102 F-101
E-105
14 15 16 17
11
20
12
22
Figure 12: Production of Ethylene by Ethane cracking process flow diagram
21
22
Unit Description
Table 9: Unit Description

No. Unit Name Description
1 Mixer M-101 Adiabatic mixing between the feed and the recycle stream of pure
ethane
2 HEX E-101 Pre heater where pure ethane is heated to 300C before entering the
cracker
3 Mixer M-102 Adiabatic mixer where steam at a weight ratio of 0.35
steam/ethane is mixed with ethane at 300C
4 Cracker R-101 Pyrolysis Ethane into many components, the cracker operates at
825C and 3bar
5 HEX E-102 Quenching, where the hot cracker effluent gases are quickly
cooled from 825C to 65C, to stop the reaction ,then further cooled
to 35C
6 Compressor C- Compresses the gases to 25bar and maintain a maximum
101 temperature of 100C to prevent any reaction from accruing
7 Dryer D-101 Rejects all the water in the stream
8 HEX E-103 Cool the stream from 100C to 15C before enter the fractionator as
super-heated
9 Fractionator T- Separate the C3+ and heavier hydro carbons from the C2 and H 2,
101 the distillate leaves as vapor at -38C
10 HEX E-104 Heat the stream to 30C to prepare it for the hydrotreater reactor
11 Reactor R-102 Adiabatic Hydrotreater reactor, which react all the acetylene,
leaves at 50C
12 HEX E-105 Cools the stream to -27 to prepare it to enter the fractionator
saturated-liq
13 Flash F-101 Separate all the hydrogen and traces of methane at purity of 95%
H2
14 Fractionator T- Separate the methane from the C2 hydrocarbons, the bottom
102 leaves as sat-liq at -14C, and the distillate is methane gas at -100C
15 Fractionator T- Separate the ethylene(top) from ethane(bottom) in a binary
103 component column, where the distillate is at -20 and a purity of
99.9% ethylene, where the liquid methane is at 2C then recycled
to be mixed with the feed
Chapter Three: Mass and Energy Balances

Material balances are required for all processes. Material balance entails calculating the
quantities of all materials that enter and exit any system or process using the "law of
conversation of mass" principle. This law states that matter is neither created nor destroyed. The
general principle of material balance calculations is to solve a number of independent equations
involving a number of unknowns of compositions and mass flow rates of streams that entered
23
and discharged from the system or process. The general steady state material equation balance
for
component j is as follows:
¿
¿
3.1 List of Assumptions

 Steady state process.
 330 days plant operation.
 35 days shutdown period.
 24hr/day working period.
 1000000 tones/year Ethylene production.
 The feed to the crackers is Ethane and Steam with 0.35 kg steam/kg ethane ratio.
 Reference condition for all the component are 25℃ gas phase.
3.2 Degree of Freedom

An analysis of the degrees of freedom of the main units was carried out to check if the process
could be calculated. The unknowns in the process are taken as the number of components in each
stream associated with the unit and the number of reactions, if any.
From the degrees of freedom analysis in Table 10, it appears that the calculations can begin with
the material balance of the reactor, R-101.
N DOF=N Unknowns −N Independent equations (2)
 If N DOF = 0, problem can be solved (in principle).

 if N DOF > 0, problem is underspecified and at least N DOF additional variables must be
specified before the remaining variable values can be determined.
 if N DOF < 0, the problem is overspecified with redundant and possibly inconsistent
relations.
Table 10: Degree of freedom for the hot section

Unit M- M- R- E-101 C-101 D-101 T- R-
101 102 (101- 101 106
DOF 105)
# Variables 3 4 11 18 18 18 18 16
# MB -1 -2 -9 -9 -9 -9 -8 -8
24
# Flowrates 0 -1 -1 0 0 0 0 0
# 0 -1 -1 0 0 0 -1 0
Composition
Reactions 0 0 5 0 0 0 0 2
Relations 0 0 -5 0 0 -1 0 0
Total 2 0 0 9 9 8 9 10
Table 11: Degree of freedom for the cold section

Unit E-102 F-101 T-102 T-103 T-104 T-105
DOF
# Variables 18 17 15 14 11 10
# MB -8 -8 -7 -6 -4 -4
# Flowrates 0 0 0 0 -0 0
# Composition 0 -1 -1 0 -1 -1
Reactions 0 0 0 0 0 0
Relations 0 -1 0 -1 0 0
Total 10 7 7 7 6 5
( Rate of Enthalpy j out ) + ( Rate of Heat of Reaction ) −¿

¿
Thermodynamic Properties:
Energy balance mostly depends on the heat capacity ( C Jpstate) of both vapor and liquid phase,
heat of reaction (HR ) and latent heat (H V ¿ of various materials. The following tables serves as a
reference to the upcoming calculations of energy balance:
Table 12: Heat Capacity Coefficient of Gases
Cp gas = A+ B∗T +C∗(T 2)+ D∗(T 3)+ E∗( T 4 ) Cp (kJ/(kmol K)) T (K)
NAME Formula MW A B C D E Tmin Tmax
ethane C2H6 30.070 28.146 0.04345 1.8946E-04 -1.908E-07 5.3349E-11 100 1500
ethylene C2H4 28.054 32.083 -0.01483 2.4774E-04 -2.377E-07 6.8274E-11 60 1500
methane CH4 16.043 34.942 -0.03996 1.9184E-04 -1.530E-07 3.9321E-11 50 1500
butadiene (1,3 C4H6 54.092 18.835 0.20473 6.2485E-05 -1.715E-07 6.0858E-11 100 1500
butadiene)
propylene C3H6 42.081 31.298 0.07245 1.9481E-04 -2.158E-07 6.2974E-11 90 1500
acetylene C2H2 26.038 19.36 0.11519 -1.2374E-04 7.237E-08 -1.6590E-11 200 1500
propane C3H8 44.097 28.277 0.11600 1.9597E-04 -2.327E-07 6.8669E-11 100 1500
25
Table 13: Heat Capacity Coefficient of Hydrogen and Water
Component A B*103 C*106 D*10-5 TminK TmaxK
Heat Capacity for Gases: Cp(T)(kJ/kmol*K)= A+ BT +C T 2 + D T −2
Water 30.092 1.86E- 1.13E-05 -2.80E+05 100 1500
02
Hydrogen 20.786 4.80E- -3.05E-07 8.20E+03 100 1500
03
Heat Capacity for Liquids
Water 72.43157 0.0104 -1.50E-06 0 0 100
( )
n
T
Table 14: the parameters to find the ∆Hvap at different temp ∆Hvap(kJ/mol)= A 1−
Tc
Name Formula MW A Tc n Tmin Tmax Tb ∆Hf
ethane C2H6 30.07 21.342 305.42 0.403 90.35 305.42 184.55 -84.68
ethylene C2H4 28.054 19.986 282.36 0.431 103.97 282.36 169.47 52.5
methane CH4 16.043 10.312 190.58 0.265 90.67 190.58 111.66 -74.9
butadiene C4H6 54.092 35.17 425.37 0.448 200 425.37 268.74 98
(1,3
butadiene)
propylene C3H6 42.081 26.098 364.76 0.358 87.9 364.76 225.43 20.4
acetylene C2H2 26.038 16.74 308.32 -0.056 192.4 200 189.15 227
propane C3H8 44.097 26.89 369.82 0.365 85.44 369.82 231.11 -104.6
Hydrogen H2 2.016 - - - - - - 0
( )
T2 0.38
∆H vap 1−T r 2 Ti
For water the ∆Hvap is calculated through Watson method = ;T ri =
, T =T b /T C
∆H
Tb
vap
1−T r 1 Tc r 1
Water H2O 18.015 - - - Tb kJ -241.82
∆ H vap=44
mol
Table 15: Heat of reaction for all the reactions

Reactions ∆H f r ∆H f P ^
H °rxn=∆ H f P-∆ H f r
of reactant of products (kJ/mol)
C2H6 ↔ C2H4 + H2 -84.68 52.5 + 0 137.18
C3H6 ↔ C2H2 + CH4 20.4 227 + -74.9 132.18
C2H2 + C2H4 → C4H6 227 + 52.5 98 -181.98
2C2H6 → C3H8 + CH4 2*-84.68 -104.6 + -74.9 -10.14
C2H4 + C2H6 → C3H6 + CH4 52.5 + -84.68 20.4 + -74.9 22.32
C2H2 + H2 → C2H4 227 + 0 52.5 -174.98
26
C2H2 + 2H2 → C2H6 227 + 2*0 -84.68 -312.16
Most processes in industry are at steady-state procedure. Therefore, the accumulation term equal
to zero. For open steady-state system, the first law is:
Q+W S=∆ H+ ∆ E K + ∆ E P
( 3)
Where:
Q : Energy (kW)
W S: shaft work (kW)
∆ H : Enthalpy (kW)
∆ E K : kinetic energy (kW)
∆ E P : potential energy (kW)
There are no moving parts in the system and no energy is transferred by electricity or radiation,
so W S = 0. No significant vertical distance separates the inlet and outlet ports, so ∆ E P = 0. Phase
changes and non-negligible temperature change occur, so ∆ E K = 0 (relative to H ). The energy
balance equation (3) reduces to:
Q=H (4)
Energy balance calculation equations
No phase change: Enthalpy Calculations (No Phase Change)

The enthalpy of component J in any stream without phase change is given by Eq. (5).
[ ] [ ]
T out Tin
J
H = ṅ
i
J
out ∫C J
p
J
dT − ṅ
¿ ∫ C Jp dT (5)
Tref Tref
27
Phase change: Enthalpy Calculations (Phase Change)
In the case of a phase change and no reaction, the enthalpy of component J is calculated
according to Eq. (2.10).
[∫ ] [∫ ]
T out Tin
J J J J J
H= ṅ out C dT − ṅ
p ¿ C p dT + ṅi ∗H v (6)
Tref Tref
Heat of Vaporization at different Temperatures: Enthalpy Calculations (Phase Change)

To calculate the heat of vaporization in a temperature other than the normal boiling point, two
method was used Steam table for water and for other component Eq.(7):
( )
n
T
∆ H vap= A ¿ 1− (7)
Tc
Reaction: Enthalpy Calculations (Reaction)

The enthalpy of component J in any stream with reaction can be calculated through the heat of
formation is given by Eq. (9):
^
H °rxn=∆ H f P -∆ H f r (8)
Heat Loads (Without Reactions)

Heat loads (Q) for all units are given by Eq. (9).
Q= ∑ outputs ṅJout J
H out - ∑ input ṅJ¿ J
H¿ (9)
28
Heat Loads (With Reactions)
Heat loads (Q) for all units are given by Eq. (11).
[ ] [ ]
T out Tin
J
H = ṅ
i
J
out ∫C J
p dT − ṅ
J
¿ ∫ C Jp dT + Ʃ( ^
H ° rxni∗ξ i) (10)
Tref Tref
Assumption
The specific enthalpy is a function of temperature and pressure. However, an ideal state is
assumed due to the low-pressure condition and the effect of pressure on enthalpy is neglected. A
convenient way to tabulate measured change in specific enthalpy is to choose a temperature,
pressure, and state of aggregation as a reference state. Since the choice has no effect on change
in enthalpy Δ𝐻. Therefore, the reference state assumed to be (25 °C, 1 bar, and gas).
3.3 Material & Energy Balance

Table 16: List of reactions in the cracker[25]
NO Reaction Forward reaction Reverse reaction
A (s-1) or (L (mol.s)-1) A (L (mol.s)-1)
E (kJ mol-1) E (kJ mol-1)
1 C2H6 ↔ C2H4 + H2 A=4.65 x1013 A=8.75 x108

E=272.8 E=136.5
2 C3H6 ↔ C2H2 + CH4 A=9.81 x108 A=3.81 x104
E=154.58 E=29.48
3 C2H2 + C2H4 → C4H6 A=1.0 x1015
E=172.6
4 2C2H6 → C3H8 + CH4 A=3.8 x1011
E=273.0
5 C2H4 + C2H6 → C3H6 + CH4 A=7.0 x1016
E=252.8
Let: A≡ethane, B≡propane, M≡methane, H≡H2, E≡ethylene, P≡propylene, AC≡acetylene, U≡

butadiene, W≡Water
ṅ Ji=molar flowrate for stream i and component J
J&Z∈{A,B,E,H,M,AC,P,U,W}
yJi= molar fraction in the vapor phase of component J in stream
i yJi=ṅ Ji/nTi (11)
29
xJi= molar fraction in the liquid phase of component J in stream
i xJi=ṅJi/nTi (12)
J
ṅ Ti= the total molar flowrate in stream i=∑ ṅJi
Z
ξ: is the extent of reaction a quantity that measures the extent to which the reaction has
proceeded. Often, it refers specifically to the value of the extent of reaction when equilibrium has
been reached. It is usually denoted by the Greek letter ξ .
ṅ J out=ṅ J ∈+ Ʃ ν i∗ξ i(13)
moles of desired component E

Selectivity= = (14)
moles of undesired component H + B+ M + AC +U + P
feed of limiting component −outlet of limiting component A ¿− A out

Conversion= = ( 15 )
feed of limiting component A¿
moles of desired
Yield=
moles reacted of limiting component
C2H6 ↔ C2H4 + H2 ξ1=ṅ6H

C3H6 ↔ C2H2 + CH4 ξ2=ṅ6B
C2H2 + C2H4 → C4H6 ξ3=ṅ6AC
2C2H6 → C3H8 + CH4 ξ4=ṅ6U
C2H4 + C2H6 → C3H6 + CH4 ξ5=ṅ6P+ ξ3
30
−E
k i=A i × e RT
( 16 )
r i=k i ∏ C j
αj
( 17 )
F j PT
C j=
F T RT
( 18 )
Where:
k: Rate coefficient (s-1 or L/mol.s).
r: Rate of reaction (kmol/m3.s).
F: Molar flow rate (kmol/s).
C: Concentration (kmol/m3).
Table 17: Rate expression and rate coefficient
Rate expression Rate coefficient (s-1) or (L KC
(mol.s)-1)
CE × CH 29.9 0.0441
−r 1=k 1 [C A − ]
Kc
C AC ×C M 131 0.0461
−r 2=k 2 [C P− ]
Kc
−r 3=k 3 [C E ×C AC ] 19500
−r 4=k 4 [C A ] 0.249
−r 5=k 5 [C A × C E ] 358
Practical industrial data Data used in the reactor

Length (m) Up to 100 95
Diameter (m) 0.1-0.15 0.12
P (bar) 1.2-3 3
T℃ 680-900 825
Conversion 60% - 70% 67.4%
Yield 70 – 85
Tube/Reactor 20 20
Production of E/Tube 10,000 10,000
(ton annually )
Material balance for R-101

Cracker reactor, where the ethane gas is thermally cracked to produce mainly ethylene and side
reaction produces hydrogen, butadiene, methane, propylene, acetylene, and propane.
31
By using equation (1) the general material balance equation for R-101 is:
Stream 6 information
Stream 5 information 5 R-101 T=825C, P=3 bar
T=300 ℃ , P=1 bar
Phase: gas
Phase: gas
Component out
Component in
6 J
A&S
¿
 To produce one million tom of ethylene per year, and the production capacity of each
1,000,000 ton/ year
tube is 10,000 ton/year N tube = =100 tube , and from the practical
10,000 ton /tube year
100 tube
data teach reactor has 20 tubes, N treactor = =5 reactors are needed .
20 tube/reactor
 For each tube the molar flow rate of ethylene is
kg year day h
∗1 ∗1 ∗1 ∗1
ton ton day h s kmol
¿ 10,000 ∗1000 =0.01253 kmol /s
year 330 24 3600 28 kg
 The molar flow rate of ethylene in each reactor
kmol tube kmol

0.01253 ∗20 =0.2506
tube reactor reactor
 The total feed for each reactor is given by the relation
ethylene produced 0.2506 kmol

ethane feed= = =0.4514
Yield∗conversion 0.674∗0.824 s
 The total feed for all the reactors:
N treactor∗ethane feed kmol

=5∗0.4514=2.257
reactor s
32
kg water
 The ratio of steam to ethane is 0.35
kg ethane
0.4514 kmol steam

∗30 kg ∗kmol
s kg ethane kmol
FS= ∗0.35 kg =0. 2633
kmol 18 kg s
Differential material balance equations:
dFA
=(−r 1−r 4−r 5 ) Ai
dL
dFE
=( r 1−r 3−r 5 ) Ai
dL
dFH
=( r 1 ) Ai
dL
dFB r 2
dL
=
2( )
Ai
dFM
dL
=
r2
2 (+r 4+r 5 Ai )
dFP
=(−r 4 +r 5 ) Ai
dL
dFAC
=( r 5−r 3 ) Ai
dL
dFU
=( r 3 ) Ai
dL
Ai is the cross sectional area of the tube = 0.011304 m2, L= 95 m
kg water
The ratio of steam to ethane is 0.35
kg ethane
0.4514 kmol steam
∗30 kg ∗kmol
s kg ethane kmol
FS= ∗0.35 kg =0. 2633
kmol 18 kg s
Solving the differential equations at the same time in polymath we get:
33
Table 18: Calculated values of DEQ variables
Variable Initial value Minimal value Maximal value Final value
1 Ai 0.011304 0.011304 0.011304 0.011304
2 D 0.12 0.12 0.12 0.12
3 FA 0.4154 0.1471447 0.4154 0.1471447
4 FAC 0 0 0.003471 0.0032517
5 FB 0 0 0.0013123 0.0013123
6 FE 0 0 0.250522 0.250522
7 FH 0 0 0.2822457 0.2822457
8 FM 0 0 0.0362878 0.0362878
9 FP 0 0 0.004154 0.0037944
10 FS 0.2633167 0.2633167 0.2633167 0.2633167
11 FT 0.7147167 0.7147167 1.000214 1.000214
12 FU 0 0 0.0123389 0.0123389
13 K1 29.9 29.9 29.9 29.9
14 K2 0.249 0.249 0.249 0.249
15 K3 14.8 14.8 14.8 14.8
16 K4 16.1 16.1 16.1 16.1
17 K5 131. 131. 131. 131.
18 K6 1.95E+04 1.95E+04 1.95E+04 1.95E+04
19 K7 1.38 1.38 1.38 1.38
20 K8 358. 358. 358. 358.
21 KC1 0.0441 0.0441 0.0441 0.0441
22 KC5 0.0461 0.0461 0.0461 0.0461
23 L 0 0 95. 95.
24 P 0.0331918 0.0331918 0.0331918 0.0331918
25 Pressure 3.03E+05 3.03E+05 3.03E+05 3.03E+05
26 R 8.314 8.314 8.314 8.314
27 r1 -0.6268002 -0.6268002 -0.0932066 -0.0932066
28 r10 0 0 0 0
29 r2 -0.0052198 -0.0052198 -0.0012159 -0.0012159
30 r3 0 0 0 0
31 r4 0 0 0 0
32 r5 0 -0.0187619 0 -0.0161255
33 r6 0 -0.0182426 0 -0.0174928
34 r7 0 0 0 0
35 r8 0 -0.0222622 0 -0.0145328
36 r9 0 0 0 0
37 T 1098. 1098. 1098. 1098.
34
Table 19: Material & Energy information of stream 5&6
ṅ5 (kmol/s) Ḣ 5 (kW) Ḣ 6J (kW)
J J J
Component ṅ6 (kmol/s)
T=300℃ , P=1 bar T=825℃ , P=3 bar
A 2.257 44400 0.7357 56470
E 0.000 0.000 1.253 75620
H 0.000 0.000 1.411 27090
M 0.000 0.000 0.1814 8317
U 0.000 0.000 0.1046 11910
P 0.000 0.000 0.015235 1399
AC 0.000 0.000 0.01626 766.9
B 0.000 0.000 0.007436 817.4
S 1.317 14032 1.317 50890
Total 3.651 58430 3.717 233300
A↔E+H ξ1=ṅ 6H ξ1=ṅ 6H=1.411 kmol/s

2A→B+M ξ2=ṅ 6B ξ2=ṅ 6B=0.007436 kmol/s
P↔AC+M ξ3=ṅ 6AC+ ξ4 ξ3=ṅ 6AC=0.01626+0.1046=0.1209 kmol/s
AC+E→U ξ4=ṅ 6U ξ4=ṅ 6U=0.1046 kmol/s
E+A→P+M ξ5=ṅ 6P+ ξ3 ξ5=ṅ 6P+ξ3= 0.015235+ ξ3=0.0315 kmol/s
A A
ṅ5 −ṅ6 2.257−0.7357
Conversion of A= A
= ∗100.0=67.4 %
ṅ 5
2.257
Selectivity
E 1.253
¿ = =0.7367
H+ B+ M + AC +U + P 1.411+ 0.1814+0.1046 + ( 1.524+1.626 +0.7436 )∗10−3
E 1.253
Yield= = =0.824
A∗conversion 2.257∗0.674
Energy Balance Calculation for R-101

Stream 5 enthalpy calculation
Ethane Energy balance
573
H˙ 5 =2.334 ∫ 28.146+0.04345∗T + 1.8946E-04∗( T ) +−1.908E-07∗( T ) +5.3349E-11∗(T )dT=44400 kW
A 2 3 4
298
35
And for steam
573
H˙ 5 =1.317 ∫ 30.092+1.86E-02∗T + 1.13E-05∗T +−2.80E+05 ¿ T dT =14032 kW
A 2 −2
298
∑ H 5J =44400+14030=58430 kW
Stream 6 enthalpy calculation

Ethane Energy balance
1098
A˙
H˙ 6 =n6 ∫ 28.146+0.04345∗T +1.8946E-04∗( T 2 ) +−1.908E-07∗( T 3 ) +5.3349E-11∗(T 4 )dT =56470 kW
A
298
Same for E&H&M&U&P&AC&B&S

∑ H J6=23330 kW
Enthalpy for the reaction
1-By heat of formation:
Eq(8) using data from table 15
Ʃ( ^
H °J-Sf *ṅ6J-S) - Ʃ( ^
H °Af *ṅ 5A)= 0.7357(-84680)+1.253(52500)+0.1814(-74900)+0.1046(98000)+
0.01524(20400)+0.01626(227000)+0.007436(-104600) – (2.334(-84680))=201010kW
2-By heat of reaction from table 15
∑ ( ^H °rxni∗ξi)= 1.411(137180)+0.007436(-10140)+0.1209(132180)+ 0.1046(-181980)+

1
0.0315(-22320)=189700kW
573
H °rxni*ξi)- Ʃ ¿5J¿ ∫ Cp dT )=233300+189700 -58430=364600kW

Q=Ʃ ¿) + Ʃ( ^ J
Tref
By using heat of formation method for energy balance for the reactor:
573
Q=Ʃ ¿) - Ʃ ¿5 ¿ ∫ CpJ dT )+ Ʃ( ^
J
H °J-Sf *ṅ 6J-S) - Ʃ( ^
H °Af *ṅ5A)
Tref
36
=233300-58430+3367-(-197600)=375800
Material balance for E-102:

Quenching Tower, where the effluent cracker gases are quickly cooled to stop the reaction from
826℃ to 64℃ then further cooled to 35℃
T=825C, P=3 bar E-102 Stream 7 information
T=35C, P=3 bar
Phase: gas 6 7 Phase: gas
Component in Component out
J J
By using equation (1)&(2) the general material balance equation for M-101 is:
¿
J J
ṅ6 =ṅ 7
Table 20:Material & Energy information of stream 6&7

Component J
ṅ6 (kmol/s) Ḣ 6J (kW) J
ṅ7 (kmol/s) Ḣ 7J (kW)
T=825C, P=3 bar T=35C, P=3 bar
A 0.7357 56470 0.7357 396.2
E 1.253 75620 1.253 554.9
H 1.411 27090 1.411 315.7
M 0.1814 8317 0.1814 66.27
U 0.1046 11910 0.1046 86.15
P 0.015235 1399 0.015235 10.00
AC 0.01626 766.9 0.01626 7.280
B 0.007436 817.4 0.007436 5.616
S 1.317 50890 1.317 443.8
Total 5.042 233300 5.042 1885.92
308 1098
Q=Ʃ ¿7 ¿ ∫ Cp ) - Ʃ ¿6 ¿
J J J
∫ Cp ) =1885.92-233300=-231400kW
J
Tref Tref
37
Material balance for C-101:
Stream 7 information C-101 Stream 7 information

T=35C, P=3 bar T=100C, P=25 bar
Phase: gas 7 Phase: gas
Component in Component out
J J
8
By using equation (1)&(2) the general material & energy balance equation for C-101 is:
¿
( Rate of Enthalpy j out ) −¿
Component J
ṅ7 (kmol/s) Ḣ 7J (kW) J
ṅ 8(kmol/s) Ḣ 8J (kW)
T=35C, P=3 bar T=100C, P=25 bar
A 0.7357 396.2 0.7357 3175
E 1.253 554.9 1.253 4407
H 1.411 315.7 1.411 2375
M 0.1814 66.27 0.1814 515.5
U 0.1046 86.15 0.1046 696.9
P 0.015235 10.00 0.015235 80.20
AC 0.01626 7.280 0.01626 56.79
B 0.007436 5.616 0.007436 45.36
S 1.317 443.8 1.317 3464
Total 5.042 1885.92 5.042 14816
373 308
Q=Ʃ ¿8 ¿ ∫ Cp ) - Ʃ ¿7 ¿ ∫ CpJ) =14816-1885.92=12930kW
J J J
Tref Tref
Material balance for D-101:

D-101
Stream 8 information 10 T=100C, P=25 bar
T=100C, P=25 bar Phase: gas
Phase: gas Component out
Component in 8 J-S
J 938
T=100C, P=25 bar
By using equation (1)&(2) the general material & energy balance equation for D-101 is:
¿
( Rate of Enthalpy j out ) =¿
Assumptions:
Stream 9 only contains water, 100% water rejection.
Table 22:Material & Energy information of stream 8&9&10
Component J
ṅ 8(kmol/s) Ḣ 8J (kW) J
ṅ10 (kmol/s) Ḣ 10J(kW) J
ṅ 9(kmol/s) Ḣ 9J(kW)
T=100C, P=25 bar T=100C, P=25 bar T=100C, P=25 bar
A 0.7357 3175 0.7357 3175 0.000 0.000
E 1.253 4407 1.253 4407 0.000 0.000
H 1.411 2375 1.411 2375 0.000 0.000
M 0.1814 515.5 0.1814 515.5 0.000 0.000
U 0.1046 696.9 0.1046 696.9 0.000 0.000
P 0.015235 80.20 0.015235 80.20 0.000 0.000
AC 0.01626 56.79 0.01626 56.79 0.000 0.000
B 0.007436 45.36 0.007436 45.36 0.000 0.000
S 1.317 3464 0.000 0.000 1.317 3464
Total 5.042 14816 3.725 11350 1.317 3464
J−S J −S
ṅ10 =ṅ8
S S
ṅ 9=ṅ 8
T=100C, P=25 bar
E-103 Stream 11 information
T=15C, P=25 bar
Phase: gas
Component in
10 11 Phase: gas
Component out
J-S J-S
39
By using equation (1)&(2) the general material & energy balance equation for E-103 is:
¿
Component J
ṅ11(kmol/s) Ḣ 11J(kW)
T=100C, P=25 bar T=15C, P=25 bar
A 0.7357 3175 0.7357 -388.0
E 1.253 4407 1.253 -545.3
H 1.411 2375 1.411 -314.2
M 0.1814 515.5 0.1814 -65.58
U 0.1046 696.9 0.1046 -84.02
P 0.015235 80.20 0.015235 -9.794
AC 0.01626 56.79 0.01626 -10.45
B 0.007436 45.36 0.007436 -3.287
S 0.000 0.000 0.000 0.000
Total 3.725 11350 3.725 -1420.6
288 373
Q=Ʃ ¿ ¿ ∫ Cp ) - Ʃ ¿ ¿ ∫ CpJ) =-1420.6-11350= -12771kW
11
J J
10
J
Tref Tref
Material balance for T-101:

T-101
T=-38C, P=24.7 bar
13 Phase: sat-vapor
Stream 11 information Component out
T=15C, P=25 bar A&E&H&AC&P
Phase: gas 11
Component in Stream 12 information
J-S T=98C, P=25.3 bar
12 Phase: sat-liquid
Component out
U&P&B&A
40
By using equation (1)&(2) the general material & energy balance equation for T-101 is:
¿
Assumptions:
A is the light key with 99% recovery in the top. P is the heavy key with 99% recovery in the
bottom.
Table 24: Material & Energy information of stream 11&12&13
Component ṅ11 J
(kmol/s) Ḣ 11J(kW) ṅ12
J
J
(kmol/s) Ḣ 13J(kW)
T=15C, P=25 bar T=98C, P=25.3 bar T=-38C, P=24.7 bar
A 0.7357 -388.0 0.7357E-3 -29.42 0.7283 -2185
E 1.253 -545.3 0.000 0.000 1.253 -3134
H 1.411 -314.2 0.000 0.000 1.411 -1877
M 0.1814 -65.58 0.000 0.000 0.1814 -384.2
U 0.1046 -84.02 0.1046 -1991 0.000 0.000
P 0.01524 -9.794 0.01508 -223.0 0.01524E-3 -0.05566
AC 0.01626 -10.45 0.000 0.000 0.01626 -41.59
B 0.007436 -3.287 0.007436 -102.4 0.000 0.000
S 0.000 0.000 0.000 0.000 0.000 0.000
Total 2.400 -1421 0.1279 -2346 3.590 -7622
P P
ṅ12=0.99 ṅ 11=0.9900 × 0.01524=0.01508 kmol /s
A A
ṅ13=0.99 ṅ11=0.9900 × 0.7357=0.7283 kmol /s
P P P −3
ṅ13=ṅ11−ṅ12=0.01524 ¿ 10 kmol /s
A A A −3
ṅ12=ṅ11−ṅ 13=0.7357 ¿ 10 kmol /s
U ∧B U ∧B
ṅ12 =ṅ 11
E∧ H ∧AC E∧H ∧ AC
ṅ13 =ṅ11
235 371 288

Q=Ʃ ¿ ¿ ∫ Cp ) + Ʃ ¿ ¿ ∫ Cp ) - Ʃ ¿ * ^
13
J J
12
J
H °JVap) - Ʃ ¿11J¿ ∫ CpJ)
J
13
J
Tref Tref Tref
=-2346-7622-(-1421)=-8547kW
** the heat of vaporization for each component in stream 12 is add to the enthalpy in table 20
T=-38C, P=24.7 bar
T=30C, P=24.7 bar
Phase: gas
Phase: sat-vapor
ComponentKing
in Saud University
13 41
14 Component out
A&E&H&AC&P A&E&H&AC&P
¿
Component J
ṅ14 (kmol/s) Ḣ 14J(kW)
T=-38C, P=24.7 bar T=30C, P=24.7 bar
A 0.7283 -2185 0.7283 195.1
E 1.253 -3134 1.253 276.2
H 1.411 -1877 1.411 257.0
M 0.1814 -384.2 0.1814 74.25
U 0.000 0.000 0.000 0.000
P 0.01524E-3 -0.05566 0.01524E-3 0.4976E-3
AC 0.01626 -41.59 0.01626 3.628
B 0.000 0.000 0.000 0.000
S 0.000 0.000 0.000 0.000
Total 3.590 -7622 3.590 802.6
303 235
Q=Ʃ ¿14J¿ ∫ CpJ) - Ʃ ¿13J¿ ∫ CpJ)= 802.6- (-7622)=8425kW
Tref Tref
Material balance for R-102:
T=30C, P=24.7 bar
R-102 Stream 15 information
T=53C, P=24.7 bar
Phase: gas
Component in
14 15 Phase: gas
Component out
A&E&H&AC&P A&E&H&P
By using equation (1)&(2) the general material & energy balance equations for R-102 are:
¿
( Rate of Enthalpy j out ) + ( Rate of Heat of Reaction ) −¿
Reactions:
C2H2 + H2 →C2H4
C2H2 + 2H2 →C2H6
Assumptions:
42
100% AC conversion, 90% of AC will convert to E.
AC+H↔E ξ1=ṅ14AC*0.9 ξ1=0.01626*0.9000=0.01463kmol/s ^
H °rxn1=-174980 kJ/kmol
AC+2H→A ξ2=ṅ 14AC*0.1 ξ2=0.01626*0.1000=1.626E-3kmol/s ^
H °rxn2=-312160 kJ/kmol
A A −3
ṅ15=ṅ14 +ξ 2=0.7283+1.626 ¿ 10 =0.7299 kmol /s
E E
ṅ15=ṅ14 +ξ 1=1.253+0.01463=1.268 kmol /s
H H −3
ṅ15=ṅ14−ξ 1−2 ξ 2=1.411−0.01463−1.626 ¿ 10 =1.393 kmol /s

Component J
T=30C, P=24.7 bar T=53C, P=24.7 bar
A 0.7283 195.1 0.7299 1150
E 1.253 276.2 1.268 1638
H 1.411 257.0 1.393 893.5
M 0.1814 74.25 0.1814 192.2
U 0.000 0.000 0.000 0.000
P 0.01524E-3 0.4976E-3 0.01524E-3 0.02929
AC 0.01626 3.628 0.000 0.000
B 0.000 0.000 0.000 0.000
S 0.000 0.000 0.000 0.000
Total 3.590 802.6 3.572 3874
AC AC
¿−out ṅ14 −ṅ 15 0.01626−0.000
Conversion of AC= ¿ = AC
= ∗100.0=100.0 %
ṅ14 0.01626
desire E ξ1
Selectivity= = = =9
undesire A ξ 2
326 303
Q=Ʃ ¿ ¿ ∫ Cp ) + ( ^
15
J J
H °rxn2*ξ2) - Ʃ ¿14J¿ ∫ CpJ)
H °rxn1*ξ1) + ( ^
Tref Tref
=3874-802.6 + 0.01463(-174980)+1.626 ¿ 10−3 (−312160) =3.870kW

By using heat of formation method for energy balance for the reactor:
( Rate of Enthalpy j out ) + ( Rate of Heat of Fomation for j reacted out )−¿
326 303
Q=Ʃ ¿15J¿ ∫ CpJ) - Ʃ ¿14J¿ ∫ CpJ) + Ʃ( ^
H ° A&Ef *ṅ 15A&E) - Ʃ( ^
H °AC&A&Ef *ṅ 14J)
Tref Tref
43
=3874-802.6 +0.7299(-84680)+1.268(52500)-(0.01626(227000)+0.7283(-84680)+1.253(52500))
Q=3874-802.6 -3039=32.4kW
Stream 15 information Stream 16 information

T=53C, P=24.7 bar
Phase: gas
E-105 T=-28C, P=24.7 bar
Phase: liquid-vapor
Component in
M&A&E&H&P
15 16 Component out
Liq(M&A&E&P)
gas(H)
By using equation (1)&(2) the general material & energy balance equation for
E-105 is:
¿
Component J
T=53C, P=24.7 bar T= -28, P=24.7
A 0.7299 1150 0.7299 -13410
E 1.268 1638 1.268 -21320
H 1.393 893.5 1.393 -1638
M 0.1814 192.2 0.1814 -1826
U 0.000 0.000 0.000 0.000
P 0.01524E-3 0.02929 0.01524E-3 -0.3527
AC 0.000 0.000 0.000 0.000
B 0.000 0.000 0.000 0.000
S 0.000 0.000 0.000 0.000
Total 3.572 3874 3.572 -38190
245 326
Q=Ʃ ¿ ¿ ∫ Cp ) - Ʃ ¿ * ^
16
J J
H °Vap(A&E&P&M)) - Ʃ ¿15J¿ ∫ CpJ)= -38190-3874=-42064kW
16
J
Tref Tref
Material balance for F- 101:

F-101 Stream 17 information
T=-28C, P=24.7 bar
17 Phase: gas
Component out
T=-28C, P=24.7 bar
16 44 H&M
Phase: liquid-vapor
Component in 18
Liq(M&A&E&P)
By using equation (1)&(2) the general material & energy balance equation for F-101 is:
¿
Assumptions:
All H will go in the top, Stream 24 contain H and M only with 95 wt% H purity.
H H kg
ṁ16=ṁ17=2.000∗1.393=2.786
s
M H 0.05 0.05000 kg
ṁ 17=ṁ 26 × =2.786 × =0.1466
0.95 0.9500 s
M M M kg M
ṁ18=ṁ15−ṁ17=2.902−0.1466=2.756 , ṅi =16∗ṁiM
s
Component ṅ16 J
J
(kmol/s) Ḣ 17J(kW) J
T= -28, P=24.7 liq-vap gas liquid
A 0.7299 -13410 0.000 0.000 0.7299 -13410
E 1.268 -21320 0.000 0.000 1.268 -21320
H 1.393 -1638 1.393 -1638 0.000 0.000
M 0.1814 -1826 9.163E-3 -17.19 0.1722 -1733
U 0.000 0.000 0.000 0.000 0.000 0.000
P 0.01524E-3 -0.3527 0.000 0.000 0.01524E-3 -0.3527
AC 0.000 0.000 0.000 0.000 0.000 0.000
B 0.000 0.000 0.000 0.000 0.000 0.000
S 0.000 0.000 0.000 0.000 0.000 0.000
Total 3.572 -38190 1.402 -1655 2.170 -36460
45
245 245 245
Q=Ʃ ¿ ¿ ∫ Cp ) - Ʃ ¿ * ^
17
J J
18
J
H °Vap(A&E&P&M)) + Ʃ ¿ ¿ ∫ Cp )- Ʃ ¿ ¿ ∫ CpJ)+ Ʃ ¿16J* ^
18
J J
16
J
H°
Tref Tref Tref
(A&E&P&M)
Vap ) =-1655-36460 –(-38190)=75kW
T-102
T=-100C, P=24.4 bar
19
Stream 18 information Phase: sat-vapor
T=-28C, P=24.7 bar Component out

M&E
Phase: sat-liquid 18
Component in
M&A&E&P
T=-13C, P=25 bar
Phase: sat-liquid
20
Component out
M&A&E&P
By using equation (1)&(2) the general material & energy balance equation for T-102 is:
¿
Assumptions:
M is the light key with 99.5% recovery in the top. E is the heavy key with 99% recovery in the
bottom.
M M
ṅ19=0.995∗ṅ18=0.9950∗0.1722=0.1713 kmol / s
M M M −4
ṅ20=ṅ18−ṅ19=0.1722−0.1713=9.000 ¿ 10 kmol / s
E E
ṅ20=0.99∗ṅ18=0.9900∗1.268=1.255 kmol /s
E E E −2
ṅ19=ṅ18−ṅ20=1.268−1.255=1.300 ¿ 10 kmol / s

Component ṅ18 J
J
T= -28, P=24.7 sat-liq T=-100, P=24.3 sat-vap T=-13, P=25 sat-liq
A 0.7299 -13410 0.000 0.000 0.7299 -12880
E 1.268 -21320 1.300E-2 -62.68 1.255 -20340
46
H 0.000 0.000 0.000 0.000 0.000 0.000
M 0.1722 -1733 0.1713 -737.5 9.000E-4 -8.560
U 0.000 0.000 0.000 0.000 0.000 0.000
P 0.01524E-3 -0.3527 0.000 0.000 0.01524E-3 -0.3394
AC 0.000 0.000 0.000 0.000 0.000 0.000
B 0.000 0.000 0.000 0.000 0.000 0.000
S 0.000 0.000 0.000 0.000 0.000 0.000
Total 2.170 -36460 0.1843 -800.2 1.986 -33230
260 173 245
Q=Ʃ ¿20J¿ ∫ CpJ) + Ʃ ¿19J¿ ∫ CpJ) - Ʃ ¿20J* ^
H °JVap) - Ʃ ¿18J¿ ∫ CpJ) + Ʃ ¿18J* ^
H °JVap)
Tref Tref Tref
=-33230+-800.2-(-36460)=2430kW

T-103 T=-20C, P=24.7 bar
Phase: sat-vap
21
Stream 20 information Component out
T=-13C, P=25 bar E&A
Phase: sat-liquid 20
Component in
M&A&E&P
T=2C, P=25.3 bar
Phase: sat-liquid
22 Component out
By using equation (1)&(2) the general material & energy balance A&M&P&E
equation for F-101 is:
¿
Assumptions:
E is the light key with 99% recovery in the top, and 99.9 wt% purity.
E E
ṅ21=0.99∗ṅ 20=0.9900∗1.255=1.242 kmol /s
E E E −2
ṅ22=ṅ20−ṅ21=1.255−1.242=1.300 ¿ 10 kmol /s
A A
ṅ22=0.9990∗ṅ 20=0.9990∗0.7299=0.7292 kmol /s
47
A A A −4
ṅ21=ṅ20−ṅ22=0.7299−0,7292=7.000 ¿ 10 kmol /s

Component ṅ20 J
J
ṅ22(kmol/s) Ḣ 22J(kW)
T=-13, P=25 sat-liq T=-20, P=24.7 sat-vap T=2, P=25.3 sat-liq
A 0.7299 -12880 7.000E-4 -1.601 0.7292 -12320
E 1.255 -20340 1.242 -2361 1.300E-2 -202.7
H 0.000 0.000 0.000 0.000 0.000 0.000
M 9.000E-4 -8.560 0.000 0.000 9.000E-4 -8.114
U 0.000 0.000 0.000 0.000 0.000 0.000
P 0.01524E-3 -0.3394 0.000 0.000 0.01524E-3 -0.3255
AC 0.000 0.000 0.000 0.000 0.000 0.000
B 0.000 0.000 0.000 0.000 0.000 0.000
S 0.000 0.000 0.000 0.000 0.000 0.000
Total 1.986 -33230 1.243 -2363 0.7431 -12530
263 275 260
Q=Ʃ ¿22J¿ ∫ CpJ) + Ʃ ¿21J¿ ∫ CpJ) + Ʃ ¿21J* ^
H °JVap) - Ʃ ¿20J¿ ∫ CpJ) + Ʃ ¿20J* ^
H °JVap)
Tref Tref Tref
=-12530-2363-(-33230)=18340kW
Material & energy balance for M-101:
Stream1&22 information
T=25C, P=1 bar
M-101 Stream 2 information
T=25C, P=1 bar
Phase: gas
Component in
1 2 Phase: gas
Component out
A 22 A
48
¿
Assumptions:
 For the recycle stream 22 assume pure A
 The streams conditions are 1 bar and 25C at gas phase (the stream will be heat integrated)
A A A
ṅ1 =ṅ5 −ṅ 22=2.257−0.7292=1.528 kmol /s
A A A
ṅ2 =ṅ1 +ṅ22=1.528+ 0.7292=2.257 kmol /s

Component ṅ1J (kmol/s) Ḣ 1J(kW) J
ṅ22(kmol/s) Ḣ 22J(kW) ṅ2J (kmol/s) Ḣ 2J(kW)
T=25C, P=1 bar T=25C, P=1 bar T=25C, P=1 bar
A 1.528 0.000 0.7292 0.000 2.257 0.000
E 0.000 0.000 0.000 0.000 0.000 0.000
H 0.000 0.000 0.000 0.000 0.000 0.000
M 0.000 0.000 0.000 0.000 0.000 0.000
U 0.000 0.000 0.000 0.000 0.000 0.000
P 0.000 0.000 0.000 0.000 0.000 0.000
AC 0.000 0.000 0.000 0.000 0.000 0.000
B 0.000 0.000 0.000 0.000 0.000 0.000
S 0.000 0.000 0.000 0.000 0.000 0.000
Total 1.528 0.000 0.7292 0.000 2.257 0.000
All enthalpy rates are zero because the components are at the reference conditions which are 25C
and 1bar at the gas phase
T=25C, P=1 bar
T=300C, P=1 bar
Phase: gas
3 Phase: gas
Component in
A
2 Component out
A
¿
49
T=25C, P=1 bar T=300, P=1
A 2.257 0.000 2.257 42930
E 0.000 0.000 0.000 0.000
H 0.000 0.000 0.000 0.000
M 0.000 0.000 0.000 0.000
U 0.000 0.000 0.000 0.000
P 0.000 0.000 0.000 0.000
AC 0.000 0.000 0.000 0.000
B 0.000 0.000 0.000 0.000
S 0.000 0.000 0.000 0.000
Total 2.257 0.000 2.257 42930
573
Q=¿3 ¿ ∫ CpA)= 42930kW
A
Tref

Stream 3 information Stream 5 information
T=300C, P=1 bar T=300C, P=1 bar
Phase: gas M-102 Phase: gas
Component in
3 5 Component out
A 4 A&S
T=300C, P=1 bar
Phase: gas
Component in
S
By using equation (1)&(2) the general material & energy balance equation
for M-102 is:
¿
The weight ratio between ethane and steam is 0.35kg steam per kg ethane
S A 23.70 kg
ṁ 4 =0.35∗ṁ 3 =2.257∗30∗0.35=
s
50
S
ṁ 4 23.70
S
ṅ= =4 =1.317
18 18.00

ṅ 4(kmol/s) Ḣ 4J(kW) J
T=300, P=1 T=300, P=1 T=300, P=1
A 2.257 42930 0.000 0.000 2.257 42930
E 0.000 0.000 0.000 0.000 0.000 0.000
H 0.000 0.000 0.000 0.000 0.000 0.000
M 0.000 0.000 0.000 0.000 0.000 0.000
U 0.000 0.000 0.000 0.000 0.000 0.000
P 0.000 0.000 0.000 0.000 0.000 0.000
AC 0.000 0.000 0.000 0.000 0.000 0.000
B 0.000 0.000 0.000 0.000 0.000 0.000
S 0.000 0.000 1.317 14040 1.317 14040
Total 2.257 42930 1.317 14040 3.574 56970
573 573 573
Q=−¿3 ¿ ∫ Cp ) −¿4 ¿ ∫ Cp )+ ṅ 5 ¿ ∫ CpJ = 56970-42930-14040=0kW
A A S S S
Tref Tref Tref
51
Chapter Four: Safety and environmental considerations
4.1 Previous plant accident
A- 2013 Explosion and Fire at Williams Olefins Plant in Geismar, Louisiana
The Williams Geismar facility produces ethylene and propylene for the petrochemical
industry and employs approximately 110 people. At the time of the incident, approximately 800
contractors worked at the plant on an expansion project aimed at increasing the production of
ethylene.
The incident occurred during non-routine operational activities that introduced heat to the
reboiler, which was offline and isolated from its pressure relief device. The heat increased the
temperature of a liquid propane mixture confined within the reboiler, resulting in a dramatic
pressure rise within the vessel. The reboiler shell catastrophically ruptured figure 12, causing a
boiling liquid expanding vapor explosion (BLEVE) and fire, which killed two workers; 167
others reported injuries, the majority of which were contractors [26].
Figure 13: Ruptured Reboiler [26]

Failure to appropriately manage or effectively review two significant changes that introduced
new hazards involving the reboiler that ruptured—(1) the installation of block valves that could
isolate the reboiler from its protective pressure relief device and (2) the administrative controls
Williams relied on to control the position (open or closed) of these block valves.
52
4.2 Identification of material and chemicals
4.2.1 NFPA 704
Standard System for the Identification of the Hazards of Materials for Emergency Response is a
stander maintained by the U.S.-based National Fire Protection Association, it defines the "Fire
Diamond" which is used to quickly and easily identify the risks posed by hazardous materials.
This helps determine what, if any, special equipment should be used, procedures followed, or
precautions taken during the initial stages of an emergency response, it is explained in figure 13.
It is an internationally accepted safety standard and is crucial while transporting chemicals.
Figure 14: NFPA 704 Explained [27]
4.2.2 Identification of material by NFPA 704

 Ethane
A colorless odorless gas. It is easily ignited. The vapors are heavier than air. It can asphyxiate by the
displacement of air. Under prolonged exposure to fire or intense heat the containers may rupture
violently and rocket. Contact with the liquid may cause frostbite.
4
1 0
0
53
 Ethylene
A colorless gas with a sweet odor and taste. It is lighter than air. It is easily ignited and a flame can
easily flash back to the source of the leak. Under prolonged exposure to fire or heat the containers
may rupture violently and rocket. Can cause explosion.
4
2 2
0
 Water
A clear, nontoxic liquid composed of hydrogen and oxygen, essential for life and the most widely used
solvent. Include water in a mixture to learn how it could react with other chemicals in the mixture.
0
0 0
 Hydrogen
Hydrogen is a colorless, odorless gas. It is easily ignited. Once ignited it burns with a pale blue, almost
invisible flame. The vapors are lighter than air. It is flammable over a wide range of vapor/air
concentrations. Hydrogen is not toxic but is a simple asphyxiate by the displacement of oxygen in the
air. Under prolonged exposure to fire or intense heat the containers may rupture violently and rocket.
Hydrogen is used to make other chemicals and in oxyhydrogen welding and cutting.
4
0 0
54
 1,3 Butadiene
Butadiene is a colorless gas with an aromatic odor. It is shipped as a liquefied gas under its vapor
pressure. Contact with the liquid can cause frostbite. It is easily ignited. Its vapors are heavier than
air and a flame can flash back to the source of leak very easily. It can asphyxiate by the displacement
of air. It must be shipped inhibited as butadiene is liable to polymerization. If polymerization occurs in
the container, it may violently rupture. Under prolonged exposure to fire or intense heat the
containers may rupture violently and rocket. It is used to make synthetic rubber and plastics, and to
make other chemicals.
4
2 2
0
 Acetylene
A colorless gas with a faint garlic-like odor. Easily ignited and burns with a sooty flame. Gas is lighter
than air. Flame may flash back to the source of a leak very easily. Under prolonged exposure to fire or
heat the containers may rupture violently and rocket.
4
0 3
0
 Methane
Methane is a colorless odorless gas. It is also known as marsh gas or methyl hydride. It is easily
ignited. The vapors are lighter than air. Under prolonged exposure to fire or intense heat the
containers may rupture violently and rocket. It is used in making other chemicals and as a constituent
of the fuel, natural gas.
4
2 55 0
 Propylene
Propylene is a colorless gas with a faint petroleum like odor. It is shipped as a liquefied gas under its
own vapor pressure. For transportation it may be stenched. Contact with the liquid can cause
frostbite. It is easily ignited. The vapors are heavier than air. Any leak can either be liquid or vapor. It
can asphyxiate by the displacement of air. Under prolonged exposure to fire or intense heat the
containers may rupture violently and rocket. It is used to make other chemicals. Can cause explosion.
4
1 1
 Propane
A colorless gas with a faint petroleum-like odor. It is shipped as a liquefied gas under its vapor
pressure. For transportation it may be stenched. Contact with the unconfined liquid can cause frostbite
by evaporative cooling. Easily ignited. The vapors are heavier than air and a flame can flash back to
the source of leak very easily. The leak may be either a liquid or vapor leak. The vapors can
asphyxiate by the displacement of air. Under prolonged exposure to fire or heat the containers may
rupture violently and rocket.
4
2 0
56
Figure 15: Layout of the Plant
57
References
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[Online]. Available: https://www.britannica.com/science/ethylene
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%2Bethylene&ab_segments=0%2Fbasic_search_gsv2%2Fcontrol&refreqid=fastly-default
%3A94efa3d4c1ec0ac6f6a34ce81828329a
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https://www.gpca.org.ae/2023/02/27/ethylene-in-focus/
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Single Event Microkinetic Model for Steam Cracking of Hydrocarbons,” 2005. [Online].
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https://webbook.nist.gov/chemistry/#Search
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[10] “ChemSpider | Search and share chemistry.” Accessed: Sep. 14, 2023. [Online]. Available:
http://www.chemspider.com/
[11] “Airgas.” Accessed: Sep. 16, 2023. [Online]. Available: https://www.airgas.com/sds-search
[12] “SAFETY DATA SHEET GHS product identifier”.
[13] “SECTION 1: Identification”, Accessed: Sep. 16, 2023. [Online]. Available: www.labchem.com
[14] “SECTION 1: Identification”, Accessed: Sep. 16, 2023. [Online]. Available: www.labchem.com
[15] “Ethylene Market Installed Capacity and Capital Expenditure, Announced Projects, 2023-2027.”
Accessed: Sep. 17, 2023. [Online]. Available: https://www.globaldata.com/store/report/ethylene-
market-analysis/
58
[16] “Top 10 Ethylene Producers in the World.” Accessed: Oct. 18, 2023. [Online]. Available:
https://www.procurementresource.com/blog/ethylene-producers-in-the-world
[17] “Ethylene prices per ton 2022 | Statista.” Accessed: Nov. 27, 2023. [Online]. Available:
https://www.statista.com/statistics/1170573/price-ethylene-forecast-globally/
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Production of Ethylene From Ethane: King Saud University College of Engineering Chemical Engineering Department

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Production of Ethylene From Ethane: King Saud University College of Engineering Chemical Engineering Department

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King Saud University

1.1. Background and History...................................................................................................3

1.1.1 Discovery of Ethylene....................................................................................................3

1.1.2 History of Ethylene in Petrochemical Industry..............................................................4

1.2. Applications and Uses......................................................................................................5

1.3.2. Safety and Toxicological Properties Related to the Project..........................................6

1.4 Initial Feasibility Study and Market Survey..........................................................................7

1.4.1 Production and Consumption: Worldwide, Regional, and National..............................7

1.4.2 Preliminary Economic Analysis.....................................................................................7

Chapter Two: Process Selection and Process Description..............................................................8

2.1 Process Selection...................................................................................................................8

2.1.1 Production of Ethylene from Methanol..........................................................................8

2.1.2 Production of Ethylene by Dehydration of Ethanol.......................................................9

2.1.3 Production of Ethylene by Oxidative coupling of Methane...........................................9

2.1.4 Production of Ethylene by Cracking of Ethane............................................................10

2.1.5 Comparison of Existing Processes................................................................................11

2.1.6 Selecting process..........................................................................................................12

2.2 Detailed Description of Selected Process............................................................................12

Chapter Three: Mass and Energy Balances...................................................................................15

1.1. Background and History

Figure 2: Ethylene chemical structure [2]

1.1.2 History of Ethylene in Petrochemical Industry

Figure 3: GCC feedstock types (mtpa)[5]

Figure 4: Ethylene breakdown by key derivatives in the GCC[5]

Ethane C2H6 30 -88 -84.68 -182 15.7 1.356 -1560.3

Ethylene 21.208 8.984 3.66 11.43 -2772.9 100 1500

Table 4: Viscosity Coefficients’[7], [9], [10]

1.3.2. Safety and Toxicological Properties Related to the Project

Ethylene 720 2.7 32.2 138 N/A N/A N/A

Figure 5: GCC Ethylene production Figure 6: Ethylene production by

1.4.2 Potential Gross Profit

2.1 Process Selection

2.1.1 Production of Ethylene from Methanol

Figure 7: Block flow diagram for MTO process

Figure 8: Block flow diagram of the dehydration of Ethanol

2.1.3 Production of Ethylene by Oxidative coupling of Methane

2.1.4 Production of Ethylene by Cracking of Ethane

Figure 10: Block flow diagram of production of Ethylene by cracking of Hydrocarbons

2.1.5 Comparison of Existing Processes

B- Criteria and the Scenarios Evaluation

Table 8: Evaluation Scenario 2

Figure 11: Production of Ethylene by Ethane cracking block diagram

Mixer Reactor Heat Compressor Dryer Fractionator

Table 9: Unit Description

Chapter Three: Mass and Energy Balances

3.1 List of Assumptions

3.2 Degree of Freedom

 If N DOF = 0, problem can be solved (in principle).

Table 10: Degree of freedom for the hot section

Table 11: Degree of freedom for the cold section

( Rate of Enthalpy j out ) + ( Rate of Heat of Reaction ) −¿

Table 15: Heat of reaction for all the reactions

Energy balance calculation equations

No phase change: Enthalpy Calculations (No Phase Change)

Heat of Vaporization at different Temperatures: Enthalpy Calculations (Phase Change)

Reaction: Enthalpy Calculations (Reaction)

Heat Loads (Without Reactions)

3.3 Material & Energy Balance

1 C2H6 ↔ C2H4 + H2 A=4.65 x1013 A=8.75 x108

Let: A≡ethane, B≡propane, M≡methane, H≡H2, E≡ethylene, P≡propylene, AC≡acetylene, U≡

i yJi=ṅ Ji/nTi (11)

ṅ J out=ṅ J ∈+ Ʃ ν i∗ξ i(13)

moles of desired component E