Abu Dhabi University

College of Engineering & Computer Science

Design of a chemical plant for the production of 140160

tons/year of low-density polyethylene

Capstone Design Project

Submitted for Partial Fulfillment of the

B.Sc. Degree in Chemical Engineering

By

Name ID
Roz Zaarour 1062898
Shama Ali 1062421
Noor Mohammed 1062948

Project Advisor: Dr. Chandra Mouli

Examination Committee:

Examiner 1: Prof. Ioannis Zuburtikudis

 Examiner 2: Dr.Omar Chaalal

Fall Semester 2019/2020

Abu Dhabi University

College of Engineering & Computer Science

Contribution of Team Members*

Project Title: Design of a chemical plant for the production of 140160 tons/year of low-density
polyethylene

Semester / Academic Year: (Fall) / 2019-20 Date: Dec 14,2019

Student 1 Student 2 Student 3

Tasks

1. Chapter One 33.3 33.3 33.3

2. Chapter Two 33.3 33.3 33.3
3. Chapter Three 33.3 33.3 33.3
4. Chapter Four 33.3 33.3 33.3
* The total percentage for each task should be 100.

Project Advisor Name and Signature:

Table of Contents

Acknowledgments......................................................................................................................5
Executive summary....................................................................................................................6
Chapter 1: Introduction..............................................................................................................9
Problem Statement.................................................................................................................9
1.2 Problem and Design Objective........................................................................................9
1.3 Intended Outcomes and Deliverables............................................................................10
1.4 Summary of Report Structure........................................................................................10
Chapter 2 Background and literature review survey................................................................11
2.1 Introduction....................................................................................................................11
2.1.1 Ethylene..................................................................................................................11
2.2 Introduction to Polyethylene..........................................................................................13
2.2.1 The History of Polyethylene...................................................................................14
2.2.2 Basic Operation of Producing polyethylene:..........................................................15
2.2.3 Manufacturers & Distributors of polyethylene is UAE:.........................................16
2.2.4 Polyethene and environment...................................................................................17
2.2.5 Annual statistics of polyethylene (polyethylene/million tons)...............................18
2.2.6 Industries producing polyethylene in the UAE.......................................................19
2.2.7 Classifications of polyethylene...............................................................................20
2.2.8 Comparison between different classification of polyethylene................................21
Chapter 3 Process Selection.....................................................................................................35
3.1Autoclave method:..........................................................................................................38
3.2Tubular method:..............................................................................................................39
3.3Process selection.............................................................................................................40
3.4 Flow sheet preparation...................................................................................................42
3.5 Process description.........................................................................................................43
Chapter 4 Mass and Energy Balance.......................................................................................44
4.1 Material balance.............................................................................................................46
 4.2 Energy Balance..............................................................................................................53
Bibliography.............................................................................................................................74

List of Tables
Table 1 Ethylene physical properties.......................................................................................14
Table 2 Manufacture and supply in UAE................................................................................19
Table 3 annual statistics inn 2013,2015,108............................................................................20
Table 4 Annual statistics for LDPE,LLDPE,HDPE................................................................20
Table 5 Catalyst used in HDPE................................................................................................25
Table 6 Pros & Cons of HDPE................................................................................................26
Table 7 Catalyst used in Cross-linked......................................................................................28
Table 8 Pros & Cons of Cross-linked......................................................................................29
Table 9 Catlyst Cost for UHMWPE........................................................................................31
Table 10 LLDPE catalyst.........................................................................................................33
[38] [8]Table 11 LDPE properties...........................................................................................36
Table 12 Catalyst used in producing LDPE.............................................................................36
Table 13 Comparison of HDPE AND LDPE in terms of their properties...............................39
Table 14 Comparison of HDPE AND LDPE In terms of their applications...........................39
Table 15 Tubular Vs Autoclave...............................................................................................42
Table 16 Material balance on tubular reactor..........................................................................49
Table 17 Material balance on high pressure separator............................................................50
Table 18 overall material balance............................................................................................56
Table 19 energy balance on control valve...............................................................................59
Table 20 energy balance on high pressure seprator.................................................................61
Table 21 energy balance on heat exchanger (E-105)...............................................................62
Table 22 energy balance on cyclone separator........................................................................63
Table 23 energy balance oncontrol valve................................................................................65
Table 24 energy balance on low pressure seprator..................................................................66
Table 25 energy balance on mixing.........................................................................................71
Table 26 energy balance mixing..............................................................................................73

List of Figures
Figure 1 General ethylene process...........................................................................................14
Figure 2 A comparison between the polyethylene types.........................................................23
Figure 3 the processes involved for each type[22]..................................................................24
Figure 4 Ziegler-Natta Catalyst production.............................................................................25
Figure 5 Properties of HDPE...................................................................................................26
Figure 6 Application Market share for cross linked................................................................29
Figure 7 Applications of UHMWPE........................................................................................30
Figure 8 Manufacturing LDPE flow sheet diagram.................................................................35
Figure 9 Classifications of polyethylene..................................................................................38
Figure 10 Polyethene 2 selected types.....................................................................................38
Figure 11 Flow diagrams of Autoclave & Tubular..................................................................40
Figure 12 Molecular mass distribution for autoclave and tubular...........................................43
Figure 13 Molecular Distribution of polyethylene..................................................................47
Acknowledgments

We express our deep sense of gratitude to Dr. Chandra Mouli, for his valuable advice and constructive
criticism during the course of the project. We are highly thankful to all the staff members of chemical
Department for their support and co-operation. We also express our sincere thanks to all the classmates
for their support and co-operation in completing the project work.
Executive summary

The assigned capstone project topic to our group is the production of low density polyethylene.
Polyethylene is one of the polymers called polyolefins. Polyethylene does not occur naturally it was
first synthesized by the British researchers in 1933 and it is manufactured by cracking ethylene gas
under high pressures and moderate temperatures. It’s the most used plastic all over the world (tens of
millions of tons are produced worldwide each year) Where its wide applications range from plastic
bags to medical devices. Depending on the density of the polyethylene, polyethylene is classified into
different types, the common ones are LDPE, LLDPE, HDPE, and Ultrahigh Molecular Weight
polyethylene. In the process selection part LDPE has been chosen among all the other types since its
products can’t be abandoned in daily life. LDPE is considered to be relatively safe but, some
precautions should be taken while dealing with it.
Chapter 1 Introduction

1.1 Problem Statement

The objective of this capstone project is to design a chemical plant that produces 16 ton/h of low-
density polyethylene from a feedstock flow of 65 ton/hr of ethylene gas entering the reaction zone
under the operating conditions of high pressure and moderate temperature along with initiator.

1.2 Problem and Design Objective

Ethylene C2H4 is an organic compound that is produced by heating ethane under high temperatures
giving a product of a mixture of gases where the Ethylene is separated.in this process Ethylene
produces Polyethylene (LDPE) which is a thermoplastic polymer with different crystalline structure,
and wide range of applications that depends on the type of polyethylene and the desired product.

The production of polyethene undergoes many different processes that differs in many aspect such as;
economical cost, quality of product, degree of polymerization, and simplicity of design. As a result, the
selected process will satisfy the demands of the region and environment which is the most sustainable
among the listed processes.
A process flow diagram was created for the selected approach to produce low density polyethene
(LDPE) from ethylene, and according to the created process a material and energy balance is applied.

1.3 Intended Outcomes and Deliverables

This project design contains significant outcomes that are achieved in this research. At the beginning of
the project a brief research and literature review should be done about the chemical that is going to be
produced and chemicals involved in the reaction. Our topic is producing low density polyethylene
where the only main chemical involved in the production is ethylene. Secondly, a process flow diagram
has been created using luciad chart website that is available online and E-DRAW software. The
following next outcome is applying mass and energy balance on each equipment present in the process
flow diagram.

1.4 Summary of Report Structure

The capstone design is spitted in 2 main parts where the first four chapters are done in capstone 1 and
the other 5 chapter are achieved in the next following semester.

Chapter 1
Gives a brief summary of the project along with a problem statement and the significant outcomes and
deliverables of the project.

Chapter 2
Covers the literature review about the topic of the project which includes the history of the chemicals
involved in the reaction, the chemical and the physical properties of the chemical, and their different
classifications along with their applications and uses in industrial field.

Chapter 3
Explains the process selection and different pathways to achieve this chemical where each pathway is
described in detail with their advantages and disadvantages.

Chapter 4
Energy and mass balance was applied on each equipment to make sure the law of conservation of
energy is not violated.

Chapter 2 Background and literature review survey

2.1 Introduction

2.1.1 Ethylene

Ethylene (H2C=CH2), is an organic compound and it’s the simplest alkene and it contains carbon-
carbon double bond. All these atoms H-C-H form an angle of 117.4°, to form a hybridized carbon sp².
This bond is rigid about the C-C bond with high energy process by breaking the π-bond.[ CITATION
BYJ \l 1033 ]Natural gas and petroleum are the natural sources of ethylene and it can also occur
hormone in plants that prevents growth and helps the leaves to fall. Moreover, it’s also found in fruits
which promotes ripening. The general properties of ethylene are colorless, flammable gas having a
sweet taste and odor and soluble in polar solvents.
Ethylene is widely used in chemical industry mostly as polyethylene. Ethylene is manufactured by
heating either natural gas (ethane and propane) or petroleum to a high temperature ranging from 800–
900 °C. After heating a mixture of gases will be produced and ethylene will be separated. The melting
point of ethylene is −169.4 °C [−272.9 °F], and its boiling point is −103.9 °C [−155.0 °F].[ CITATION
Fra19 \l 1033 ]
Ethylene physical properties

Formula C2H4
Molecular Weight (lb/mol) 28.05
Critical Temp. (°F) 49.1
Critical Pressure (psia) 742.7
Boiling Point (°F) -154.8
Melting Point (°F) -272.5
Gas Density @ 70°F 1 atm (lb/ft3) 0.0730
Specific Volume @ 70°F 1 atm (ft3/lb) 13.70
Specific Gravity 0.992
Specific Heat @ 70°F (Btu/lbmol-°F) 10.28
[ CITATION
air19 \l 1033 ]
Table 1 Ethylene physical properties

Ethylene production

Ethylene has two primary feed stocks naphtha and natural gas. The first step is the pyrolysis or steam
cracking where the feed stock will be cracked into ethylene and other products in the furnace. Cracked
gases leave the furnace at a high temperature from 1382F to 1607F (750C to 875C). After that the
gases must be rapidly cooled in order to preserve the gas's current composition and to avoid unwanted
side reactions this step occurs at the quench towers. After the cooling step the gas undergoes the
compression step at A turbine driven centrifugal compressor there 4 or 5 stages with intermediate
cooling. Since the cracked gas is filled with water during compression and the moisture must be
removed after each intercooler stage to prevent hydrates and ice from forming. [ CITATION Eme \l
1033 ]
 Figure 1 General ethylene process

Ethylene Products & Uses

It’s not unusual that ethylene has many uses since it’s the most common organic compound. The
following are some of everday’s life uses:
 Polyethylene production - Polyethylene is the most commonly used plastic in the world.
It is recyclable and can be reused for the manufacture of other materials. Currently some
reseaches are under process to discover more about how to make it more biodegradable.
 PVC – stands for polyvinyl chloride which comes in two basic forms, rigid and flexible. The
rigid form is used in construction for pipe and door and window profiles. It is also used for
bottles, non-food packaging and credit cards. The flexible form is used in plumbing, electrical
cable insulation, signage and inflatable products.
 MEG - It is an ethylene derivative used in the manufacture of polyester resins, films and fibers,
as well as in the manufacture of water-based adhesives, pulp, antifreeze, coolant, de-icers and
solvents.
 Surfactants production - They represent a significant variety of chemical compounds used as
detergents, wetting agents, emulsifiers, foaming agents and dispersants..
 Other uses - ethylene is also used as a welding gas , and to ripe a fruit, and has many more
everyday applications.[ CITATION LAC16 \l 1033 ]

2.2 Introduction to Polyethylene

Polyethylene is a thermoplastic polymer with different crystalline structure. It contains the chemical
elements carbon and hydrogen and it is created through polymerization of ethene. It is the most widely
used plastic in the world, so it has a wide range of applications which depends on the type of
polyethylene and the desired product. When talking about polyethylene product many specifications
should be mentioned like whether it’s a  high density or low density or linear low density or polar
ethylene copolymer, what catalyst or comonomer was used ,what manufacturing process was used, and
what resultant molecular structure[ CITATION Raj16 \l 1033 ]. There are different common types of
polyethene produced and used:
 Low density polyethylene (LDPE)
It is a type of polyethylene with high flexibility, and specific flow properties which allows the it to
stretch when strained.
 Linear low-density polyethylene (LLDPE)
It is very similar to LDPE, but with an additional advantage that is properties of LLDPE properties can
be changed by altering the formula constituents. In addition, the LLDPE production process requires
less energy than LDPE.
 High density polyethylene (HDPE)
It is a stiff, strong kind of plastic with high crystalline structure.
 Ultrahigh molecular weight polyethylene (UHMW)
Is it extremely dense type of polyethylene with a greater molecular weight than HDPE. Moreover, its
tensile strength is many times greater than steel.

Polyethylene is widely used in many industries and processes because of its various types. LDPE is
used in producing films (cling film, and milk carton lining), extrusion (flexible water pipes, cable
jacketing), injection moulding (buckets, and bowls), and in manufacturing wires and cables. While
HDPE is in same area as LDPE but producing different kinds of products. It produces producing films
(food packages, and shopping bags), extrusion (water pipes), injection moulding (dustbins, and crates).
[ CITATION the \l 1033 ]UHMWPE is used in making bulletproof vests, and LLDPE produces film
application such as stretch film. [CITATION Ton15 \l 1033 ]

The world demand will keep increasing. Gains would balance global economic growth, driven by
increased consumer spending and investment in manufacturing. Polyethylene will remain to be most
used plastic in the world taking advantage of its flexibility
, ease of storage, low cost and recyclability. [ CITATION fre \l 1033 ]

2.2.1 The History of Polyethylene

Polyethylene which is the most used plastic nowadays was first found in 1898 and by time was later
found again by scientist and chemists wondering what’s the use of the white, waxy material. March
27 ,1933 is the date in which the first factory named Imperial Chemical Industries in Northwich,
England produced useful polyethylene production that was discovered by Chemists Eric Fawcett and
Reginald Gibson which was unintentionally.

While the chemists where doing some experiments requiring high pressure on ethylene, one of the
testing vessels had leaked and left a drop of oxygen into an unexperimented ethylene sample in which
the next day polyethylene was produced due to an reaction between the chemicals. Chemists realized
that they are a lot of benefits of polyethylene and started to look forward in producing and enhancing
the material[ CITATION Suz19 \l 1033 ]. Although they discovered it in 1933 but it took them 5 years
to replicate and improve the material and the first material made from polyethylene was cream-colored
walking stick. In 1983, the industry started the manufacture of plastic on industrial scale rather than on
sample.

However, when World War II began many industries started the production of polyethene in a massive
amount because polyethylene acts as an insulator for radar cables which was helpful during the war
struggle. However, the British kept it as a top-secret when they start producing the substance which
gave them an advantage in long distance air warfare against the German submarines which they told
the told the Britain that they will suffer from starvation from food. Once the war has finished,
polyethylene started being produced all around the world from food packaging to carrier bags, plastic
pipes and so many useful materials. Although discovering of polyethylene was an advantage to whole
world but not the environment. Polyethylene takes time to get recycled which could need centuries,
therefore is said that it is destroying the environment and polyethylene bags have developed a mark of
Mans pollution of the earth as they say. Overall, Chris Browning is honored of his grandfather and the
researchers on this discovery in Norwich [ CITATION His10 \l 1033 ]. Producing ethylene was
accidentally but it led to industries producing this material over 700,000 tons a year.

2.2.2 Basic Operation of Producing polyethylene:

From plastics bags to bottles to children’s toys, all are made from polyethylene. The word poly means
long chains or repetitive chains of molecules in which these molecules are carbon and hydrogen atoms
only. The easiest way to produce polyethylene in small scale is by purifying amount of ethylene which
is the feedstock before the addition of any type of catalyst. The purifying process will allow a reaction
to begin that results in ethylene molecules form into polymer polyethylene.
The following steps of making polyethylene:
1. Purify Ethylene
2. Ethylene can catch easily impurities present in air such as moisture, sulfur and ammonia so
therefore it has to run through a purity regulator device.
3. The purity regulator machine will blend many gasses with ethylene and then extract off the
impurities and foreign matter. Note: This step should be made under high pressure.
4. After purifying ethylene is complete, then its passed down into a reaction tank.
5. Catalyst the can be added once ethylene is in the tank reaction. The most common used catalyst
is Benzyl peroxide. This kind of catalyst have molecules that can fall apart in which they can
break down and be left with unpaired electrons. The unpaired electrons will bond up with the
purified ethylene.
6. Once the benzyl peroxide is reacted with ethylene completely, empty the polyethylene into a
pelletizer machine. This machine is for shaping small quantity of polyethylene into pellets so it
could be for storage and transportation.
7. The small pellets can be reheated and molded into any shape required.[ CITATION Rob17 \l 1033
]

This process is one of the many other ways of producing ethylene which is quite easy and a does not
requires to many different chemicals however it is a slow process.

2.2.3 Manufacturers & Distributors of polyethylene is UAE:

Polyethylene is being produced each year in a very enormous quantity. That why there are plenty of
companies and different brands that produce and sell polyethylene. UAE produces a very good amount
each year in which they manufacture and also import. This table represent different manufacturers and
suppliers in United Arab Emirates. [ CITATION Pan19 \l 1033 ]

Manufacture & Supply In UAE

 Borouge Pte Ltd

Pantex Mena Fz Llc

Octal S.A.O.C Fzc

Abu Dhabi Polymers

Saudi Ethylene & Polyethylene Co.

Polyworld Fzco

Table 2 Manufacture and supply in UAE

2.2.4 Polyethene and environment

The use of polyethylene is seen in every aspect and field around us which is why it is produced in huge
amounts, and its production is increasing everywhere where in India and the world it is expected that it
will increase by 129% in 2023 due to the high demand in various activities. Polyethene showed its
tragical effect in all five environment categories aquatic, desert, forests, grassland, and tundra. The
plastic polluting the marine life is around 25 million tons which is 64% of the produced plastic.
[ CITATION Alk15 \l 1033 ]

According to an article that discusses the impact of the production of polyethylene in Nigeria the
increase of population lately has resulted in dramatic increase in the domestic waste produced also the
demand of products such as polyethylene. Not providing solid waste management in all of Nigeria has
resulted in the spread of the waste in water, agricultural areas, and open sites which also resulted
emission of toxic chemicals into the atmosphere, water, and soil which its continuity could cause death.
Specifically, in water the accumulated polyethylene creates small pools is a great breeding ground for
mosquitoes which increases the spared of malaria, which is a killer disease.[CITATION AOA12 \l
1033 ]
Polyethylene effect on wildlife is fatal. Animals both terrestrial and aquatic eat plastic and because it
cannot be digested readily in animals’ digestive tracts it fills their stomach which might lead to their
death because of starvation which is a long, slow, and very painful death.

People now are more aware of the impact of polyethylene (plastic) and try to reduce and raise
awareness of its dangers. Fees on consuming plastic was applied which reduced the plastic bags
consumption in Ireland by 93.5%, In addition people are encouraged to get rid of the use and toss habit
and try to reuse their plastic bags rather than consuming more or shifting to reusable bags like
Envirosax. This will save 685 of gallons of oil which is used in synthesizing plastic, reduce pollution,
save electricity, and save wildlife.[ CITATION gre18 \l 1033 ]

2.2.5 Annual statistics of polyethylene (polyethylene/million tons)

Table 3 annual statistics inn 2013,2015,108

The production of polyethylene is increasing throughout the years due to the demand in many different
sectors that uses it in different ways and for different purposes.
As shown in table 3 , Asia is the most producing and using area of polyethylene, while Europe comes
last with 12.9 polyethylene/ million tons.
 Table 4 Annual statistics for LDPE,LLDPE,HDPE

As shown in table 4 , Overall production and usage of polyethylene in the world shows that HDPE is
produced in higher quantities (37.5 polyethylene/ million tons) in comparison to LDPE (18.7
polyethylene/ million tons) and LLDPE (24.1 polyethylene/ million tons) [ CITATION the \l 1033 ]

2.2.6 Industries producing polyethylene in the UAE

 Borouge company

is AbuDhabi polymers company which produces 40% of the plastic in the UAE.Its total production of
plastic of polyethylene and polypropylene (polyolefins) is 4.5 million tonnes per annum. The advanced
technologies that Borouge uses lead to an excellent final product in terms of light weight and fast
processing. Polyolefins are used for industrial infrastructural applications, for domestic water pipeline
networks, and for onshore and offshore oil and gas transportation pipelines. The company contributed
to the UAE vision 2021 to enhance the production to be eco-friendly and a less cost and packaging. In
the future, as the demand of the polyethylene is increasing Borouge will continue to creative plastic
solutions and to become one of the plastic leaders among all the companies.[ CITATION Mar18 \l
1033 ]

 Al Bayader International
is an International leader in manufacturing and supplying food packaging solutions. It established at
Dubai at 1991 they produce one single use products like tableware, containers, baking molds, food
wrapping ect. The company aims to a friendly environment path that supports the customer needs
without ruining it’s quality.[ CITATION AlB \l 1033 ]

 Paklite
Is a plastic recycling company in the UAE. It deal with several polymers such as, Polyethylene,
Polystyrene ,Polyacrylonitrile, Polypropylene, Polyester and etc….They handle all type of wastes
coming out of a polymerization plants like: plant sweeps , blow down powders, reactor powders ,
lumps etc.[ CITATION pak \l 1033 ]

 Rakha Al-Khaleej International (RAI)

is an Emirati company that distributes polymer products over the GCC. Regarding the polyethylene it
distributes different types for different process including LDPE, HDPE,LLDPE,MDPE and other types
[ CITATION RAI \l 1033 ]

2.2.7 Classifications of polyethylene

Polyethylene is Commonly classified into different types depending on its melting point including Low
Density Polyethylene (LDPE), Linear Low-Density Polyethylene (LLDPE), High Density Polyethylene
(HDPE), and Ultrahigh Molecular Weight Polypropylene.

 Low Density Polyethylene (LDPE):

is a very flexible material with high ductility but low tensile strength. It is produced at high pressure
1000-3000 bar and a temperature of 80-300°C.The properties of the LDPE are a Melting point of 105
to 115°C, Density of 0.910 to 0.940 g/cm3 , an excellent electrical insulator , low water absorption and
low costing material.
The disadvantages of the LDPE are low strength and stiffness which leads to a susceptible stress
cracking, limited ability of handling high temperatures which limits its applications and highly
flammable.
The most common Application of LDPE is plastic bags. Other applications include are plastic bag
industrial containers, wash bottles, plastic bags for computer components, laboratory equipment and
Pipes and Fittings

 Linear Low-Density Polyethylene (LLDPE)

very similar to LDPE but its production process requires less energy than LDPE.It’s very flexible with
high strength, Good stress crack, translucent and an excellent for strong buffers.
Applications of LLDPE: good for film application such as stretch film, general purpose film, garment
packaging and agriculture film.

 High Density Polyethylene (HDPE)

Is stiff, strong and has a high density. It is manufactured at low temperature (70-300°C) and pressure
(10-80 bar). It’s Melting point: 120-140°C and a density of 0.93 to 0.97 g/cm3 , low cost polymer and
excellent electrical insulator.[ CITATION omn \l 1033 ]
HDPE is usually used for packaging applications like bottles, trays and cans. Since HDPE has a high
density it’s also used for cable protection, steel pipe coating and fuel tank

 Ultrahigh-Molecular-Weight Polyethylene (UHMWPE)

Is the most dense among the other types, it has a low coefficient of friction. 
used in the most corrosive environments at moderate temperatures because it is totally inert. It has a
high resistance at high temperatures.
UHMWPE is suitable for high wear applications such as tubes, liners, silos, containers and other
equipment.
 Figure 3 the processes involved for each type[ CITATION the17 \l 1033 ]

2.2.8 Comparison between different classification of polyethylene

Since the production of polyethylene has only one main reaction which is:

Therefore, the production will mainly depend on the different classifications which was mentioned
before briefly of polyethylene in which they mostly vary on the pressure, type of catalyst, type of
reactor, and it depends on the type of product that will be produced. The selection will be made based
on the costs of catalysts, pros and cons of each classification and quality of product needed.

2.2.8.1 High Density Polyethylene (HDPE)

High density polyethylene is the most used type household packaging material since it has the lower
cost between polymers. However, HDPE is a linear addition polymer of ethylene in which the
production of HDPE and LLDPE are produced at slightly different temperature and
pressure[ CITATION Els19 \l 1033 ]. HDPE is usually producing with molecular weight between
(200,000-500,000) g/mol and low-pressure between (1- 20) atmospheres.

Types of catalysts used to produce HDPE:

There are two types of catalysts that can be used which are:
Ziegler-Natta which is an organometallic catalyst which means titanium compound that have aluminum
alkyl[ CITATION Shi18 \l 1033 ]. The most common type of Ziegler-Natta catalyst in the production
of polyethylene is shown in figure (4) :

Figure 4 Ziegler-Natta Catalyst production

 Inorganic compound called Phillips Catalyst which contains of chromium oxide

supported on silica. This type of catalyst which 50% of the world uses it to produce
polyethylene[ CITATION Kla14 \l 1033 ].

Catalyst Cost (AED)

Ziegler-Natta(Titanium Tetrachloride + 4627.34 AED/25g
Triethyl-aluminum)
Phillips Catalyst( Chromium(VI) oxide on 411.94 AED/100G
silica)

Table 5 Catalyst used in HDPE

Since HDPE can be manufactured with 3 different type of process, they all function at very low
pressures between 10-80 atm and with temperature range of (350-42) K. These ranges of pressure
temperature can be used only with addition of Ziegler-Natta or Inorganic compound catalyst.
Pros & Cons of HDPE
Advantages Disadvantages
Stronger intermolecular forces and Highly Flammable
tenisle strength more than LDPE

Resist high temperatures (-40 C to 90 C) Takes a long time to break down (hard to
recycle )

Low cost High thermal expansion

Food grades available Poor weathering resistance.

Good chemical resistance Difficult to bond

Low strength and hardness, but is very Subject to stress cracking

ductile and has good impact strength

Almost transparent creates it suitable for Low strength/stiffness

packaging
Table 6 Pros & Cons of HDPE

Properties of HDPE:

 Density of HDPE can range from 930 to 970 kg/m3

 Melting point: 120-140°C

Figure 5 Properties of HDPE

Uses and Applications Of HDPE:

  Packaging Applications for an example: crates, trays, bottles for milk and fruit juices, cans for
food packaging, jerry cans, drums, industrial bulk containers and many more.
 Household products such as garbage containers, housewares, and ice boxes due to its low cost.
 Fibers and Textiles, due to its high tensile strength its most used it ropes, fishing and sport net,
nets for agricultural use, Industrial and decorative fabrics, etc.
 Pipes and fittings [ CITATION Spe19 \l 1033 ]

2.2.8.2 Cross-linked polyethylene

Cross linked polyethylene also stands for PEX, XLPE or PEX, is a type of polyethylene
classifications which is based on the method of cross-links. It has a wide range in devolving in
particular technology since the bonds are bonded which develop a stronger product and also it
enhanced the product wear resistance.
There are 2 main process that uses catalyst for the production of cross-linked polyethylene
which are:
A. By means of peroxide,
B. By moisture cross-linking

(A) By means of peroxide

In this method, the process needs a type of an initiator which organic peroxide is mostly used and
requires special downstream cross-linking equipment. The organic peroxide has to be on its original
state with no treated chemical structure. The initiator is set at low temperatures but then the
 equipment has to be at very high temperature and pressure so that bonds can be form and until all
the peroxide is consumed. Producing this type of polyethylene is more difficult than the other types.

(B) By moisture cross-linking

There are also two type of process by moisture cross-linking:

 Polymerizing ethylene with vinyl silane (copolymer)
 Extruder grafting of polyethylene with the vinyl silane.

This process can be straightly done in the reactor; however, the copolymer consists of catalyst and
additives may be added if wanted. The process is made at a very high pressure in the reactor. The
product will have highly branched low-density product since it was operated at a very high pressure.
The drawback of this process is that it limits the types of product that can be produced. However, it
plays a low importance today in medical field[ CITATION SAf08 \l 1033 ].

Catalyst Cost
organic peroxide 163.10 AED/100G

Trimethoxyvinylsilane (copolymer) 293.51 AED/100ML

Table 7 Catalyst used in Cross-linked

Pros & Cons of Cross-linked polyethylene

Advantages Disadvantages
Lower materials cost Difficult to produce
 Leak Resistant Odors, chemical taste, and possible health
effects

Flexibility Degradation from sunlight

Suitable for hot and cold pipes Fitting expenses

Higher tensile strength Perforation by insects

Table 8 Pros & Cons of Cross-linked

Uses and Applications of PEX

 Plumbing: usually industries uses cross-linked process to produce plumbing due to is elasticity
during installation

 Radiant Heating: tubing that is used for radiant floor heating in residential housing.

 Chemical Industry: is used for storage tanks that can hold all types of different chemicals.

 Water service lines, sizes ½ to 3 inch

Figure (6 ) shows that percentages of uses of cross linked polyethylene in different applications
:

Figure 6 Application Market share for cross linked

Properties of PEX

1. Does not have a melting point since its thermally resistant of up to 120 °C
2. All PEX is made up from HDPE
3. Consists of cross-linked bonds in their structure.
2.2.8.3 Ultrahigh-Molecular-Weight Polyethylene (UHMWPE)

Is the densest among the other types where it has a very long chain reaching to a molecular weight
between 2 and 6 million g/mole. This long chain backs up the bone by strengthening intermolecular
interactions.it is used in the most corrosive environments at moderate temperatures because it is totally
inert and it is suitable for high wear applications such as tubes, liners, silos, containers and other
equipment.Usually it’s available as poweder,sheets,rods or fibers.

UHMWPE is odorless, tasteless, and non-toxic. It has a Low moisture absorption and the ability of
Self-lubricating and highly resistant to corrosives except for oxidizing acids and abrasion as
well. Moreover, it is a good combination between high strength and low density were its yield strength
as high as 2.4 GPa and density as low as 0.97 kg/L.[ CITATION Int11 \l 1033 ]
Although UHMWPE has many properties and advantages it also has some disadvantages that should be
aware of. It has a low melting point ranging from 297 ⁰F to 305 ⁰F which indicates that it can’t be used
for high temperature applications. in addition, UHMWPE will deform continually as long as the stress
is present, an effect known as creep [ CITATION Eri17 \l 1033 ].

TYPICAL APPLICATIONS OF UHMWPE

 FOOD PROCESSING EQUIPMENT
 WATER TREATMENT

 CONVEYOR LINES

 WEAR STRIPS

 BEARINGS

 GEARS

 PISTONS

 VALVES

 MARINE EQUIPMENT

 WET ENVIRONMENTS THAT REQUIRE REGULAR HARSH CLEANING

[ CITATION flu16 \l 1033 ]
Figure 7 Applications of UHMWPE
 The production of UHMWPE takes 3 stages:

Stage 1: polymerization
Polymerization is the stage where the ethylene is transferred into
UHMWPE in a powder form. It is synthesized in a heterogenous
system where it’s composed of hexane solvent , ethylene gas and a
catalyst which is Ziegler Natta TiCl4 anchored on MgCl2, under the
conditions of low pressure ( 0.4 MPA to 0.6 MPA) and a moderate
temperature of (66 ⁰C to 90 ⁰C) and then it is fed into a reactor.[ CITATION use16 \l 1033 ]
Stage 2: consolidation
In this stage the powder is being transferred into final products using conventional processes like
compression molding or ram extrusion. A well combination of temperature, pressure, time and proper
equipment is needed to get the best results in this stage. [ CITATION pey15 \l 1033 ]
Stage 3: machining and polishing
After getting the bulk product final machining processes are bring processes For example, Sawing,
turning, drilling and grinding.[ CITATION pey15 \l 1033 ]

Catalyst Cost
Ticl4 4627.34 Dh for 25 G
Mgcl2 218.88 h for 1 ML
Table 9 Catlyst Cost for UHMWPE

2.2.8.4 Linear Low-Density Polyethylene (LLDPE)

LLDPE is very similar in structure to LDPE.It's like LDPE branching, but the branches are much
shorter.It has a milky color that is transparent and organic and it has a spectrum of densities between
0.915 and 0.925 g / cm3 .LLDPE is produced in a low pressure either using a gas phase reactor or a
solution process with1-butene, some1-hexene, and1-octene polymerization of ethylene .. LLDPE's
tensile strength is lower than LDPE.. Because of its effect and puncture resistance, both of which are
higher than those in LDPE, it succeeded in replacing LDPE in a few applications and In comparison to
HDPE and LDPE, LLDPE has good resistance to stress cracking.
LLDPE is desirable from an ecological point of view because it burns without any residue. It just turns 
to water and carbon dioxide. There is no release of toxic fumes in the process. LLDPE is mainly used
in making films. LLDPE can produce films with a lower thickness than what LDPE can manage to
produce. LLDPE is used to make agricultural films, general purpose films, stretch films, garment
packing films, and films for sheets and bags. Saran wrap, bubble wrap, and other multilayer films are
commonly used items made with LLDPE.[ CITATION Jos19 \l 1033 ]

Advantages of LLDPE
 Versatile and cost effective
 Lower seal initiation temperature balanced with mechanical properties
 Can reduce costs in high-performance structures

Applications of LLDPE
Due to its higher tensile strength and superior impact and puncture resistance, the popularity of linear
low-density polyethylene (LLDPE) is due to its rival low-density polyethylene (LDPE). This made it
possible for converters to make thinner films without sacrificing strength, saving material and cutting
costs. The strong durability of LLDPE compared to other goods has opened up new areas of use.

Generally, about 80% of LLDPE is used in film applications such as food and non-food packaging,
shrink / stretch film, and non-packaging applications. The trend in food packaging films is towards
high-performance film structures that are less permeable in order to improve shelf life and flavours.
Growth stems from the shift of products packed in rigid containers to flexible boxes of high quality.
LLDPE is used in extrusion coating applications where it helps to protect liquid container contents, part
icularly for paper and paperboard packaging. [ CITATION Jos19 \l 1033 ]

Synthesis of LLDPE
LLDPE is obtained through the copolymerization of ethylene with 1-hexene using (nBuCp)2ZrCl2 co-
catalyzed by methylaluminoxane (MAO).[ CITATION Lin99 \l 1033 ]

Catalyst Cost
methylaluminoxane 488.44 for 100 ml
Table 10 LLDPE catalyst
2.2.8.5 Low density polyethylene (LDPE)

It is a type of polyethylene with high flexibility, and specific flow properties which makes it especially
appropriate to plastic film applications like shopping bags. This particular type of polyethylene has
high ductility, and low tensile strength which is obvious because of its tendency to stretch when
strained.[CITATION Ton15 \l 1033 ]

LDPE applications

1. It is used to produce thin, and flexible products such as the plastic bags used to store different
kinds of products (newspapers, bread, frozen foods.. etc)
2. Shrink-wrap and thin films.
3. Coating disposable beverages cups.
4. Create thin container lids that manufacturers use.
5. Squeezable bottles and toys.
6. Wires and cable insulations.
7. Pipes.

Recycling LDPE

Recycling this type of polyethylene or any other type will decrease the load on our environment,
reduce energy usage, and decrease greenhouse gas emissions. All types of plastic require hundreds of
years to decompose, so many area offer recycling to LDPE and LLDPE. If area does not offer
recycling to this kind of products it is advised to reuse them instead of purchasing new ones. LDPE is
known by recycling code 4.

Products produced by recycling LDPE

1. Floor tiles.
2. Shipping envelopes.
3. Trash can liners.
4. Furniture.

And many more.[ CITATION Ama17 \l 1033 ]

Manufacturing process of LDPE

Manufacturing LDPE has five operations which are:

1. Compression of gas:

Ethylene in the gas phase is supplied and being melted with apart from the unreacted gas, in order to
compress in reactor #1. The produced compressed gas is again melted with the unreacted gas and
being compressed in compressor #2.

2. Polymerization:

An organic peroxide is being added to the second compressor gas into the reactor, the material gets
mixed using a stirrer. Polymerization occurs at a certain pressure and temperature.

3. Separation of gas:

Unreacted gas (unreacted ethylene) gets separated by 3 levels of separators. This unreacted gas will
be injected before the compressor.

4. Extrusion:

Since the unreacted gas is removed, the polymers can be extruded and pelletized.

5. Storage and packing:

The pellets get dried using a dryer and classified according to pellet size. Degassing is done by hot
air injection.[ CITATION htt2 \l 1033 ]
 Figure 8 Manufacturing LDPE flow sheet diagram

Advantages and Disadvantages of LDPE

Advantages:
o Inexpensive
o Impact resistant from -40℃ to 90℃
o Moisture resistance
o Chemical resistance
o Processed by all thermoplastic methods.
Disadvantages:
o High thermal expansion
o Subject to stress cracking
o Hard to bond
o Flammable
o Poor temperature capability [ CITATION uni \l 1033 ]
LDPE properties

Density 0.910–0.940 g/cm3

Pressure 1000-3000 atm
Temperature 80℃ continuously 95℃ for shorter time
Melting temperature 105-115℃
Tensile strength 7MPa
Specific gravity 0.92 ***
Flexural strength 6MPa

[ CITATION ess \l 1033 ] [CITATION Ton15 \l 1033 ]Table 11 LDPE properties

Catalyst used in producing LDPE

radical polymerization process and an initiator, such as a small amount of oxygen, and/or an organic
peroxide is used.

Catalyst Cost
Oxygen 1.10AED per 100g
2-Butanone peroxide 119.25AEDper 100ml

Table 12 Catalyst used in producing LDPE

Chapter 3 Process Selection

Producing polyethylene can be produced in so many ways that each has its own classification name.
From the above section in process synthesis all of the polyethylene classification has been explained
very well in terms of everything needed to make comparison. However, in every product being
produced, the selection among the different options that can be available can be tricky to choose in
order to maximize the profit and the percentage yield. In producing polyethylene there is only one
reaction of same reactants leads to the product but their catalyst, method, manufacturing and the type of
the product can vary.
So, the production of the polyethylene is branched to its classification:

Polyethylene
 LLDPE UHMWPE

HDPE Cross-linked LDPE

(PEX) Polyethylene

Figure 9 Classifications of polyethylene

By comparing all the classifications of the production of polyethylene, LDPE and HDPE were the most
common use types nowadays in which the products are very important and used everywhere and
however both of the process are not complicated such as the other classification but that does not mean
the other classifications are not important. For an example UHMWPE is a complicated process that
need 3 stages but it’s important in water treatment and production of gear and etc. Also, PEX Type is
important in devolving in particular technology but some of the catalyst used in this type needs special
downstream cross-linking equipment which makes it a more complex to produce. Last but not least,
HPDE and LDPE are the most important types of polyethylene in which has so many various
applications used all around the world.

By eliminating the 3 classifications of polyethylene, the remaining are:

Polyethylene

HDPE LDPE
Polyethylene
Figure 10 Polyethene 2 selected types
So, a comparison between these 2 common types should be made in order to select one of them in
terms of their properties, cost, and application which also means the material of the product produced.
Although they are polyethylene, but they vary completely. So, to start with their properties in which
they differ:

HDPE LDPE
Much denser and rigid Less dense

High tensile strength Less tensile strength

Melts at high Temperature Melts at lower than HDPE

Thick and rigid products Thin products
Ductile but less than LDPE Greater ductility

Table 13 Comparison of HDPE AND LDPE in terms of their properties

In terms of their applications:

HDPE LDPE
Milk and detergent jugs Plastic Bottles
Ropes Buckets
Garbage cans Grocery Bags

Water pipes Shrink-wrap and thin films

Table 14 Comparison of HDPE AND LDPE In terms of their applications

The last thing to compare with is their costs of catalyst which is mentioned before. Therefore, the
prices of catalyst used in LDPE was cheaper than HDPE. However, the prices of the catalyst can differ
from one supplier to the other. Both of the LDPE and HDPE are being produced in the UAE because
each type has its own quality and product, and both are needed.
To come the final decision, LDPE is selected from among all the other types due to its many useful
applications, inexpensive, and easy to operate.

Flow Diagram Selection of LDPE:

There are various methods for processing LDPE which is developing along the years. The main used
processes for the production of LDPE are:
 Autoclave method
 Tubular Method
 Figure 11 Flow diagrams of Autoclave & Tubular

[ CITATION
lyo16 \l 1033 ]
3.1 Autoclave method:

An overview
The gas that is fed into the process comes as 15 bar pressure from the cracker the pressure of ethylene
is increased in three stages to achieve the desired pressure of reaction. As the pressure increases the
temperature increases therefore after each rise cooling is required. The first step is to feed into the
booster compressor the source of ethylene the pressure will compress from 15 to 40 bar and then it will
cool down. The 40-bar gas is then fed to the main compressor and it will be compressed to 250 bars.
Because the secondary compressor converts the pressure from 250 to 2500 bar it is considered to be the
most important compressor. After that the gas is fed into the reactor with the reaction initiators.
Approximately 20 percent of the gas fed into the reactor
polymerizes during the reaction and the remaining is separated the gas that did not polymerize is fed ba
ck into the process after
the reaction. The material and any nonpolymer compounds will be separated in two stages
 immediately after the reaction. The first stage is the HPS (high pressure separator). The gas mixture is
cooled and separated and recycled back to the secondary compressor. At the second stage, the LPS
(low pressure separator), the rest of the gas is separated with the remaining of initiators from the
polymer. From the LPS the gas cycles into the Flash gas circulation. In the Flash gas circulation, the
gas it cooled down, separates from solvents, compressor oils and wax using a slop system and then the
gas is pressurized back to 40 bars and fed back to the primary compressor. To keep the gas clean from
any inert components some of the gas will be recycled back to the cracker.

3.2 Tubular method:

An overview

Ethylene feedstock is compressed to 250

bar by a
primary compressor and then to
between 2000 and
2500 bar by a secondary compressor. It
is preheated to an initiation temperature
of 14 °C and enters
the reactor in a plug flow regime where
polymerization is started by adding
peroxide initiator. T h e
reaction being exothermic, the
temperature rises until all initiator is
consumed. Temperature peaks of
up to 350 °C have been recorded. This
way conversion rates up to 37 % can be
obtained, depending on
product grade and required quality.
Reactor tubes are cooled, using a jacket
lled with high-pressure
water at 200 °C. When the temperature
has dropped suciently, fresh initiator is
added. The
tubular
reactor
can be as long as 0.5 to 1.5 km, usually
divided into a number of straight
sections connected by
180° curves. The inside diameter of the
tubes can range from 25–75 mm, and
due to the high pressure
Ethylene feedstock is compressed to 250
bar by a
primary compressor and then to
between 2000 and
2500 bar by a secondary compressor. It
is preheated to an initiation temperature
of 14 °C and enters
the reactor in a plug flow regime where
polymerization is started by adding
peroxide initiator. T h e
reaction being exothermic, the
temperature rises until all initiator is
consumed. Temperature peaks of
up to 350 °C have been recorded. This
way conversion rates up to 37 % can be
obtained, depending on
product grade and required quality.
Reactor tubes are cooled, using a jacket
lled with high-pressure
water at 200 °C. When the temperature
has dropped suciently, fresh initiator is
added. The
tubular
reactor
can be as long as 0.5 to 1.5 km, usually
divided into a number of straight
sections connected by
180° curves. The inside diameter of the
tubes can range from 25–75 mm, and
due to the high pressure
Ethylene feedstock is compressed to 250
bar by a
primary compressor and then to
between 2000 and
2500 bar by a secondary compressor. It
is preheated to an initiation temperature
of 14 °C and enters
the reactor in a plug flow regime where
polymerization is started by adding
peroxide initiator. T h e
reaction being exothermic, the
temperature rises until all initiator is
consumed. Temperature peaks of
up to 350 °C have been recorded. This
way conversion rates up to 37 % can be
obtained, depending on
product grade and required quality.
Reactor tubes are cooled, using a jacket
lled with high-pressure
water at 200 °C. When the temperature
has dropped suciently, fresh initiator is
added. The
tubular
reactor
can be as long as 0.5 to 1.5 km, usually
divided into a number of straight
sections connected by
180° curves. The inside diameter of the
tubes can range from 25–75 mm, and
due to the high pressure
Ethylene is fed to a primary compressor and it’s compressed to 250 bars then it goes to secondary
compressor and it’s being compressed from 2000 to 2500 bar. After compressing the ethylene will be
preheated to a temperature of 14 ⁰C to enter the reactor in a plug flow regime with a peroxide initiator
and the polymerization will start. The temperature will keep rising to a peak of 350 ⁰C until all the
amount of the initiator is consumed. The tubes of the reactor will be cooled using a high-pressure water
jacket at 200 ⁰C. After it cools down fresh initiator is added to the straight sections connected to 180⁰
curves of the tubular reactor.
After the polymerization ends both polyethylene and unreacted ethylene are fed to the high pressure
separator and expanded to a pressure of 250 bar where the unreacted ethylene will be fed back to the
suction side of the secondary compressor and the rest of the ethylene dissolved in the LDPE will be
separated using low pressure separator.

Tubular Vs Autoclave
Tubular Method Reactor Autoclave Method
Reactor
Conversion Conversion up to 36% Conversion up to 21%
--reaction heat partly --adiabatic, reaction
removed by coolant. heat adiabatic, reaction
heat removed by
reactant only removed
by reactant.

Capacity Tubular capacities of up to autoclave capacities of

450 kt/a up to 125 kt/a

Type of flow Plug flow CSTR

Mixing No Stirrer: • Laminar flow Mixing• Residence

behavior time distribution

Initiator used Cheaper oxygen initiator Organic peroxide

possible initiators only

Cost Less Expensive More Expensive

Operating pressure pressures between 2000 and 1300--2000 bar
3100 bar inlet of the first operating
reaction zone,

Size Larger Capacity Limited Size

Power Lower power consumption Higher power needed

Monomer conversion Monomer conversion can tubular process

reach values up to 40% compared with up to
25% in autoclaves

Table 15 Tubular Vs Autoclave

 Figure 12 Molecular mass distribution for autoclave and tubular

3.3 Process selection

LDPE is mainly processed using the two methods mentioned above the autoclave method and the
tubular. Choosing the best method for the project will be according on the factors mentioned in table
(15). From the conversion point which is an important factor that should be taken under consideration
while choosing the tubular has a higher conversion reaching to 36% while the autoclave has a 21%
conversion. Moreover, the capacity of the tubular is larger that that in the autoclave for a value of 450
kt/a and 125 kt/a respectively. In addition, tubular consumes less power that the autoclave which saves
cost and energy of the plant. Furthermore, the tubular reactor can use oxygen as an initiator which is
considered cheap while the autoclave uses organic peroxide initiators only. Besides the cost of the
autoclave reactor is more expensive than the tubular reactor. According to figure (12) tubular method
has a narrower MMD than that in the autoclave since the tubular reactor can be a very long tube where
it reaches 2000-3000m long and the mass transported as a plug flow. The pressure and temperature are
high, and no stirrer is used for mixing and at the wall the flow is laminar so the residence time is
approximately the same for each polymer chain, leading to a smaller molecular weight distribution with
less long chain branching. On the other side the autoclave reactor can be considered as a continuous
stirred tank reactor (CSTR), comparing to tubular reactor the pressures and temperatures are a little bit
lower. But there is abroad molecular weight distribution in combination with long chain branching. To
conclude, tubular reactor technology serves the demands of the plants nowadays so in this project
tubular reactor is selected.
 3.4 Flow
sheet
preparation
3.5 Process description

The process of production of LDPE, is divided into three main stages. The first stage is the
pretreatment which is an important step to prepare the ethylene gas to enter the tubular reactor with the
proper conditions, this stage is consist of a mixing point where the ethylene feed get mixed with the
unreacted ethylene and it’s also consists of compressors hyper and primary compressors and heat
exchangers until the gas reaches a temperature of 150 ⁰C and a pressure of 2000 bar. The second stage
is the reaction zone which it is the tubular reactor. Tubular reactor is a plug flow reactor that is divided
into four zones and it has a water vapor stream that maintain the temperature at the required degree
there are injection points where the organic initiator can enter from it. 65ton/hr of fresh ethylene gas is
fed into the reactor. The conversion of ethylene into LDPE is 20% and the rest of unreacted ethylene
will be recycled back into the feed. The last stage is the separation areas consisted of high- and low-
pressure separators that evaporates the unreacted ethylene and send it back to the feed, purge the wax
and oil out of the process and gets the LDPE as a product out of the process.
When ethylene gas enters the process it get mixed with the unreacted ethylene that is recycled back
from the reactor then it get compressed and cooled repeatedly two times and get mixed again with the
second recycling stream that is carrying unreacted ethylene as well. After that the ethylene passes
through primary compressor and hyper compressor which raise the pressure of the ethylene to the
operating pressure of the reactor and then enters a cooler right before the reactor. In the reaction zone
the organic peroxide initiator is being fed to the reactor along with the ethylene. Next after the reactor a
control valve reduces the pressure before entering the heater. After the heater a high-pressure separator
separates the LDPE and the ethylene where all of the LDPE will be at stream 16 while the unreacted
ethylene will be at stream 14 and 16. From stream 14 onwards the unreacted ethylene will be cooled
and then separated using a cyclone separator which separated the gas from the wax while on stream 16
the control valve reduces the pressure and then at the low pressure separator the LDPE separates from
the unreacted ethylene and get purged and the unreacted ethylene gets separated again using the
cyclone which purges the wax and oil and the ethylene gets recycled.

Chapter 4 Mass and Energy Balance

Reaction Structure:

T=150oC
P=2900Bar

To find n of the main reaction, select two points from MW distribution figure which at first point
logMW = 4 and the Second LogMW=5 and use the following equation:

Average Mw = n Mw

Figure 13 Molecular Distribution of polyethylene

Known Values:
g
Mwethylene= 28.05 mol
g
Mw1= 81.5 mol
g
Mwethylene= 181.3 mol

Average Mw1 = n1 Mwethylene

g
81.5 mol = n1 (28.05)

n1= 2.9055 = 3

Average Mw2 = n2 Mwethylene

g
181.3 mol = n2(28.05)

n2 = 6.399 = 6.4

n 1+ n 2
Average n = 2 = 4. 7 = 5
4.1 Material balance

Material balance is an important step when designing a chemical plant. It’s all about applying the law
of conservation of mass which states that mass can neither be created nor destroyed therefore, the total
mass of input should be equal to the total mass of output.

Material balance on tubular reactor (R-101)

In this part the fresh ethylene is fed in the tubular reactor to get polymerized

Stream 10 – 11

ṁ C 2 H 4 , 10=ṁ C 2 H 4 , 11 (1−x )

ton ton
ṁ C 2 H 4 , 10=65 ( 1−0.2 )=52
hr hr

ṁC 2 H 4 , 11 52
Y C 2H 4= = =0.8
ṁC 2 H 4 ,10 65

ṁ LDPE 13
Y LDPE= = =0.2
ṁtotal 62

Stream number 10 11

Total mass flow rate (ton/hr) 65 65

C2H4 (ton/hr) 65 52
Y C 2H 4 1 0.8
LDPE (ton/hr) 0 13
 Y LDPE 0 0.2

Material balance on high pressure separator (V-101)

Stream 13 – 14+16

ṁ 13=ṁ 16+ ṁ 14

Material balance on ethylene

ṁ13=ṁ16+ ṁ14
52 ( 0.8 )=90 % ( 0.8∗52 )+10 % (52∗Y C 2 H 4 )

Y C 2 H 4 =0.8

Stream number 13 14 16

Total mass flow rate (ton/hr) 65 46.8 18.2

C2H4 (ton/hr) 52 46.8 5.2

Y C 2H 4 0.8 1 0.8

LDPE (ton/hr) 13 0 13

Y LDPE 0.2 0 0.2

 ton
w=10 % ( 52 ) =5.2
hr

ton
Enew =52−5.2=46.8
hr

ton
ṁ 14=0.9∗(5.2+ 42.12)=42.12
hr

ton
ṁ C 2 H 4 , 16=9.88
hr

ton
ṁ 14=5.2+ 42.12=47.32
hr

ton
ṁ 16=LDPE+10 % ( C 2 H 4 )=13+ 9.88=22.88
hr

ton
ṁ 14=90 % ( 52 )=46.8
hr

ton
ṁ 16=5.2∗10 % ( C 2 H 4 ) +13=18.2
hr

Material balance on LDPE

ṁ 16 , LDPE= ṁ14 , LDPE + ṁ13 , LDPE

13∗0.2=0+ Y LDPE∗13=0.2
Material Balance on Cyclone Separator

Stream 14A - 14B + 14C

ṁ 14 , A =ṁ 14 ,C + ṁ 14 , B

46.8=4.68+ ṁ14 ,B

ton
ṁ 14 , B=42.12
hr

Material balance on low pressure separator (V-103)

Stream 17- 18

ṁ 17=ṁ 17 , A + ṁ18
18.2= ṁ17 , A +1.82
 ton
ṁ 17 , A =16.38
hr

Material balance on Cyclone separator (V-104)

Stream 18 – 20

ṁ18=ṁ19 , A + ṁ20

1.82=5 % (1.82)+ ṁ20

ton
ṁ 20=1.729
hr

Material balance on mixing point on stream 15

ṁ 7= ṁ15 + ṁ 6

65=42.12+ ṁ6

ton
ṁ 6=22.88
hr

Material balance on mixing point on stream 24

Material balance on ethylene:

ṁ 2=ṁ24 + ṁ1

22.88=1.729+ ṁ1

ton
ṁ 1=21.151
hr

Primary Stages material mass balance:

Form stream 2 up till stream 6, the inlet will equal the outlet therefore stream 2 and stream 6 has same
flow rate and this is assumed as one stage unit.
Material balance on ethylene:

ṁ 2=ṁ 6

ton
ṁ 2=22.88
hr

Overall Material Balance on the LDPE

Overall Mass Balance(ton/hr)

Stream 1 19, A 14, C 17, A

Number
Ethylene 21.151 0 0 0

LDPE 0 0 0 16.38

Wax 0 0 4.68 0

Wax Oils 0 0.091 0 0

ṁ1=ṁ19 , A + ṁ14 , c + ṁ17 , A

21.151=0.091+ 4.68+16.38

ton ton
21.151 =21.151
hr hr

4.2 Energy Balance

To obtain the energies thought the system, an energy balance should be done on each equipment. In
this part, the energies coming in and out are calculated for each stream where for compressors only the
compressor work is been calculated since it’s the required work for the equipment where the efficiency
of each compressor is 85 %. The heat enthalpies are calculated for streams entering the equipment and
leaving the equipment where the change in enthalpy is the change of of energy system.

ADDITIONAL
INFORMATION:
For C 2 H 4 ,
For (C 2 H 4 )5
SG = 0.992
3
1 −3 m
1 −7 m
3 =V =1.0752 ×10
=V =7.8 ×10 ρ kg
ρ kg
Tubular reactor(R-101)

- From Stream 10 to 11

T =150 ℃ P=2000 ¯¿

˙ kg
mLDPE =11793.4
hr
−92 kj kj
∆ Hr= =−38749.7
mole hr

ṁC p ∆ T ( reactants )+ ∆ Hr+Q=ṁC p ∆ T ( products )

58967 ×1.98 × ( 150−25 )−38749.7+ Q=11793.4 ×1.85+47173.6 × 1.98¿ (150−25)

 kj
Q=1.5 × 105
hr

Control valve

- From Stream 11 to 12

Species kmol kj kmol kj

ṅ¿ ( ) H ¿( ) n ˙out ( ) H out ( )
hr hr hr hr
C2 H4 1681.76 H1 1681.76 H3
LDPE 84.2 H2 84.2 H4
kj 31851.92 kj 2949551.39
Total H ¿ ( ) Total H out ( )
hr hr

∆ H =V ∆ P+ C p
 423
H 1=(7.8× 10 )×(2.9 ×10 −101325)+ ∫ 40.75 x 10−3 +11.47 x 10−5 T −6.89 x 10−8 T 2−17.66 x 10−12 T 3 dT ¿
−7 8

298

423
−3 8 kj
H 2=(1.0752× 10 )×(2.9 ×10 −101325)+ ∫ (35.4 dT ¿)=316126.56 ¿
298 hr

423
H 3=(7.8 ×10−7 )×(2.9 × 108−2 ×107 )+ ∫ 40.75 x 10−3+ 11.47 x 10−5 T −6.89 x 10−8 T 2−17.66 x 10−12 T 3 dT ¿=
298
423
kj
H 4 =(1.0752 ×10−3) ×( 2.9× 108−2 ×107 )+ ∫ (35.4 dT ¿)=294731.5 ¿
298 hr
kj
Q=∆ H out −∆ H ¿=2949551.39−31851.92=2917699.47
hr

Heat exchanger, heating (E-104)

- From stream 12 to 13

C p mix=∑ yiCpi

kj
C p mix=( 0.8 )( 9.238 )+ (1.85 )( 0.2 ) =7.761
kg k

Q=∆ H=m C p mix ∆T

kj
¿(58967.008) (7.761 ¿ ( 423−298 )=56943434.9
hr
High pressure separator (V-101)

- From stream 13 to 14,16

Species kmol kj kmol kj

ṅ¿ ( ) H ¿( ) n ˙out ( ) H out ( )
hr hr hr hr
C 2 H 4 ( 14) 1681.76 H1 1516.29 H3

C 2 H 4 (16) 1681.76 H1 168.477 H5

LDPE( 16) 84.2 H2 84.2 H4

kj 50.28 kj 16618.34
Total H ¿ ( ) Total H out ( )
hr hr

∆ H =V ∆ P+ C p

Stream 13
 523
H 1=(7.8× 10−7 )×(2 ×107 −101325)+ ∫ 40.75 x 10−3 +11.47 x 10−5 T−6.89 x 10−8 T 2−17.66 x 10−12 T 3 dT ¿=
298
523
−3 7 7 kj
H 2=(1.0752× 10 )×(2.8 ×10 −2× 10 )+ ∫ (35.4 dT ¿)=23.62 ¿
298 hr

Stream 14
523
H 3=(7.8 ×10−7 ) ×(2.8 × 107−2 ×107 )+ ∫ 40.75 x 10−3 +11.47 x 10−5 T −6.89 x 10−8 T 2−17.66 x 10−12 T 3 dT ¿=23.62
298 h
Stream 16
523
kj
H 4 =(1.0752 ×10−3)×(2.8× 107−2 ×107 )+ ∫ (35.4 dT ¿)=23.62 ¿
523 hr
kj
Q=∆ H out −∆ H ¿=16618.34−50.28=16568.06
hr
Heat exchanger, cooling (E-105)

- From stream 14- 14, A

Species kmol kj kmol kj

ṅ¿ ( ) H ¿( ) n out
˙ ( ) H out ( )
hr hr hr hr
C2 H4 1513.5918 H1 1513.5918 H2
LDPE - - -
kj 5.2 ×10 7
kj 3.2 ×10 7
Total H ¿ ( ) Total H out ( )
hr hr

∆ H =Q=ṁ C p ∆ T

Stream 14

400
¿ ( 42456.3 )
(∫
523
)
40.75 x 10−3+11.47 x 10−5 T −6.89 x 10−8 T 2−17.66 x 10−12 T 3 dT ( 400−523 )= ( 42456.3 ) (−9.925 ) (−12
Cyclone separator (V-102)

- From stream 14, A-14,B-14,C

Species kmol kj kmol kj

ṅ¿ ( ) H ¿( ) n ˙out ( ) H out ( )
hr hr hr hr
C2 H4 1513.5918 H1 1362.2325 H2
LDPE - - -
wax - - H3
kj 3.2 ×107 kj −2.28 ×107
Total H ¿ ( ) Total H out ( )
hr hr

H= ṁC p ∆T

Stream 14,B
360
H 2=( 38210.621 )
(∫
400
)
40.75 x 10−3 +11.47 x 10−5 T −6.89 x 10−8 T 2−17.66 x 10−12 T 3 dT ( 360−400 )=( 38210.621 ) (−3.0

Stream 14,A
 400
H 1=( 42456.3 )
(∫
298
)
40.75 x 10−3 +11.47 x 10−5 T −6.89 x 10−8 T 2−17.66 x 10−12 T 3 dT ( 400−298 )=( 42456.3 ) ( 7.456 ) ( 10

Stream 14,C
kj kj kj
H 3=H 2 −H 1=4.6 ×10 6 −3.2 ×107 =−2.74 ×107
hr hr hr
7 7 7 kj
Q=∆ H out −∆ H ¿=−2.28 × 10 −3.2 ×10 =−5.48× 10
hr
Heat exchanger, cooling(E-106)

-From stream 14 to 15

E-106

∆ H =ṁC p ∆ T

Stream 14,B

360
¿ ( 38210.621 )
(∫
400
)
40.75 x 10−3 +11.47 x 10−5 T −6.89 x 10−8 T 2−17.66 x 10−12 T 3 dT ( 360−400 ) =( 38210.621 )(−3.01 ) (−
Control Valve

From Stream 16 - 17

Species kmol kj kmol kj

ṅ¿ ( ) H ¿( ) n ˙out ( ) H out ( )
hr hr hr hr
C2 H4 165.52 H1 165.52 H3
LDPE 84.2 H2 84.2 H4
kj 3203228.75 kj 3212415.11
Total H ¿ ( ) Total H out ( ))
hr hr

523
H 1=165.52 ×(7.8× 10 ×( 2.8× 10 −101325)+ ∫ 40.75 x 10−3+11.47 x 10−5 T −6.89 x 10−8 T 2−17.66 x 10−12 T 3 dT )
−7 7

298
523
¿ 3601.87+165.52 ∫ 40.75 x 10−3 +11.47 x 10−5 T −6.89 x 10−8 T 2−17.66 x 10−12 T 3 dT ¿
298
kJ
¿ 6478.45
hr
523
−3 7
H 2=84.2 ×(1.0752× 10 ×(2.8× 10 −101325)+ ∫ 35.4 dT )
298
523
¿ 84.2 ×( 29921.33+ ∫ 35.42)
298
 kJ
¿ 3196750.3
hr
523
H 3=165.52 ×(7.8× 10−7 ×(5.6 ×107−2.8× 107)+ ∫ 40.75 x 10−3 +11.47 x 10−5 T −6.89 x 10−8 T 2−17.66 x 10−12 T 3 dT
298
523
¿ 3614.96+165.52 ∫ 40.75 x 10−3 +11.47 x 10−5 T −6.89 x 10−8 T 2 −17.66 x 10−12 T 3 dT ¿
298
kJ
¿ 6491.69
hr
523
−3 7 7
H 4 =84.2 ×(1.0752 ×10 ×(5.6 ×10 −2.8 ×10 )+ ∫ 35.42 dT )
298
523
¿ 84.2 ×( 30105.6+ ∫ 35.42 dT )
298
kJ
¿ 3205923.42
hr
kJ
⁖ Δ H=Q=9186.36
hr

Low Pressure Separator

- From Stream 17 – 17A& 18

Species kmol kj kmol kj

ṅ¿ ( ) H ¿( ) n out
˙ ( ) H out ( )
hr hr hr hr
C 2 H 4 ( 17) 165.52 H1 - -
LDPE (17) 84.2 H2 - -
C 2 H 4 ( 18) - - 58.97 H3
LDPE (17, A) - - 106.14 H4
 kj 484243024 kj −588075671.8
Total H ¿ ( ) Total H out ( ))
hr hr

523
H 1=165.52 ×(7.8× 10 ×(5.6× 10 −101325)+ ∫ 40.75 x 10−3+11.47 x 10−5 T −6.89 x 10−8 T 2−17.66 x 10−12 T 3 dT )
−7 7

298
kJ
¿ 10093.57
hr
523
−3 7
H 2=84.2 ×(1.0752× 10 ×(5.6 × 10 −101325)+ ∫ 35.4 dT )
298
kJ
¿ 5731262.901
hr

523
H 3=58.97 ×(7.8 ×10 ×(50000−5.6× 10 )+ ∫ 40.75 x 10−3 +11.47 x 10−5 T −6.89 x 10−8 T 2 −17.66 x 10−12 T 3 dT )
−7 7

298
kJ
¿−1548.61
hr
523
−3 7
H 4 =106.14 ×(1.0752× 10 ×(50000−5.6 ×10 )+ ∫ 35.4 dT )
298

kJ
¿−5539705.58
hr
kJ
⁖ Δ H=Q=−1072318696
hr

Heat Exchanger
- From Stream 18 – 19

ΔH =ṁ cp ΔT
 523
ΔH =1651.076 × ∫ 40.75 x 10−3 +11.47 x 10−5 T−6.89 x 10−8 T 2−17.66 x 10−12 T 3 dT ¿ ×(523−473)
473
kJ
¿ 342598.27
hr

Cyclone Separator

- From Stream 19 – 19A & 20

H= ṁcp ΔT

For stream 19

473
H ¿ ,c 2 H 4=1651.076 × ∫ 40.75 x 10−3 +11.47 x 10−5 T −6.89 x 10−8 T 2−17.66 x 10−12 T 3 dT ¿ ×(473−298)
298
kJ
¿ 3823520.524
hr
For stream 20
400
H out , c2 H 4=1565.704 × ∫ 40.75 x 10−3 +11.47 x 10−5 T −6.89 x 10−8 T 2−17.66 x 10−12 T 3 dT ¿ ×( 400−473)
473
kJ
¿ 660290.26
hr
For stream 19,A

H out , wax ,oil=H out ,c 2 H 4 − H ¿,c2 H 4

kJ
660290.26−3823520.524=−3163230.26
hr

kJ
⁖ Δ H=Q=−6326460.524
hr
Compressor (C-105)

- From Stream 20 – 21

Compressor work:

for Ethylne γ =1.24

T 1=400 k
p2 m
T 2=T 1 ( )
p1
∴ T 2=423.7 K
m=0.194

p 2 75000 pa
CPR= = =1.5
p 1 50000 pa
y
T 2 y−1
CPR=( )
T1
y
432.7 y−1
1.5=( )
400
y=1.24

y
cp T 2
Cw= (CPR y−1 −1)× ŋ̇
ŋ

(2.44)( 432.7)
¿-1)×55.918
0.85
 = 52300.88 kw

Heat exchanger

-From Stream 21 – 22

ΔH =ṁ cp ΔT
432.7
ΔH =1789.370 × ∫ 40.75 x 10−3 +11.47 x 10−5 T −6.89 x 10−8 T 2−17.66 x 10−12 T 3 dT ¿ ×(523−473)
372.7
kJ
¿ 495403.8243
hr

Compressor C-106
- From Stream 22 – 23

Compressor work:
γ =1.24
T 1=372.7 k
p2 m
T 2=T 1 ( )
p1
∴ T 2=395.099 K
m=0.194

p 2 101325 pa
CPR= = =1.351
p 1 75000 pa
 y
T 2 y−1
CPR=( )
T1
y
395.099 y−1
1.351=( )
372.7
y=1.241
y
cp T 2 (2.44)(395.099)
Cw= (CPR y−1 −1)× ŋ̇= ¿-1)×55.918
ŋ 0.85
= 1418.4 kw

Heat exchanger (E-109)

- From Stream 23 – 24

ΔH =ṁ cp ΔT
298
ΔH =1789.376 × ∫ 40.75 x 10−3+11.47 x 10−5 T −6.89 x 10−8 T 2−17.66 x 10−12 T 3 dT ¿ ×(298−395.099)
395.099
kJ
¿ 1230126.1
hr

Mixing

- From Stream 1 ,24 – 2

Species kmol kj kmol kj

ṅ¿ ( ) H ¿( ) n ˙out ( ) H out ( )
hr hr hr hr
C 2 H 4 (1) 685.25 H1
C 2 H 4 (24) 63.9 H 24 741.299 H2
kj 1230126.1 kj 1230126.1
Total H ¿ ( ) Total H out ( ))
hr hr

Where H1 is zero since it’s the first stream into the system:
H 1=0
kj
H 24=1230126.1
hr

H 1 +¿ H 24 = H 2
kj
H 2=1230126.1
hr
kj
⁖ Δ H=Q=1230126.1
hr
Compressor C-101

From Stream 2 -3
From 1 Bar- 12 Bar

Compressor work:

P2 12
T2= T1( P 1 )m= 298( 1 ¿0.194= 482.589 K

12
CPR= 1 = 12

y
482.589 y−1
12=( ¿¿ , y=1.25
298

(2.44)( 482.589) 1.25

Cw = (12 1.25−1 −1 ¿(741.3)= 2.5 ×10 11 kw
0.85

Heat Exchanger E-101

ΔH =ṁ cp ΔT
 350
ΔH = (20756.34 kg/hr)( ∫ 40.75 x 10−3+11.47 x 10−5 T −6.891 x 10−8 T 2+17.66 x 10−12 T 3 dT)
482.589

kj
=2.33 ×10 7
hr

Mixing

- From Stream 6 ,15 – 7

Species kmol kj kmol kj

ṅ¿ ( ) H ¿( ) n ˙out ( ) H out ( )
hr hr hr hr
C 2 H 4 (6) 741.299 H1
C 2 H 4 (15) 1364.66 H2 2105.96 H3
kj 1.48153 ×10 10
kj 1.489 ×1010
Total H ¿ ( )) Total H out ( ))
hr hr

From the before streams we know:

kj
H 1=¿ 1.53 ×10 7
hr
10 kj
H 2=1.48 ×10
hr

H 1 +¿ H 2= H 3
kj
H 2=1.489 ×1010
hr
kj
⁖ Δ H=Q=7.5 ×107
hr
Compressor (C-103) (Primary Compressor)

-From Stream 7 -8
-From 24 Bar- 250 Bar

Compressor work :

P2 250
T2= T1( P 1 )m= 350( 24 ¿0.194= 551.45 K

250
CPR= 24 = 10.42

y
551.45 y−1
10.42=( ¿¿ , y=1.2406
350

(2.44)(551.45) 1.2 406

Cw = (10.42 1.24069−1 −1 ¿(2105.96)= 5.879 ×10 11 kw
0.85
Compressor C-104 (Hyper Compressor)

-From Stream 8-9

-From 250 Bar- 2000 Barr

Compressor work :

P2 2000
T2= T1( P 1 )m= 551.45 ( 250 ¿0.194= 825.48 K
2000
CPR= 250 = 8

y
825.48 y−1
8=( ¿¿ , y=1.24069
551.45

(2.44)( 825.48) 1.2407

Cw = (8 1.2407−1 −1 ¿(2105.96)= 2.25496 ×10 11 kw
0.85
Pre-Cooler E-103

ΔH =ṁ cp ΔT

423
ΔH = (20756.34 kg/hr)( ∫ 40.75 x 10−3+ 11.47 x 10−5 T −6.891 x 10−8 T 2+17.66 x 10−12 T 3 dT )(423-
825.48
825.48) =
kj
= 2.9 ×1 08
hr

Nomenclature

Variable Symbol Units

Molecular Weight Mw g/mol

Number of moles N mol

Mass flow rate ṁ 1 Kg/hr

Mole fraction in the gas Y mol

phase
Conversion percentage x %

Molar flow rate entering nin kmol/hr

Molar flow rate leaving nout kmol/hr

enthalpy entering hin kj/hr

enthalpy leaving hout kj/hr

Change of enthalpy ΔH kj/hr

change of energy of the Q kj/hr

system
pressure ratio CPR Unitless

Heat capacity coefficient y (gamma) unitless

Density ρ Kg/m3

Volume V M3

Compressor work Cw KW

Heat Capacity Cp Kj/K

Change in temperature T K
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