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CAB 4013

PLA T DESIG I
July 2010 Semester

I TERIM REPORT :

POLYETHYLE E TEREPHTHALATE (PET) PRODUCTIO


BASED O ESTERIFICATIO PROCESS TECH OLOGY

GROUP 28

MUHAMMAD AIMEN BIN ISA 10284


MUNIRAH BINTI SAMSUDDIN 9813
NIK ASMADI BIN AZNAN 9603
AHMAD NIZAR BIN YUNUS 10216
NUR FATHIAH BINTI JASMARI 10233

CHEMICAL ENGINEERING PROGRAMME


UNIVERSITI TEKNOLOGI PETRONAS
Bandar Sri Iskandar, 31750 Tronoh, Perak Darul Ridzuan
CERTIFICATIO OF APPROVAL

CAB 4013
PLA T DESIG I
July 2010 Semester

I TERIM REPORT :

POLYETHYLE E TEREPHTHALATE (PET) PRODUCTIO


BASED O ESTERIFICATIO PROCESS TECH OLOGY

GROUP 28

MUHAMMAD AIMEN BIN ISA 10284


MUNIRAH BINTI SAMSUDDIN 9813
NIK ASMADI BIN AZNAN 9603
AHMAD NIZAR BIN YUNUS 10216
NUR FATHIAH BINTI JASMARI 10233

APPROVED BY,

( IR. DR. ABD HALIM SHAH MAULUD )


CHEMICAL ENGINEERING PROGRAMME
UNIVERSITI TEKNOLOGI PETRONAS

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EXECUTIVE SUMMARY

Polyethylene Terephtalate is a thermoplastic polymer resin of the polyester family and


most often used to make synthetic fibers, containers for food and beverages, pharmaceuticals,
make-up and other thermoforming applications, where engineering resins often come out in
combination with glass fiber. Polyethylene terephthalate is frequently shortened to PET or
PETE. In order to produce PET, there are two major processes, called esterification and
transesterification, where esterfication used ethylene glycol (EG) and terephthalic acid (TPA)
as its raw material while transesterification used EG and dimethylterephthalate (DMT).
Regarding these two process, both will be further explain in the next chapter as well as why
esterification process is being choose in this project.

Technically speaking, PET is a linear thermoplastic resin that has several advantages,
especially when it’s being used for packaging. PET does not break easily and edibles stored
since it acts as a good barrier to elements outside of the container. The main objective of this
project is to investigate the feasibility of setting up a polyethylene terephthalate (PET)
producing plant based on the selected process technology.

Throughout this project, Chapter 1 will mainly emphasize on the project background,
problem statement as well as scope of work, while the Chapter 2 gives details of the project
background, market survey, properties of chemicals used, site feasibility study and feedstock
supply. The location chosen for the plant is Kerteh because of the availability of raw material
utilities and transportation. On the other hand, Chapter 3 discusses the preliminary hazard
analysis which includes identification of material and chemical hazard, safety aspects in order
to reduce potential accidents and also local safety regulations.

Then analysis on the conceptual process design was done in Chapter 4. It is important
to understand the basic principle of the whole process ; such as what reaction is taken place,
chemical reaction involved and types of reactor that we should used. In this chapter, the plant
is to be operated in continuous mode and the type of reactor used is the conversion reactor.
The separation units required for the process route is including distillation column for the
purification of ethylene glycol (EG) or act a main medium to separate water during reaction.

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In achieving better conversion, unreacted EG is recycled to the main stream. Overall, the
whole process of producing PET was done by using iCON simulation result.

Chapter 5 mainly describes the process flow and process flowsheet as well as manual
calculation on iCON simulation result of material balance. Heat integration calculation is also
mentioned by using pinch technology, in order to maximized energy used. Meanwhile, in
Chapter 6, the description about the process is determine by types of reactor used.

Throughout the project, estimate production rate of the plant is 30,449 ± 1.72 kg/year,
which is equivalent to 30.449 ± 0.00172 tonnes per annum with high purity of PET produced,
98 ± 0.4%. Thus, the proposed plant design will be justified based on the economic potential
of the process, by comparing the price of PET and price of raw materials needed (TPA and
EG). Hence, overall process description on this project will be further explained in each
chapter that has been mentioned earlier.

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ACK OWLEDGEME T

Alhamdulillah, thanks to Allah for giving us opportunity to complete this Plant


Design 1 course for this semester after have been struggling with all the problems and
challenges in completing this design project for the past several months.

There were about fourteen (14) weeks have been given to us in completing the design
project in Plant Design Project 1 (CAB4013) course under the supervision of our keen
supervisor, Ir Dr Abd Halim. We as the member of this group would like to pass our highest
gratitude to Ir Dr Abd Halim for all his guidance and continuous supports throughout the
semester. He has been a very supportive supervisor and willing to share his knowledge, in
order ensure that we could learn and understand every single thing in this project. Our
gratitude is also extended to PDP 1 coordinator, Dr. Rajashekhar Pendyala and Dr. Ridza for
their efforts in arranging the iCon seminar and planning the course structures so that we could
complete our project smoothly throughout this whole semester.

Last but not least our appreciation is to our beloved group mates, course mates and
also friends, thanks for all the supports and motivations that help us to complete this project
with a successful ended. Not to forget to those who directly or indirectly involved in giving
us the opportunity to learn and work as a team while designing our first plant project.

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TABLE OF CO TE TS

EXECUTIVE SUMMARY ..................................................................................................... 3

ACK OWLEDGEME T ....................................................................................................... 5

ALHAMDULILLAH, THA KS TO ALLAH FOR GIVI G US OPPORTU ITY TO


COMPLETE THIS PLA T DESIG 1 COURSE FOR THIS SEMESTER AFTER
HAVE BEE STRUGGLI G WITH ALL THE PROBLEMS A D CHALLE GES I
COMPLETI G THIS DESIG PROJECT FOR THE PAST SEVERAL MO THS. ... 5

LIST OF FIGURES ................................................................................................................. 9

CHAPTER 1 : I TRODUCTIO ........................................................................................ 11

1.1 BACKGROU D OF DESIG PROJECT .................................................................................. 11


1.2 PROBLEM STATEME T ........................................................................................................ 11

FIGURE 1 : GLOBAL PET DEMA D ............................................................................... 12

1.3 OBJECTIVE ........................................................................................................................... 13


1.4 SCOPE OF WORK.................................................................................................................. 14

CHAPTER 2 : LITERATURE REVIEW ........................................................................... 15

2.1 BACKGROU D OF DESIG PROJECT .................................................................................. 15


2.1.1 Overview of product, feedstock and byproducts ........................................................... 15
2.1.2 Process Primary Routes to PET Production ................................................................. 19
2.1.3 Process Alternative Routes ........................................................................................... 20
2.1.4 History, Applications and Usage .................................................................................. 22
2.2 PRODUCT MARKET SURVEY ............................................................................................... 24
2.2.1 Resources and raw Materials ....................................................................................... 24
2.2.2 Global Market Outlook ................................................................................................. 27
2.2.3 Asian Market Outlook ................................................................................................... 28
2.2.4 Overall Market Outlook ................................................................................................ 30
2.2.5 Overall Production Estimation ..................................................................................... 31
SITE FEASIBILITY STUDY................................................................................................................ 32
2.2.6 Introduction................................................................................................................... 32
2.2.7 Selection Criteria .......................................................................................................... 32
2.2.8 Contributing Factors in Site Selection .......................................................................... 33
2.2.9 Summary Of Characteristic at Each Location .............................................................. 35

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2.2.10 Concluding Remark............................................................................................... 41
2.3 PHYSICAL A D CHEMICAL PROPERTIES............................................................................ 43
2.3.1 Polyethylene Terephthalate (PET) ................................................................................ 43
2.3.2 Ethylene Glycol (EG) .................................................................................................... 43
2.3.3 Diethyl Glycol (DEG) ................................................................................................... 44
2.3.4 bis-hydroxyethyl terephthalate (BHET) ........................................................................ 44
2.3.5 Terephthalic Acid (TPA) ............................................................................................... 45
2.3.6 Water ............................................................................................................................. 45
2.4 FEEDSTOCK SUPPLY ............................................................................................................ 46
2.4.1 Supplier Profile ............................................................................................................. 46

CHAPTER 3 : PRELEMI ARY HAZARD A ALYSIS .................................................. 48

3.1 SAFETY ISSUES A D PRELIMI ARY HAZARD A ALYSIS ................................................... 48


3.2 IDE TIFICATIO OF MATERIAL A D CHEMICAL HAZARD .............................................. 48
3.3 EMERGE CY SITUATIO PROCEDURE ............................................................................... 58
3.4 LOCAL SAFETY REGULATIO S ........................................................................................... 59

CHAPTER 4: CO CEPTUAL DESIG A ALYSIS ....................................................... 62

4.1 PRELIMINARY REACTOR OPTIMIZATION .................................................................................... 62


4.1.1 Reactions Involved ......................................................................................................... 62
4.1.2 Esterification Reaction .................................................................................................. 62
4.1.3 Polymerization Reactions .............................................................................................. 64
4.2 PROCESS SCREE I G .......................................................................................................... 66
4.2.1 Heuristic Approach for Separation System Synthesis.................................................... 66
4.2.2 Sequencing of Separators .............................................................................................. 66
4.2.3 Operating Conditions for Separators ............................................................................ 68
4.3 ECO OMIC POTE TIAL (EP) .............................................................................................. 69
4.3.1 Economy Analysis .......................................................................................................... 69
4.3.2 Total Capital Investment ............................................................................................... 69
4.3.3 Fixed Capital Investment .............................................................................................. 70
4.3.4 Working Capital Investment.......................................................................................... 72
4.3.5 Start Up Cost................................................................................................................. 72
4.3.6 Total Capital Investment ............................................................................................... 73
4.3.7 Utilities .......................................................................................................................... 73
4.4 MASS BALANCE BY MANUAL CALCULATION & ICON SIMULATION ......................................... 77
4.4.1 Block Diagram for Production of PET Process ............................................................ 82

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CHAPTER 5 : HEAT I TEGRATIO .............................................................................. 83

5.1 PI CH A ALYSIS .................................................................................................................. 83


5.5.1 Pre-design Target for Utility Consumption .................................................................. 83
5.2 DIFFERE CE I HEAT EXCHA GER DUTY REQUIREME T BEFORE A D AFTER HEAT
I TEGRATIO (HI) .......................................................................................................................... 90

CHAPTER 6 : PROCESS DESCRIPTIO ........................................................................ 91

6.1 PROCESS DESCRIPTION ............................................................................................................... 91


6.2 FEED RAW MATERIAL ................................................................................................................ 92
6.3 REACTIONS INVOLVED................................................................................................................ 92
6.31 Esterification Process ..................................................................................................... 92
6.32 Separation Process ......................................................................................................... 93
6.33 Purging system ............................................................................................................... 95
6.34 Polycondensation Process .............................................................................................. 96

CHAPTER 7 : CO CLUSIO S .......................................................................................... 99

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LIST OF FIGURES

Figure 1 : Global PET Demand ............................................................................................... 12


Figure 2 : Usage of PET........................................................................................................... 24
Figure 3 : World Consumption of Ethylene Glycol ................................................................. 25
Figure 4 : Usage of Ethylene Glycol........................................................................................ 24
Figure 5 : World Consumption of TPA ................................................................................... 26
Figure 6 : TPA World Consumption In Year 2009.................................................................. 27
Figure 7 : Global PET Demand by Regions ............................................................................ 28
Figure 8 : World Consumption of PET Resins ........................................................................ 29
Figure 9: Tariff for High Voltage Industries............................................................................ 70
Figure 10 : Overall Esterifiction Reaction ............................................................................... 60
Figure 11 : Pre-Polycondensation Reaction ............................................................................. 61
Figure 12 : Final Polycondensation Reaction .......................................................................... 62
Figure 13 : Block Diagram of the Process ............................................................................... 80
Figure 14: Heat Balance By Manual Calculation .................................................................... 82
Figure 15 : Problem table Algorithm By manual Calculation ................................................. 83
Figure 16 : Composite Curve generated by using Aspen HX-Net 2006 software ................... 85
Figure 17 : Grand Composite Curve generated by using Aspen HX-Net 2006 software ........ 86
Figure 18 : Heat Exchanger Network ...................................................................................... 87
Figure 19 : Reaction Flow of PET Production......................................................................... 89
Figure 20 : Esterification Process ............................................................................................ 91
Figure 21 : Series of Esterification Reactor ............................................................................. 91
Figure 22 : Ethylene Glycol Recovery System ........................................................................ 92
Figure 23 : Purging Syatem ..................................................................................................... 93
Figure 24 : Series of Polycondensation Process ...................................................................... 95
Figure 25 : Reactions of Functional Group in PET Production Stage ..................................... 96

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LIST OF TABLES

Table 1 : Contributing Factors to Operability and Economy Aspects ..................................... 30


Table 2 : Summary Of Justification On Site Location............................................................. 35
Table 3 : Weighted marks and explanation on the plant site location factors ......................... 38
Table 4 : Weight Matrix On Site Location .............................................................................. 39
Table 5 : PET Properties .......................................................................................................... 41
Table 6 : EG Properties ............................................................................................................ 41
Table 7 : DEG Properties ......................................................................................................... 42
Table 8 : BHET Properties ....................................................................................................... 42
Table 9 : TPA Properties.......................................................................................................... 43
Table 10 : Water Properties ..................................................................................................... 43
Table 11 : Equipment Required and Estimated cost for PET Plant ......................................... 67
Table 12 : Fixed Capital Investment for PET Production Plant .............................................. 68
Table 13 : Plant Utilities ......................................................................................................... 71
Table 14 : MSDS for Selected Chemical ................................................................................. 47
Table 15 : Safety Risk and Mitigation Measures ..................................................................... 54
Table 16 : Separators with types of mixtures and Operating Condition .................................. 65
Table 17: Data from iCon Simulation...................................................................................... 81
Table 18 : Summary Of % Saving After Heat Integration....................................................... 88

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CHAPTER 1 : I TRODUCTIO

1.1 Background of Design Project

Polyethylene Terephthalate (PET) has been widely used, especially when plastics
bottles or food container popped-out in our mind. Thus, the advantages of PET have been
explored to understand its importance in industries. In Malaysia, we do understand that there
is no PET production plant exists, but somehow, Malaysia does have several companies
whom buy PET from other countries and process PET into plastics or any other necessary
PET-based products. These companies act as a supplier to supply and process PET, before
they distribute them in the form of desired products. Referring to our title ‘PET Production
Based On Esterification Process’, there are two basic raw material involved, which consists
of Ethylene Glycol (EG) and Terephthalic Acid (TPA).

Consequently, depending on PET processing and thermal history, PET may exist both
as an amorphous (transparent) or as a semi-crystalline material. The semi-crystalline material
might appear transparent or opaque and white, depends on its crystal structure and particle
size. During esterification process, reaction between Ethylene Glycol (EG) and Terephthalic
Acid (TPA) will produce monomer bis-hydroxyethyl terephthalate (BHET) and water as
byproduct.

1.2 Problem Statement

Based on the increasing number of PET demand, a petrochemical plant of


Polyethylene Terephthalate (PET) has been discussed to be constructed in Malaysia. As being
mentioned earlier, PET production plant will considered esterification process as its produce
only water as its byproduct. Generally, the plant is expected to operate for 330 days in a year,
including maintenance work or plant shutdown. The interest rate for the project is estimated
to be 10% per year and the project life is about 20 years. Thus, the whole study about this
coming construction plant needs to be developed to cater its manufacture and economical
feasible production capacity.

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The majority of the world's PET production is for synthetic fibers (in excess of 60%)
with bottle production accounting for around 30% of global demand. In discussing textile
applications, PET is generally referred to as simply "polyester" while "PET" is used most
often to refer to packaging applications. PET consists of polymerized units of the monomer
ethylene terephthalate, with repeating C10H8O4 units. PET is commonly recycled, and has the
number "1" as its recycling symbol.

Referring to below diagram on the Global PET demand, it is expected that year 2020
will needed huge amount of PET, which is approximately reaching 27 Million Tons. As the
demand increase proportionally with time, huge PET production is also expected to increase
by the existing number of plant or manufacture. By also considering the usage of PET
whether in industries or non-industries, Malaysia is about to take one step ahead in planning
and setting up a new plant for its own benefits.

Figure 1 : Global PET Demand

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1.3 Objective

Plant Design Project (PDP) 1 has come out with its own objective, especially to
educate and develop simulation skills among students. The project of designing industrial
plant required knowledge, passion and attitude in solving design problems for typical process
exists in industrial plant. Hence, this project is given with its own purpose ;

• To complete the design of PET Production plant by conducting literature survey,


which includes its process routes, properties, uses, and market cost data.
• To identify chemical and physical properties for all raw materials, intermediate
products, final products and environmental and safety considerations.
• To study and select the best process route of producing PET for a selected design
project (chosen process - esterification).
• To perform energy balance calculations and apply related computer-aided design
engineering software (iCON) as a tool for the design.
• To make necessary decisions, judgments and assumptions in design problems.
• To execute the process design and mechanical design of the major process units by
doing research on equipment used.
• To perform economic evaluation including capital cost estimation and manufacturing
cost estimation.
• To understand the environmental and safety issues related to the plant, by discussing
potential chemical hazard in the process.
• To develop working skills in a team and understand the basic principles of plant
design as well as reaction involved
• To generate cost effective process and maintain operation safety

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1.4 Scope of Work

There are several guidelines or scope of work that has been highlighted in this design
project, which mainly includes ;

• Conduct literature review survey about the product including its properties, usage,
cost, process involved, chemical and physical properties of raw materials, final
products, environmental considerations and safety considerations
• A clear complete Process Flow Diagram (PFD) of optimized process including all the
equipment.
• Provide stream flow table including all the stream variables e.g. temperature,
pressure, total flow rate and component flow rate.
• Identify and select the best process route for this design project
• Develop and performed complete material and energy balance calculations for
selected process
• Use related computer-aided design/engineering software (e.g. iCON, HYSYS, Visio
and Microsoft Excel) as the main tools for the design
• Make necessary decisions, judgments and assumptions based on plant design
knowledge, especially to solve design problems
• Perform economic evaluation including economic potential and initial cost estimation
• Consider environmental and safety issues which related to the plant
• Prepare preliminary and interim report as per standard format and do a presentation
on the design plant

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CHAPTER 2 : LITERATURE REVIEW

2.1 Background of Design Project

2.1.1 Overview of product, feedstock and byproducts

Product : Polyethylene Terephthalate (PET)

Polyethylene Terephthalate (PET)

In the 1950s, Polyethylene terephthalate (PET) came into prominence as a textile


material. PET is supplied by resin manufacturers in the form of small pellets, which each of
them are approximately 0.05 gram in size. Its strength, temperature tolerance and wear-
resistance made it an ideal replacement for or addition to natural fibers such as silk, cotton
and wool. PET is also a linear thermoplastic, which have long-chain molecule and consists of
repeating units, with white but bluish characteristics of resin. PET is made from terephthalic
acid and ethylene glycol through poly-condensation.

PET is also belongs to semi-crystalline polymer group and when heated above 72°C,
PET will change from a rigid glass-like state into a rubbery elastic form. In this condition,
polymer molecular chains can be stretched and aligned in either one direction to form fibres,
or in two directions to form films and bottles. Consequently, if the material melt is cooled
quickly, the chains will be frozen, with their orientation remaining intact in the stretched
state. Crystallization of PET in this condition makes the material starts to become opaque,
more rigid and less flexible. However, nowadays, many modifications are introduced to
develop specific properties for the various packaging applications to suit particular
manufacturing equipment. Special grades are offered with the required properties for the
different applications.

In industries, the best thing about PET is that it can be recycled to make many new
products, including fiber for polyester carpet; fabric for T-shirts, long underwear, athletic

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shoes, luggage, upholstery and sweaters; fiberfill for sleeping bags and winter coats; and new
PET containers for both food and non-food products.

By recycling, there are lots of advantages has been proved, such as ;


• Recycling a ton of PET containers saves 7.4 cubic yards of landfill space.
• According to the EPA, recycling a pound of PET saves approximately 12,000
BTU's.
• The average household generated 42 pounds of PET plastic bottles in the year
2005.
• Custom bottles (which are bottles used for products other than carbonated soft
drinks) represent 62% of all PET bottles available for recycling.

Feedstock : Terephthalic Acid (TPA) and Ethylene Glycol (EG)

Terephthalic Acid (TPA)

Terephthalic acid is an organic compound with formula C6H4(COOH)2. The


abbreviation used for this acid is TPA. The common properties for TPA are colorless solid,
and it is being used in the application of polyester PET, especially for clothing and plastic
bottles. In industries, several billion kilograms are produced annually to cater the needs of
TPA in many sectors. TPA also considered as one of the three isomeric phthalic acids. In this
project, TPA used is assume to be 100% purified. Another characteristic for terephthalic acid
is including poorly soluble in water and alcohols, and most of the crude terephthalic acid was
converted to dimethyl ester for purification. PTA also sublimes when heated (since it is
already mentioned that PTA is in a solid condition).

Virtually the entire world's supply of terephthalic acid is consumed as precursors to


polyethylene terephthalate (PET), as TPA is plays very important role for PET production
(raw material). With lots of application of PTA, by 2006, global purified terephthalic acid
(PTA) demand had exceeded 30 million tonnes. While in the research laboratory, terephthalic
acid has been popularized as a component for the synthesis of metal-organic frameworks.

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Ethylene Glycol (EG)

Ethylene glycol is an organic compound widely used as an automotive antifreeze and


also the main precursor to polymers. Ethylene glycol falls under alcohol group with formula
C2H6O2. The short form for ethylene glycol is EG, where in its pure form, it is odorless,
colorless, syrupy and sweet-tasting liquid. Ethylene glycol is also known to be toxic, and
ingestion can result in death.

Ethylene glycol is produced from ethylene (ethene), via the intermediate ethylene
oxide. In this reaction, the major byproducts are ethylene glycol oligomers, diethylene glycol,
triethylene glycol, and tetraethylene glycol. In industries, about 6.7 billion kilograms of EG
are produced annually. Another application of EG are includes ; medium for coolant and heat
transfer, hydration inhibition to remove water and inorganic salts, and in niche application.

Byproducts : Diethyl glycol (DEG), bis-hydroxyethyl terephthalate (BHET) and Water

Diethyl glycol (DEG)

Diethyl glycol (DEG) is a class of organic chemicals groups that contribute to high
water solubility and reactivity with many organic compounds, usually linear and aliphatic
carbon chain. The general formula for DEG is O(CH2CH2OH)2. Ethylene glycol is the
simplest member of the glycol family. Mono-, di- and triethylene glycols are the first three
members of a homologous series of dihydroxy alcohols. The basic characteristic of EG is a
colorless, odorless, involatile and hygroscopic liquid with a sweet taste. It is somewhat
viscous liquid, which miscible with water. In plastic industries, EG has become increasingly
important for the manufacture of polyester fibers and resins, including polyethylene
terephthalate, which is used to make plastic bottles for soft drinks (PET bottles). Ethylene
glycol is by far the largest volume of the glycol products in a variety of applications including
anti-freezing additive, intermediate polymer, solvent or plasticizer for plastic, dehydrating
and textile conditioning.

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bis-hydroxyethyl terephthalate (BHET)

Throughout this project, bis-hydroxyethyl terephthalate (BHET) is known as


monomer in the production of PET. BHET is then polymerized up to about 30 in
polymerization process. One of the characteristic found in BHET is that it is obtained as an
amorphous to very finely crystalline mass and difficult to separate. This BHET can undergo
polycondensation process and to be removed during PET production process without any
further additives. However, polycondensation of BHET with the addition of a corresponding
molar amount of terephthalic acid makes it possible to utilize this ethylene glycol to produce
huge amount of PET.

Water (H2O)

In this project of PET production plant, we have decided to choose esterification


process as the main route. Thus, the main byproduct produced is water. Water is widely
known as a liquid at ambient conditions, but it often co-exists on Earth with its solid state,
ice, and gaseous state, water vapor or steam. Water is a tasteless, odorless liquid at standard
temperature and pressure. The color of water and ice is, intrinsically, a very slight blue hue,
although water appears colorless in small quantities. Water is also transparent, where sunlight
can be seen through water.

Water is a good solvent and is often referred to as the universal solvent. Substances
that dissolve in water, for example ; salts, sugars, acids, alkalis, and some gases – especially
oxygen, carbon dioxide (carbonation) are known as hydrophilic (water-loving) substances,
while those that do not mix well with water such as fats and oils, are known as hydrophobic
(water-fearing) substances. All the major components in cells (proteins, DNA and
polysaccharides) are also dissolved in water. Pure water has a low electrical conductivity, but
this increases significantly with the dissolution of a small amount of ionic material.

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2.1.2 Process Primary Routes to PET Production

Production of Polyethylene Terephthalate (PET) has two major processes, which are
esterification and transesterification. In this project, we have decided to choose esterification
process instead of transesterification process. In this context, overview of feedstock, product
and byproducts will be highlighted, while details about transesterification process will be
discussed later in the process alternative routes, where we put this process as our second
option. By referring to esterification basic definition, the process is the general name for a
chemical reaction in which two reactants (typically an alcohol and an acid) form an ester as
the reaction product. During the process, main chemicals involved are ethylene glycol (EG)
and terephthalic acid (TPA) with water as the byproducts.

The primary reaction for esterification process is ;

During the process, ethylene glycol (EG) and terephthalate acid (TPA) react with each other
at 190°C in the presence of an inert gas, such as nitrogen, yielding bis-hydroxyethyl
terephthalate (BHET) :

bis-hydroxyethyl terephthalate (BHET)

The terephthalic acid and ethylene glycol are mixed to form a paste, allowing more
accurate control of the feed rates to the esterification vessels. The number of reactors and
their operating conditions depends on the type of PET being produced. In this case, ratio of
EG and TPA is 1:1.2 respectively (by considering recycle stream). Typically, in this process,
there are two stage of esterification processes, two stage of polycondensation process and one
distillation column involved mainly for water removing. Esterification process 1 converts
95% of reaction involved while the second process converts 98% of the first reaction. As for
polymerization process, both processes are assumed to be 100% conversion.

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Consequently, TPA and EG process generally involves a system similar to that of the
DMT process. The major difference is the lack of a methanol recovery step and it involved
only one catalysts ; Antimony Trioxide.

2.1.3 Process Alternative Routes

One of the alternative PET process routes is known as transesterification.


Transesterification process used dimethylterephthalate (DMT) and ethylene glycol (EG). In
this process, EG is drawn from raw material storage and fed to a mix tank, where catalysts
and additives are mixed along with DMT, to the esterifiers. This reaction produces the
intermediate BHET monomer and methanol as the byproduct. During transesterification,
methanol vapor must be removed from the esterifiers to shift the conversion to produce more
BHET.

Chemical reaction involved during transesterification ;

The BHET monomer, with other esterifier products, is fed to a polymerization reactor
where the temperature is increased and the pressure is decreased. At these operating
conditions, residual methanol and ethylene glycol are vaporized, and the reaction that
produces PET resin starts, where the final temperature and pressure depend on whether low
or high viscosity PET is being produced. For high-viscosity PET, more process vessels are
used to achieve higher temperatures and lower pressures, compared to low-viscosity.

Throughout this process, ethylene glycol can be recovered by using recovery system,
which is usually a distillation composed of a low boiler column, a refining column, and
associated equipment. Product from the polymerization reactor (referred to as the polymer
melt) may be sent directly to fiber spinning and drawing operations. Alternatively, the
polymer melt may be chipped or pelletized, put into product analysis bins, and then sent to
product storage before being loaded into hoppers for shipment to the customer.

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Below is a simple comparison between the two existence process, esterification and
transesterification ;

ESTERIFICATIO DETAILS TRA SESTERIFICATIO


New Technology - 1963 History Old Technology – 1940
EG + TPA Raw material EG + DMT

Produce H20 By product Produce Methanol

H20 can be recycled for Need to establish Recovery


Recovery Unit
other usage (Low Cost) Unit (High cost)

No unit required Purification unit Required for methanol recovery


Produce hazardous material
Less harm to environment
Environments (Higher VOC content),
(Low VOC content)
Lead to respiratory problem

Table 1 : Process Comparison

Based on above table, esterification process involved EG and TPA as its raw material
and produced water as the byproducts. Since the technology was introduced in year 1963, it is
newer process than transesterification process. Water can be recycled to other types of usage
such as for reducing heat, thus it lower down the process cost for cooling purposes. Water
produced is less harmful to the environment since it contains low VOC (Volatile Organic
Compound) number. While for transesterification process, it has been introduced since year
1940 where the chemicals involved are EG and DMT. The process produced methanol as the
byproduct, thus it is crucial to establish recovery unit for methanol. This might increase plant
cost. Transesterification also produce hazardous material where the VOC content is high and
lead to respiratory problem.

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2.1.4 History, Applications and Usage

PET History

Polyethylene was discovered in 1933 by Reginald Gibson and Eric Fawcett at British
industrial giant Imperial Chemical Industries (ICI). There are two material forms, which is
low density polyethylene (LDPE) and high density polyethylene (HDPE). In early 1950s,
polypropylene (PP) was discovered after the existence of polyethylene. Polypropylene was
invented by two American chemists, who worked for Phillips Petroleum of the Netherlands,
Paul Hogan and Robert Banks. Previously, before PET was introduced, polypropylene is
being used in almost everything ; from plastic bottles to carpets to plastic furniture, and also
heavily used in automobiles.

In year 1941, John Rex Whinfield and James Tennant Dickson, British chemists and
employee of a company named Calico Printer's Association of Manchester, has patented
‘polyethylene terephthalate’ or also known as PET or PETE. It is actually a continuous effort
from early research of Wallace Carothers, who is an American chemist, inventor and the
leader of organic chemistry. Realizing that Carothers's research had not investigated polyester
formed from ethylene glycol and terephthalic acid, Whinfield and Dickson took this
opportunity along with inventors W.K. Birtwhistle and C.G. Ritchiethey to create the first
polyester fiber called Terylene in the same year, 1941.

According to Whinfield and Dickson, polyethylene terephthalate is the basis of


synthetic fibers such as polyester, dacron, and terylene, while the second polyester fiber was
from DuPont's Dacron company. According to DuPont, there was indirect competition with
Britain’s recently formed Imperial Chemical Industries in the late 1920s. Thus, in October
1929, both companies agreed to share information about patents and research developments.
However, even after both companies alliance, DuPont chose to concentrate more on the
promising nylon research. When DuPont resumed its polyester research, ICI had patented
Terylene polyester, to which DuPont purchased the U.S. rights in 1945 for further
development. In 1950, a pilot plant at Seaford, Delaware, was established to produced
Dacron, or polyester fiber with modified nylon technology. Dupont's polyester research lead

22
to a whole range of trademarked products, for example is Mylar (1952), an extraordinarily
strong polyester (PET) film that grew out of the development of Dacron in the early 1950s.
As being mentioned earlier, polyesters are made from chemical substances found
mainly in petroleum and are manufactured in fibers, films, and plastics. According to Dupont
Teijin Films, plain polyethylene terephthalate (PET) or polyester is most commonly
associated with a material from which cloth and high-performance clothing are produced.
Over the last ten years PET has increasingly gained acceptance as a material of choice
especially for beverage bottles. Other that PET, glycolised polyester (PETG) is also being
used in the production of cards. While polyester film (PETF), a semi-crystalline film has
proved its importance in many applications such as videotape, high quality packaging,
professional photographic printing, X-ray film, as well as floppy disks.

PET Application and Usage

Nowadays, polyethylene terephthalate (PET) has been widely used in our daily life, as
it is cheap, flexible, durable, and chemically resistant. As mentioned earlier, two types of
materials formed, which are low density polyethylene (LDPE) and high density polyethylene
(HDPE). LDPE is used to make films and packaging materials, including plastic bags, while
HDPE is used more often to make containers, plumbing, and automotive fittings. In addition,
PET is more impermeable than other low-cost plastics, where this condition has help PET to
become a popular material, especially for making drinking bottles for a giant company, Coke.

PET is also strong and abrasion resistant, and is used for making mechanical parts,
food trays, and other items that have to endure abuse. PET films, which its trade-named is
‘Mylar’ are used to make recording tape. PET manufacturing process has been developed by
using various forming, molding, casting, and extrusion processes, to churn out plastic
products in vast quantities. Other than mentioned PET applications, one of the most visible
parts of this plastics invasion was Earl Tupper's or famously known as ‘Tupperware’. The
Tupperware line of products was well thought out and highly effective, greatly reducing
spoilage of foods in storage. Thin-film "plastic wrap" that could be purchased in rolls also
helped keep food fresh.

23
Another prominent element in 1950s homes was "formica," a plastic laminate that
was used to surface furniture and cabinetry. Formica was durable and attractive. It was
particularly useful in kitchens, as it did not absorb, and could be easily cleaned of stains from
food preparation, such as blood or grease. With formica, a very attractive and well-built table
could be built using low-cost and lightweight plywood with formica covering, rather than
expensive and heavy hardwoods like oak or mahogany. Apart from that, composite materials
like fiberglass came into use for building boats and, in some cases, cars.

From above discussions, PET has been proved that it is widely used in our daily life
as the demand of PET is kept increasing. Thus, PET production plant is become crucial to be
built in Malaysia to cater the needs of recent PET products. Summary of PET usage has been
summarize as per below diagram ;

Figure 2 : Usage of PET

2.2 Product Market Survey

2.2.1 Resources and raw Materials

This project of producing PET is proposed to follow easterification process, where


raw materials involved are ethylene glycol (EG) and terephthalic acid (TPA). Further
explanations on both chemicals are as follows ;

24
Ethylene Glycol (EG)

Below figure emphasized on the world consumption of Ethylene Glocol, where Asia
has falls under top five of EG consumer.

Figure 3 : World Consumption of Ethylene Glycol

By taking Malaysia into considerations, the consumption of EG is also considered


higher. Thus, large amount of EG is needed for various types of industries. Ethylene glycol is
a colorless, odorless, low-volatility, low-viscosity hygroscopic liquid. It is completely
miscible with water and many organic liquids. In industries, there are at least five grades of
ethylene glycol are manufactured, which include commercial polyester, industrial, low
conductivity, polyester, and antifreeze.

Figure 4 : Usage of Ethylene Glycol

25
Referring to Figure 4, in 2009, almost 85% of the ethylene glycol (EG) is consumed
worldwide into the production of PET, which in turn was converted into fibers, film and
bottles. Another 10% was consumed in antifreeze and 5.5% in other uses. In 2009, 69% of
the EG consumed worldwide was in Asia, followed by 13% in North America and 8% in
Western Europe. With the huge amount needed for PET production, EG production must also
be increase from time to time to catch up with its consumption.

Terephthalic Acid (TPA)

Consumption of TPA for the production of PET polymer has been more than 90% of
the worldwide consumption. The following pie chart shows world consumption of TPA ;

Figure 5 : World Consumption of TPA

By taking the year of 2009 as TPA based world consumption, more than 60% of the
TPA produced in the world is used to manufacture PET polymer for polyester fibers. Another
31% goes into the manufacture of PET solid-state resin for bottles and other packaging
applications.

26
Figure 6 : TPA World Consumption In Year 2009

TPA for PET solid-state resins has grown strongly followed by the replacement of
glass in soft drinks and water bottles. In five years, PET solid-state resins are estimated to be
the fastest-growing sector in the next five years. Referring to Figure 4, Asia falls under fifth
major contributor to consume TPA, where the opportunity to set up PET production plant is
being study in Malaysia.

2.2.2 Global Market Outlook

PET packaging resin markets have seen very strong growth over the last 20 years. It
first penetrated the carbonated soft drinks market because it is lightweight and strong. PET
bottles are virtually unbreakable while a typical 1.5 litre bottle weighs about 40-45gm, about
one-tenth the weight of glass. PET has taken market share in the bottled water market due to
its good clarity and not leaving any taste in the water. It has also found applications in more
niche markets such as sports drinks and fruit juices, and is used to make bottles for cooking
and salad oils, sauces and dressings.

An untapped market for PET is beer packaging with substantial conversion where it
has captured 5% of the beer market, 62% of glass and 33% of metal cans, according to
Canadean, the UK-based beverage research consultant, while the largest market is Russia,
which accounts for 60% of PET’s use in the global beer market. Other east European
countries are prominent users, but outside these countries, only Germany, South Korea and
Spain make any significant contribution to PET use for beer packaging.

27
The highest demand for PET is Asia, which its demand by volume for PET in 2009
was nearly 4.7 million tons, while Europe is the second largest consumer of PET in the
world. Russia, Italy and Germany are the major consuming countries in Europe. The demand
in some Western European countries, such as Germany, France, Spain and the UK, is
approaching the maturity stage. Growth in European PET demand is driven mostly by Russia.
The demand for PET in Europe was around 3.7 million tons in 2009. The North American
economy is the most developed and advanced, and the scope for growth is lowest as the
demand is close to saturation. However, certain new and upcoming applications of PET are
driving the North American market. The North American demand for PET in 2009 was close
to 3.1 million tons in 2009. The PET demand in South and Central America is growing fairly
strongly. This region consumed around 2 million tons of PET in the year 2009. The Middle
East and African demand for PET is the second fastest growing after that of Asia. The Middle
East and Africa region consumed around 1.2 million tons PET in 2009.

Then again, factor that could impact the supply and demand balance for PET is the
growth in recycling. PET is probably the most recycled polymer taken and being increasingly
used in bottles and retail packaging as well as carpet fiber and clothing. Still, the Global
Market outlook for PET is expected to grow based on the global demand for over the last
decade. The global PET market in 2009 was about 15.3 million tons. In the year of 2020, the
consumption demand for PET is estimated to grow at CAGR of 4.9%.

2.2.3 Asian Market Outlook

Based on Figure 7 on the demand shares by region, shows that Asia is the biggest
consumer of PET with 30.5%, followed by Europe 24%, North America 20.3%, South and
Central America 13.4%, Middle East and Africa 8% and other region is about 3.7%. Thus, it
makes the highest demand for PET is Asia, which its demand by volume for PET in 2009 was
nearly 4.7 million tons.

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Figure 7 : Global PET Demand by Regions

Since the growth in PET demand is coming from Asia, the Gross Domestic Product
(GDP) countries like China and India in Asia are growing at rates higher than the global GDP
growth rates. Thus, the key markets consuming PET are also growing with strong economic
growth along large population that enables large consumption of Carbonated Soft Drinks
(CSDs) and bottled water in the region. Another factor that supports PET demand is rapid
changing of lifestyle that consumes packaged food.

In Asia, China is the largest producer of PET in the region and exports to many
countries as well as the largest PET consuming markets are Carbonated Soft Drinks (CSD)
and Bottled Water. This is due to its light weight, toughness and clarity, PET is the most
preferred material for CSD bottles. CSD and bottled water together account for more than
65% of the global PET demand. However, the packaged food segment is also a very
important and growing market for PET.

29
2.2.4 Overall Market Outlook

Development and growth of the global PET solid-state resin market since 1996 has
been impressive after their thirty-two years of introduction in the mid-1970s. Global
consumption of these resins continues to grow especially in these three regions ; North
America, Europe and Asia, which accounted for the majority of world production and
consumption. Asia and Middle East are expected to achieve double-digit consumption growth
through 2012, while Eastern Europe and South America have created import opportunities.
Asian and Middle Eastern producers are expected to be the major suppliers of PET exports to
Eastern Europe, Central and South America, and Oceania as its continuous production and
relatively lower feedstock costs as the primary drivers.

The following pie chart shows world consumption of PET solid-state resins:

Figure 8 : World Consumption of PET Resins

PET bottle resin is a very important material driving growth in the developed
economies, but growth of PET fiber remains dominant in terms of total polyester. PET
growth is driven differently depending on the geographic region. In North America and
Western Europe, PET growth is associated primarily with PET bottle resins; demand for PET
fiber has been in decline since the late 1990s. PET growth in most other regions is primarily
associated with PET fiber. Global polyester growth will continue to be driven by Asia and,
more specifically, by the Chinese market.

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2.2.5 Overall Production Estimation

To estimate the production capacity of a new polyethylene terephthalate (PET) plant,


we assume that the production capacity of world depends largely on the world population. In
2015, the world population is estimated to be around 6.8 billion people. We assume that we
want to produce PET solely in Malaysia. To estimate the amount of PET to produce, we need
to do a calculation based on the population in Malaysia and the world’s population.

Based on “Catalytic and Mechanistic Studies of PET Synthesis” by Faissal-Ali El-Toufaili, in


2015, the PET demand in 2015 is about 58 x 106 MT/yr.

Calculation:

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Site Feasibility Study

2.2.6 Introduction

Choosing strategic plant location is one of the most crucial decisions needs to be
done. The construction of a chemical plant requires a preliminary feasibility study to be done
in order to make certain that the proposed 30,000 kg/year PET plant is feasible, economically
and environmentally. The location of the plant site takes relatively high precedence and it
mainly depends on the availability of feedstock, cost of production, marketing of the
products, land availability and also the infrastructure. The right location allows maximum
profit with a minimum operating cost and allowance for future expansion.

2.2.7 Selection Criteria

Based on the study done in the selecting strategic plant location, there are several
factors that should be taken into consideration when undertaking the process of selecting a
suitable site. There are two major factors that contribute to the operability and economic
aspects of a site location for a plant, which are the primary factor and specific factor.

Primary Factors Specific Factors


1. Raw material availability for Availability of low cost labor and
industry services
2. Reasonable land price Safety and environmental impacts
3. Source of utilities, such as Incentives given by government :
electricity, water and etc. Pioneer Status
Investment Tax Allowance (ITA)
Effluent and waste disposal facilities
4. Climate status
Wind Transportation facilities
Rainfall
Temperature Local community consideration
Relative Humidity

Table 2 : Contributing Factors to Operability and Economy Aspects

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2.2.8 Contributing Factors in Site Selection

General Factors

i. Availability of Raw Material


To minimize the transportation cost of the raw material, a closer source of the
raw material to the operating plant is needed. If the needed raw material is to be
imported, it would be important to consider a location near to a seaport with excellent
infrastructure.

ii. Reasonable land price


Most of the industrial land price depends on the location. It is very important
to choose an economical land price which can reduce the total investment cost.
Besides that, it is important to choose the lowest land price when starting a new plant
to gain the highest economic value.

iii. Utilities
In petrochemical industries, large quantities of water supply are usually
needed for cooling and general use in a chemical plant. Besides that, petrochemical
plants need power in the form of electricity to run machines and equipments. Thus it
is important to have sufficient power and local water supply in order to ensure the
plant running smoothly.

iv. Climate
Budget and cost operation can be affected by climatic conditions. A general
analysis of the yearly weather conditions would be an important consideration.

33
Specific Factors

i. Availability of low cost labor and services


Plant should be located where sufficient labor supply is available. Skilled
construction workers will usually be brought in from outside local area but there
should be an adequate pool of unskilled workers available locally and workers
suitable for training to operate the plant. Available, inexpensive manpower from the
surrounding area will contribute in reducing the cost of operation.

ii. Transport facilities


The plant should be located close to at least three forms of major
transportation facilities, which are road network, seaport and airport. These will help
facilitate any import and export activities. Seaport facilities will help in the
exportation and importation of the product and raw materials via tankers while the
availability of airport is convenient for the movement of personnel and essential
equipment supplies.

iii. Government incentives


Most state governments offer attractive incentives to investors. Some
incentives grant partial or total relief from income tax payment for a specified period,
while indirect tax incentives come in the form of exemptions from import duty, sales
tax and excise duty. This can help reduce initial operating costs.

iv. Local community consideration


The proposed plant will have to fit in with and acceptable to the local
community. Full consideration must be given to be safe location of the plant so that it
does not impose a significant additional risk to the community. On a new site, a local
community must be able to provide adequate facilities for the plant personnel: school,
banks, housing, and recreational and cultural facilities.

34
v. Waste and effluent disposal facilities

Site selected should have efficient and satisfactory disposal system for factory
waste and industrial effluent if it is decided that the waste should be treated off-site.

2.2.9 Summary Of Characteristic at Each Location

The manufacture of PET is categorized as a petrochemical project. The plant must


therefore be sited in a special zone provided by the government. After conducting the
feasibility and site survey, four (4) main locations have been short listed to be considered as
strategic site location for the construction of a 30,000 kg/year, PET plant.

i) Kerteh Industrial Estate,Terengganu


Kertih Integrated Petrochemical Complex, Terengganu located at the south of
Terengganu, is developed by PETRONAS. Plants can be sited within the vicinity of
raw materials thus saving in production cost. Availability of cheap industrial land and
supply of relatively productive and adaptable labor from a young and literate
population give merit to the location. Special incentives are offered such as cheaper
land and lower quit rent and assessment rates. Terengganu is also home of the
Malaysia deepest port versioned to be the new gateway to the Asia Pacific.

ii) Gebeng (Phase IV) Industrial Estates, Kuantan, Pahang.


Gebeng Industrial Estate is promoted by the Pahang State Development
Corporation (PSDC) as an industrial predecessor in the East Asian region for
petrochemical and chemical based plants. The federal government’s move to develop
the eastern industrial corridor ensures beneficial and rapid progression for the
industrial growth of Gebeng estate. According to Kuantan Port Consortium (2007),
the first and second phase category, comprises about 900 hectares. A third phase,
spanning some 1,600 hectares, has attracted mega industries from multinational
companies, namely from the US, Japan, Germany and Belgium. Kuantan proximity to
Malaysia’s oil and gas fields make it a logical choice for petrochemical industry
growth.

35
iii) Teluk Kalong Industrial Estate, Terengganu.
Teluk Kalong is an industrial town of Kemaman district, Terengganu,
Malaysia. Teluk Kalong insdustrial Estate was built by Terengganu State through
Perbadanan Memajukan Iktisad Negeri Terengganu (PMINT) to support petroleum
industry at Terengganu. It is located at strategic location which is 35 minutes to
Gebeng Kuantan Industrial Area and 40 minutes to Kerteh Industrial Area.

iv) Pasir Gudang, Industrial Estate,Johor.


Pasir Gudang, Industrial Estate is located 36 km from Johor Bahru. The type
of industry develop in Pasir Gudang is light, medium and heavy industry. Johor Port
is about 5 km from Pasir Gudang, and this will enable easier import and export
processes. Good infrastructure facilities are also available here, such as North-South
highway to Kuala Lumpur and the main road to Singapore. Railroads are also
available here. The line runs from northern terminal in Butterworth to Singapore and
Pasir Gudang in the South.

Evaluation for each site location was made which is based on primary and specific
factor which had been justified earlier. Summary of justification can be seen in Table 2 and
Table 3.

36
Table 3 : Summary Of Justification On Site Location

Teluk Kalong Industrial Pasir Gudang Industrial


Selection Criteria Kerteh Industrial Estate Gebeng Industrial Estate
Estate Estate

Location 5 km from Paka 30km from Kuantan City 9.6km from Kemaman 36km from Johor Bharu

Type of industry Chemical and plastic Chemical and plastic Medium & Heavy Light, Medium & Heavy

Preferred Petrochemical Petrochemical Sea related


Area available 500 hectare 900 hectare 160 acres 430 acres

Land price(per m2) RM 1.94 – 60.26 RM 21.52 - 96.84 RM 1.94- 60.26 RM 86.08 – 236.72

Raw material Optimal, Kerteh Amoco Chemicals, Gebeng Optimal, Kerteh Optimal, Kerteh
Supplier Amoco Chemicals, Gebeng Optimal, Kerteh Amoco Chemicals, Gebeng Amoco Chemicals, Gebeng

Tasik Kenyir Hydroelectric Tanjung Gelang TNB Tasik Kenyir Hydroelectric Sultan Iskandar Power Station
Power Supply Dam (1200MW), Dam (644 MW)

IPP YTL Power Generation


IPP YTL (600 MW) CUF Gebeng (42MW) IPP YTL (600 MW)
Sdn. Bhd.

Paka Power plant (900 MW) Paka Power plant (900 MW)

CUF Kertih CUF Kertih


Teluk Kalong Industrial Pasir Gudang Industrial
Selection Criteria Kerteh Industrial Estate Gebeng Industrial Estate
Estate Estate
Bukit Sah Loji Air Semambu Bukit Sah Loji Air Sungai Layang

Sungai Cherol CUF Gebeng Sungai Cherol Syarikat Air Johor


Water Supply
Sungai Kemasik Sungai Kemasik Loji Air Sungai Buluh

CUF Gebeng CUF Gebeng


Kerteh Port and Kuala
Port Facilities Kuantan Port Kemaman Port Pasir Gudang Port
Terengganu port
Senai International Airport,
Kerteh Airport and Sultan Sultan Ahmad Shah Sultan Mahmud Airport, and
Airport Johor and Changi International
Mahmud Airport Airport, Kuantan Kerteh Airport
Airport, Singapore
Railway facilities Singapore and North
Kuantan-Kerteh Railway Kuantan-Kerteh Railway Kuantan-Kerteh Railway
Peninsular Malaysia
Roadways Kuala Terengganu-Kuantan Karak-Kuantan Highway Kuala Terengganu-Kuantan- Main road to Singapore

Karak Highway Karak Highway PLUS Highway

Infrastructure Allowance. Infrastructure Allowance. Infrastructure Allowance. Incentive for exports


Five-year exemption on import Five-year exemption on Five-year exemption on Incentives for research
Incentives duty. import duty. import duty. development
5 % discount on monthly
5 % discount on monthly 5 % discount on monthly Incentives for training tariff
electrical bills for first 2
electrical bills for first 2 years. electricity bills. protection
years.

38
Teluk Kalong Industrial Pasir Gudang Industrial
Selection Criteria Kerteh Industrial Estate Gebeng Industrial Estate
Estate Estate
25-38 % exemption on daily 25-38 % exemption on daily Exemption from import duty
85% tax exemption on
water cost for 4545 m3 of water cost for 4545 m3 of on direct raw
gross profit
water water materials/components
Pioneer Status and Investment Pioneer Status and Pioneer Status and Pioneer Status and Investment
Incentives Tax Allowance and Investment Tax Allowance Investment Tax Allowance Tax Allowance and
Reinvestment Allowance. and Reinvestment and Reinvestment Reinvestment Allowance.
Allowance. Allowance.
Incentives for high tech Incentives for high tech Incentives for high tech Incentives for high tech
industries industries industries industries
Local people
650 000 peoples 350 000 peoples 650 000 peoples 1500 000 peoples
(15-30 years old)
Kualiti Alam Sdn Bhd, Bukit Kualiti Alam Sdn Bhd, Kualiti Alam Sdn Bhd, Bukit Kualiti Alam Sdn Bhd, Bukit
Waste water Nenas, Negeri Sembilan Bukit Nenas, Negeri Nenas, Negeri Sembilan Nenas, Negeri Sembilan
management Indah Water Konsortium Sembilan Indah Water Konsortium Kualiti Alam Sdn Bhd
Indah Water Konsortium
Selection :
Kerteh Industrial Estate

39
Table 4 : Weighted marks and explanation on the plant site location factors

Factors: 7 – 10 Marks 4 –6 Marks 0 – 3 Marks


• Able to obtain large supply locally • Source of raw materials from • Unable to obtain raw material
thus saving on import cost. neighbouring states or countries from close sources with the
• Having long pipeline networks for with the distance not exceeding distance exceeding 80km.
Supply of raw material the transportation of raw materials. 80km. • Forced to import from foreign
• Uses a pipeline system as well. countries
• Use a pipeline system as well.
• Land area exceeding 60 hectares • Land area below 60 hectares • Land area below 40 hectares
Price and area of land • Price of land below RM 20 per m2 • Price of land more than RM 20 • Price of land exceeding RM30 per
per m2 m2
• Incentives from the Local • Incentives from the Local • No incentives from the Local
Organization of Country Organization of Country Organization of Country
Local Government Incentives Development Development. Development.
• Incentives from special company
• Complete network and well • Good federal road and highway • Average road systems
maintained highways, expressways systems • No highway or expressway
and roads. • Limited railway system access system in close proximity.
• International Airport facilities • More distant from the ports • No railway system.
access to the main locations around • Airport facilities which may not • Very distant from the ports or
Transportation the world. have international flight harbors.
• Location near to international port facilities – only providing • Distant from the nearest airport –
with import and export activities. domestic flights. more than 100km away.
• Reliable railway lines to remote
areas not accessible by roads.

40
Table 5 : Weight Matrix On Site Location

Teluk
Criteria Kerteh Gebeng Pasir Gudang
Kalong
Supply of raw material 6 6 7 3
Price and area of land 7 6 7 3
Local government incentives 8 8 8 8
Transportation 9 7 8 7
Workers supply 6 5 6 8
Utilities, water and electricity 8 6 7 7
Type of industrial and its
location 8 8 6 6
Waste water disposable 8 8 8 7
Total 60/80 54/80 57/80 49/80
75.00% 67.5% 71.25% 61.25%

2.2.10 Concluding Remark

Based on the matrix comparison made, Kerteh Industrial Estate has been chosen as
the site for the PET plant. The location of Kerteh Industrial Estate is highly strategic
compared to others where the reason is focused on the nature and the requirements of the
plant ;

• Kerteh industrial estate is situates at east coast of peninsular Malaysia and it is


only 9 km from Paka and 7 km from Kerteh.

• Low land prices compared to other location, which is at RM 1.94 – 60.26 per
metre square.

• Since this location if near the Kerteh Port, Kuala Terengganu port, and Kemaman
port, any trade involving the import and export of products and, if necessary, raw
materials can be achieved with relative ease
• Attractives incentives given by the Malaysia government and local government
which is :
 Infrastructure Allowance.
 Five-year exemption on import duty.
 5 % discount on monthly electrical bills for first 2 years.
 25-38 % exemption on daily water cost for 4545 m3 of water for 2 years
 Pioneer Status and Investment Tax Allowance and Reinvestment Allowance.
 85% tax exemption on gross profit

• Constant supply of utilities such as cooling water, power supply and waste
management.
 Power supply : Tasik Kenyir Hydroelectric Dam , IPP YTL (600 MW) , IPP
YTL (600 MW), Paka Power plant (900 MW) and CUF Kertih
 Water supply : Bukit Sah ,Sungai Cherol ,Sungai Kemasik , and CUF Kerteh
 Waste management: Kualiti Alam Sdn Bhd Bukit Nenas, Negeri Sembilan and
Indah Water Konsortium

• Excellent transportation link by railway, road and airpot. Kerteh is connected to


Kuala Terengganu, Gebeng and Kuantan via main road and also railway.

Good pipeline connection between Gebeng, Kuantan, and Kerteh. Transportation


of raw material had been eased by the connection of pipeline between these two
petrochemical industrial plants. A good network of pipe racks is crucial as it creates for a
cheaper and efficient method in transporting chemicals from designated plants to the port. In
addition, a Centralized Utility Facilities (CUF) is also offering its services to plant owners in
Kerteh to provide the supply of electricity, industrial gases and utilities such as steam and
pretreated water.

42
2.3 Physical and Chemical Properties

2.3.1 Polyethylene Terephthalate (PET)

Molecular Structure :

Properties Values
Formula (C10H8O4)n
Molecular weight Depends on n number
Density 1.4 g/cm3
Melting point 260 °C
Boiling Point ~930 °C
Colour Colourless
Physical state Solid

Table 6 : PET Properties

2.3.2 Ethylene Glycol (EG)

Molecular Structure :

Properties Values
Formula C2H6O2
Molecular weight 62.1
Density 1.11 g/cm3
Melting point -13 °C
Boiling Point 198 °C
Colour Clear liquid
Physical state Liquid

Table 7 : EG Properties

43
2.3.3 Diethyl Glycol (DEG)

Molecular Structure :

Properties Values
Formula C4H10O3
Molecular weight 106.12
Density 1.12 g/cm3
Melting point -10.45 °C
Boiling Point 245 °C
Colour Colourless
Physical state Liquid

Table 8 : DEG Properties

2.3.4 bis-hydroxyethyl terephthalate (BHET)

Molecular Structure :

Properties Values
Formula C12H14O6
Molecular weight 254.2
Density 1.34 g/cm3
Melting point 110 °C
Boiling Point 409.9 °C
Colour Colourless
Physical state Liquid

Table 9 : BHET Properties

44
2.3.5 Terephthalic Acid (TPA)

Molecular Structure :

Properties Values
Formula C8H6O4
Molecular weight 166.14
Density 1.52 g/cm3
Melting point 300 °C
Boiling Point sublimes
Colour White Crystal Powder
Physical state Solid

Table 10 : TPA Properties

2.3.6 Water

Molecular Structure : H–O–H

Properties Values
Formula H2O
Molecular weight 18.02
Density 1.00 g/cm3
Melting point 0 °C
Boiling Point 100 °C
Colour Colourless
Physical state Liquid

Table 11 : Water Properties

45
2.4 Feedstock Supply

2.4.1 Supplier Profile

OPTIMAL GLYCOLS (MALAYSIA) SD BHD

The Company was established in July 1998 to develop a world class integrated
petrochemical facility in Kertih, Terengganu, Malaysia. Centered within the PETRONAS
Petroleum Industry Complex, Malaysia’s most sophisticated and advanced petrochemical
facility, the OPTIMAL GLYCOLS (MALAYSIA) SDN BHD is located 3 km from Pekan
Paka and 10 km from Kerteh.

OPTIMAL GLYCOLS (MALAYSIA) SDN BHD produces three main products ie.
Mono-Ethylene Glycol (MEG), Di-Ethylene Glycol (DEG) and Re-Distilled Ethylene Oxide
(RDO), using world-renowned EOG METEOR™ Technology from Dow, the most advanced,
efficient and cost competitive technology for the production of MEG, DEG and high purity
EO for derivatives.

Both, MEG (the largest volume product manufactured by OPTIMAL GLYCOLS) and
DEG are sold within Malaysia and to various countries throughout the Asia Pacific region.
OPTIMAL Glycols (M) Sdn Bhd is a wholly owned subsidiary of Petronas.

Products & Production Capacity of OPTIMAL GLYCOLS (M) SD BHD:

Products kTa
Mono-Ethylene Glycol (MEG) 365
Di-Ethylene Glycol (DEG) 20
Re-Distilled Ethylene Oxide (RDO) 140

*NOTE: kTa: Kilo Metric Ton Per Annum (1000 MTY)

46
BP Amoco SD BHD

The purified terephthalic acid (PTA) plant is located in the State of Pahang on the east
coast of the Malaysia peninsula, 25 km from Kuantan town. This BP wholly owned unit
began production in 1996 with an annual PTA capacity of 600,000 tons. Shipments are made
by truck, bulk containers, and FIBC bags.

The Kuantan plant employs over 270 full-time residents and 150 contractors.
Commissioned in 1996, the plant had received ISO 9002 certification in 1998 and ISO 14001
in 2001. The site had achieved many awards including the 1999 National Occupational Safety
& Health Award, the Prime Minister Hibiscus Award 2000/2001 for Exceptional
Achievement in Environmental Performance, National OSH Award 2001 for Transportation,
Logistics & Communications.

47
CHAPTER 3 : PRELEMI ARY HAZARD A ALYSIS

3.1 Safety Issues and Preliminary Hazard Analysis

Development of a complete plant design involves consideration of many different


topics .The overall picture of designing involves extensive study of engineering including the
most important parameter beside economic is the safety.

Chemical handling, processing and storing consist of many safety issues. The hazard
may simply come from storage of the chemicals and towards the reaction of the chemicals
itself. Hazards existed in some chemical because of its natural behavior to explode or react
dynamically with or without any external factors. Potential hazard will depend on inherent
toxicity of materials and also inherent toxicity of the materials frequency and duration of any
exposure .It is essential for designer to aware of these hazards and develop a design that will
minimize the potential hazards as minimum as possible.

This chapter will emphasize the important of Preliminary Hazard Analysis which
include identification and assessment of hazards and general safety procedure. Some of the
topic that will be included in this chapter are particular hazard for each chemical and law
requirement in Malaysia regarding set up a process plant in Malaysia.

3.2 Identification of Material and Chemical Hazard

The chemicals that are used in our process are listed as below:

Feed • Terephthalic acid


• Ethylene Glycol
Product • BHET
• PET
Byproducts • DEG
• AA
Catalyst • Antimony Trioxide

48
From all of material and chemical involved in the production, certain critical factors must be analyzed from each Material Safety Data
Sheets (MSDS) as in the Table 14 ;

Stability and
Material Health Affect Fire and Explosion Corrosivity Toxicity
Reactivity
Hazardous in case of skin
contact (irritant), of eye The substance is toxic to blood,
contact (irritant), of kidneys, liver, bladder, brain,
ingestion, of inhalation May be flammable in cardiovascular system, eyes,
TPA Not Available Not Available
(lung irritant). Repeated or high temperature Nutritional and Gross
prolonged exposure to the Metabolic, ears, nose/sinuses,
substance can produce throat
target organs damage

Hazardous in case of Instability when excess Chronic effects:Mutagenic for


ingestion. Slightly heat and incompatible mammalian somatic cells. Non-
hazardous in case of skin materials. Reactivity mutagenic for bacteria and/or
Non-corrosive
Ethylene contact (irritant, May be flammable in special remarks: yeast. May cause damage to the
in presence of
Glycol permeator), of eye contact high temperature Hygroscopic. Absorbs following organs: kidneys,
glass
(irritant), of moisture from the air. liver, central nervous system
inhalation. Severe over- Avoid contamination (CNS).
exposure can result in with materials with
death. hydroxyl compounds.
Also incompatible
with aliphatic amines,
isocyanates,
chlorosulfonic acid,
and oleum

No flah point data but


Irritating to eyes,
PET N/A n/a avoid temperature
respiratory system and skin
above 235 °

carcinogenic effects: Classified


Hazardous in case of skin Non-flammable.Risk
Non corrosive A2 (Suspected for human.) by
Antimony contact (irritant, sensitizer), of explosion when
in presence of Stable ACGIH. Causes damage to the
Trioxide of eye contact (irritant), of presence of static
glass following organs: lungs,
ingestion, of inhalation discharge
mucous membranes.

Table 14 : MSDS for Selected Chemical

50
Item Potential Hazards Potential Mitigating Measures
Reduce Reactor
• Over pressurization due to vaporization of • Choose continuous or semi batch operation since batch
Inventories
liquid because of high energy release. operation requires large inventory safety incentive.
• Overheated condition since the removal of • Overpressure relief protection such as rupture disk,
heat produced is less than its cooling rate, pressure safety valve, or combination of the two is
where pressure will increase as temperature needed for the reactor.
change. • Proper process control system to avoid overheated and
• Rate of temperature rise will be faster once over pressurization conditions at the reactor.
heat generation exceeds the available cooling • For reactor with runaway reaction, the set pressure of
capacity. the safety valve or rupture disk should be close to the
normal operating pressure as possible.

Distillation • High pressure may cause flooding. • Select suitable sequence that tends to minimize the
• Large inventories of boiling liquid, flowrate of non key components.
sometimes under pressure, in the distillation • Use suitable column to reduce the inventory as well as
column both in the base and held up. potential leakage problem.
• Overpressure relief system is needed.

51
Item Potential Hazards Potential Mitigating Measures
Heat • Common safety problems include tube • Flammable materials needs to be substitute with less or
Transfer rupture, leaking, fouling, tube vibration, non-flammable materials.
Operation polymerization, and solidification. • Less hazardous refrigerant fluid used at low pressure
• Failures in heat exchangers result in pressure operation may lead to major hazard, but it is allowable
changes and contamination of the heat when the process is at higher pressure.
transfer, fluid or process fluid. • Double tube sheets are recommended for highly toxic
materials.
• Overpressure relief is needed for protection of heat
exchangers against effect of tube rupture

Chemical Reaction • When more hazardous components involve • Select process route that involves less hazardous
in chemical reaction, more hazardous chemicals.
condition (e.g. explosion, accident etc) may • If substitution is not possible, isolation of the process
occur. from the workers is necessary.
Chemical Storage • Chemical leakage from storage tank can lead • Storage equipments need to be at a low temperature,
to vapor cloud and toxic cloud. well ventilated area, under an atmosphere of dry
• Improper chemical storage and flow control nitrogen, and away from sources of fire hazard.
may lead to the possibilities of explosion of • Usage of closed spherical or cylindrical tanks to
the storage equipments since most chemicals prevent the escapes of volatiles and minimize
being stored are flammable. contamination.

52
Item Potential Hazards Potential Mitigating Measures
• Chemicals that leak can flow to electrical • To maintain the pressure of storage tank, pressure
component, which is a source of ignition that safety valve should be installed on top of it. Vapors
may lead to explosion. that should be vented from the tank must be sent to the
• Storage tank may easily corrode since the incinerator instead of atmosphere.
chemicals being stored are mostly corrosive. • Vent should be positioned so that the outlets cause the
least possible contamination to the working
atmosphere or any neighbouring location.
• Equipment for storage tank need to be made from
glass, polyethylene, polypropylene, or stainless steel.
Material of Construction • Usage of poor materials may lead to leakage, • Stainless steel is recommended for process stream to
rupture, corrosion, or explosion. prevent corrosion.
• Usage of carbon steel can lead to corrosion • The thickness of the equipment need to be on-
when corrosive components flow through it. specification.
• High pressure process within vessels and • Electrical equipments should be spark resistance to
columns may cause cracking. avoid incident and property loss.
• Electrical components may cause a spark • Suitable materials of construction include steel,
that can lead to explosion if any leakage of stainless steel, and aluminum. Galvanized steel and
flammable chemical occurs. plastics should not be used.
Temperature and Pressure • High pressure operation may cause serious • Appropriate design, operating, and maximum pressure
leakage problem. and temperature are needed to ensure safe processes.

53
Item Potential Hazards Potential Mitigating Measures
• Possible access of air low pressure operation, • Protection by instrument is important to maintain
which may cause flame or explosion when temperature and pressure to the normal operating
react with flammable component. pressure.
• High temperature can lead to rupture of tubes
carrying process fluids and possible
explosions.
Toxicology and Health • Most chemicals in the process or product • Proper PPE should be used to avoid any direct contact
Hazards streams have toxicity amount if ingested or and inhalation of the toxic chemical.
inhaled. • Proper chemical handling procedure with high
• Frequent exposure of the chemicals may lead supervision from expert personnel is needed to ensure
to human mutagenic. safe procedures of operation.
• Direct contact may cause corneal injuries,
severe eye irritation or burns to the eyes.
Flammability • Explosion may occur if the chemicals in • Prohibited and eliminate all sparks and ignition sources
reboiler or heater are overheated. as well as any flame usage in the plant area (e.g.
• Spark can be produce from tools and smoking).
vehicles during maintenance operation. • Usage of hot work permit is needed if any flame or
• When flammable chemical leaks reach sparking equipment is being used. Lower explosive
electrical components, explosion may occur. limit (LEL) of the area must be at safe level before any
operation starts, with supervision while it is in

54
Item Potential Hazards Potential Mitigating Measures
progress.
Environmental Impact • Waste water stream from the process plant • Proper waste water treatment is needed to reduce the
can be hazardous if not well treated before toxicity of water and the components released.
being released to surrounding or river.
Sitting and Safe Location • Emission of toxic and hazardous chemicals • Consider safe living conditions for plant operation as
into the atmosphere can affect the plant well as the nearby community.
personnel and the community of nearest • Suitable plant location should be far from residential
residential areas. area, with the availability of nearby sources of raw
materials and other facilities such as transportation and
fire station.
• High risk of disaster (e.g. earthquake, • Provide accessibility for fire fighting in case of
flooding etc) may cause serious problem to emergency involving flame and explosion.
the plant operation. • Provide adequate locations of emergency exits for
rapid evacuation and rescue.
• Locate in-situ automatic fire detection and suppression
systems components for effective respond with
minimal reliance on plant personnel.
• Eliminate ignition sources from the vicinity of the
most flammable and explosive materials and
equipment.

55
Item Potential Hazards Potential Mitigating Measures
• Isolate the most hazardous materials and processes to
maintain special precautions in these hazardous areas.
The size and extent of any hazardous area must be
limited to ensure that the plant is not at risk from any
accident
• Provide passive barriers for fire containment and
explosion resistance, which should effectively limit
fire or explosion propagation and damage even in the
absence of active detection and suppression.
Plant Layout • Poor arrangement of processing areas, • Consider safe operational sequence in the layout based
storage areas, and handling areas facilities on the flow of materials, unit operations, storage and
may trouble the plant operation, since more future expansion.
damage and accidents will occur. • Separate process and non-process area. Flaring and
storage area should be located far from process area.
• Assembly areas must be provided in case of
emergency at both process and non-process area.
• Consider the placement of raw water tank near the high
potential of flaming area.
• Enough lighting and color coding for recognition of
hazardous and non hazardous areas.

56
Item Potential Hazards Potential Mitigating Measures
Transportation • Spillage of toxic chemicals may cause • Employees need to wear personnel protective
serious injuries when directly be in contact. equipment for protection from toxic and hazardous
• Vapor may pass through the container’s cap chemicals.
if it is not properly sealed. • Containers must be sealed properly and clearly labeled
• With improper road system, the occurrence before being transported.
of accidents is of high risk. • Prohibit unauthorized vehicles from entering process
area.
• Piping arrangements and joining must be properly
design to avoid leakage.
• Provision of proper road system is very necessary.

Table 15 : Safety Risk and Mitigation Measures

57
3.3 Emergency Situation Procedure

Accidents could be happened regardless of time and place. There is a need to list the
emergency procedure guideline.
General Procedure

Some of the procedures that must be taken when the emergency situation happened in the
plant are :

i. Do not panic and stay alert.


ii. Assess the situation around your area.
iii. Wait for instructions from supervisor or shift manager.

Fire/Explosion/>atural Disaster

This procedure should be taken for fire , explosion or natural disaster are same.Basically ,the
procedures especially for the above situation are:
i. Raise the alarm.
ii. Immediately inform the supervisor or shift manager.
iii. Assess the situation.
iv. Wait and follow the instruction from them.

Hazardous Substance Discharge

If any hazardous substance discharge incident occurred, without taking any unnecessary
personal risk, the following procedure had to be followed:

i. Immediately inform the supervisor or shift manager


ii. Minimize substance discharge
iii. Identify substance and act accordingly
iv. Neutralize the substance discharge
v. Wait for the instructions from supervisor or shift manager
The following are the basic precaution for the two common hazardous substances:

1. Inflammable liquid
• Use only spark-proof materials
• Do not make any ignition
• Beware with electrical switchgear that can cause a spark.

2. Corrosive Liquid
• Use the safety clothes
• Check location and operation of safety shower or cold water supply
• Use breathing equipment if the substance emits toxic flames.

Instrument Protective System

Hazard not only comes from chemicals itself, it may come from the instrument use in the
process. Therefore there is a need to check the instrumentation protective system and should
be tested regularly to ensure it is in good condition. Some of the protective system is listed
below:

i. Air monitoring
ii. Leak detection system
iii. Emergency valves
iv. Labels and sign
v. Controlling leaks

3.4 Local Safety Regulations

Laws and regulations are major tools for protecting people and also environment
.Local safety and environmental regulations must be compiled with when developing new
plant, in order to ensure safe workplace and prevent accidents or any environmental pollution
that can adversely affect the whole plant operation as well as the surroundings. Listed are
several related acts and regulations for compliance:

59
Occupational Safety and Health Act (OSHA) 1994

OSHA was created with a purpose to reduce work-related injuries, illness and death and
incidentally, to cut resulting cost (lost wages and productivity, medical expenses, disability
compensation).

The following is the related act of OSHA for the process plant safety:-

• Factories and Machinery Act 1967


• Occupational Safety and Health (The Control of Industrial Major Accident
Hazards) Regulations 1996
• Occupational Safety and Health (Classification, Packaging, and Labeling of
Hazardous Chemicals) Regulations 1997
• Occupational Safety and Health (Use and Standards of Exposure of Chemicals
Hazardous to Health) Regulations 2000

Environmental Quality Act (EQA) 1974

Environment Quality Act 1974 has the objective for prevention, abatement and
control of pollution and enhancement of environment by restricting discharge of waste which
applies to the whole Malaysia. The act control pollution by licensing and approval for
existing operation, through prohibition of equipment and material, and Environmental Impact
Assessment (EIA) requirement.

60
Before starting any industry, EIA report has to be prepared to report the information
about the industry itself and the consequences to the environment, where it has to be
submitted to the Department of Environment of the state to be approved before license is
given. The following are the related act regarding to process plant industry:-

• Environmental Quality (Licensing) Regulations, 1977


• Environmental Quality (Clean Air) Regulations 1978
• Environmental Quality (Sewage and Industrial Effluents) Regulations 1979
• Environmental Quality (Prescribed Activities) Regulations 1986
• Environmental Quality (Prescribed Activities) (Environmental Impact
Assessment) Order 1987
• Environmental Quality (Scheduled Wastes) Regulations 1989
• Environmental Quality (Prescribed Premises) (Scheduled Treatment and
Disposal Facilities) Order 1989
• Environmental Quality (Prescribed Premises) (Scheduled Wastes Treatment
and Disposal Facilities) Regulations 1989

61
CHAPTER 4: CO CEPTUAL DESIG A ALYSIS

4.1 Preliminary Reactor Optimization

4.1.1 Reactions Involved

There are three reaction paths involved in the process for the production of polyethylene
terephthalate (PET). The first path is esterification reaction, the second path is pre-
polycondensation reaction and the third path is final polycondensation reaction.

Esterification reaction:
C8H6O4 + 2 C2H6O2 ⇌ C12O6H14 + 2 H2O

Pre-polycondensation reaction:
nC12O6H14 ⇌ C2H5O(C10H8O4)nOH + (n-1)C2H6O2 n = 30

Final polycondensation reaction:


mC2H5O(C10H8O4)nOH ⇌ C2H5O(C10H8O4)n.mOH + (m-1)C2H6O2 m = 3.733

4.1.2 Esterification Reaction

In the esterification reaction, terephthalate acid (TPA), C8H6O4 is reacted with ethylene
glycol (EG), C2H6O2 producing monomer known as bis-(2-hydroxyethyl) terephthalate
(BHET), C12O6H14 and water, H2O. The reaction is reversible; therefore water formed during
the reaction has to be removed in order to convert the starting materials completely into the
monomer. A catalyst is not required in this reaction and conventionally no catalyst is
employed (Kathleen L. Trojan, 1999). Esterification is generally accepted as a third order
reaction, thus the acid behaves both as a reactant and a catalyst. The rate constant of
esterification was found to increase with pKa of the carboxylic acid (Faissal-Ali El-Toufaili,
2006).

62
ESTERIFICATION
Mol flow rate (kmol/hr) Mol flow rate (kmol/hr)
C8H6O4: 161.08 REACTOR
C12O6H14: 158.02
C2H6O2: 628.45 H2O: 315.72

Figure 10: Overall Esterification Reaction

The figure above describes the overall esterification reactions that occurred in the reactor.
Based on the figure, the limiting reactant is TPA and the excess reactant is EG. The amount
of EG that is use as feed in the process is 192.52 kmol/hr, however since the pre-
polycondensation and final polycondensation reaction produced EG as well, some of the EG
produced from the reactions will be recycle into the esterification reactor, making the
amount of feed into the first esterification reactor become 628.45 kmol/hr. The reaction
mixture in this reactor is a heterogeneous system in which solid, liquid and vapor phase are
jumbled together. Due to the solid TPA, a monomer in PET synthesis has very low solubility
in EG (Ju-Youl Kim, Hee-Young Kim & Yeong-Koo Yeo, 2001). A high operation
temperature of the esterification reactor is needed to dissolve the TPA in EG and to increase
the rate of reaction.

In the reaction system, it is assumed that the vapor pressure is contributed only by EG and
water because oligomer is not volatile, the vapor pressure of TPA and DEG are negligible,
and only EG vapor is recycled completely. All reactions proceed in liquid phase, and the
density of the reaction mixtures is assumed to be constant. Even though the reaction mixtures
are slurry with high viscosity, the assumption of perfect mixing is the reactor is applicable
since various mixing units are used in the actual plant to prevent loss due to imperfect mixing
(Ju-Youl Kim, Hee-Young Kim & Yeong-Koo Yeo, 2001).

63
The reactor operates at 250ºC, at a pressure of about 265 kPa. Under these conditions and
with continuous removal of water by-product, it takes about 3 hours for the esterification
reaction to reach 85-95% conversion. The second esterification reactor operates at
temperature around 250ºC and at a pressure 250 kPa. The lower pressure reflects the fact that
in the second reactor, less volatile are being generated and the volatiles composition in
shifted from being rich in water to being rich in EG. After 2 hours, the esterification in the
second reactor is about 98% complete (S. M. Aharoni, 2002).

4.1.3 Polymerization Reactions

For the pre-polycondensation reaction, the BHET will further react to form the first polymer
of PET that has a degree of polymerization of 30 and EG. At this point, antimony trioxide is
added as catalyst. The reaction is also reversible; therefore the EG formed during the reaction
need to be removed to convert the monomer into the polymer. For the pre-polycondensation
reactor, the operating temperature is about 260ºC and the pressure is gradually decreased to
6.661 kPa where polyester with a degree of polymerization of around 30 is created. The pre-
polycondensation reactor is stirred tank reactors with unusual ratio of diameter or height to
provide large gas-liquid interface.

PRE-
POLYCONDENSATION
Mol flow rate (kmol/hr) REACTOR Mol flow rate (kmol/hr)
C12O6H14: 158.02 C2H5O(C10H8O4)30OH: 5.27
C2H6O2: 168.17

Figure 11: Pre-polycondensation Reaction

64
The final polycondensation reaction will proceed by expanding the polymer chain to produce
PET with a higher degree of polymerization, 112 (m x n = 112). This reaction is also
reversible and producing EG, therefore the EG formed need to be removed as well in order to
convert the reaction into the desired polymer. For this reactor, the operating condition is
280ºC with a pressure of 1.33 kPa. This reactor consist of horizontal vessels supplied by a
series of horizontal stirrers, which were optimized to provide a plug flow of the melt with
little back mixing in order to keep the residence time distribution narrow and to achieve
higher average polycondensation rate (Faissal-Ali El-Toufaili, 2006).

FINAL
POLYCONDENSATION
Mol flow rate (kmol/hr) REACTOR Mol flow rate (kmol/hr)
C2H5O(C10H8O4)30OH: C2H5O(C10H8O4)112OH: 1.41
5.27 C2H6O2: 3.91

Figure 12: Final Polycondensation Reaction

Both of the reactors for polycondensation operate at a very high vacuum pressure to remove
the EG that is produced in the reaction. The final degree of polycondensation can be
controlled by adjusting vacuum, reaction temperature and average residence time.

Recycling of undesired product will increase the selectivity of the reaction. For example, in
the pre-polycondensation and polycondensation reactions, the EG that is produced can be
recycle into the esterification reactor and favor the reaction to produce more BHET. Another
advantage of recycling the by-product from polycondensation reaction is that the amount of
fresh feed (EG) that is needed to be feed into the reactor can be reduce and this will reduce
the cost of raw material.

65
4.2 Process Screening

4.2.1 Heuristic Approach for Separation System Synthesis

In conceptual design, other than the optimization of the reactor, separation sequence train is
also a major concern in designing a chemical processes.
i) Selection of separation techniques
ii) Sequencing of separation techniques
iii) Adapting operating conditions for integration and optimization

The objective of this separation train is to develop the overall flow sheet that indicates which
components need to be separated and where they are expected to leave the process. For this
process, two types of separators will be use depends on the inlet phase;
i) Distillation column – for single phase liquid mixture
ii) Two-Phase Separator – for two phase liquid-vapor mixture

4.2.2 Sequencing of Separators

For sequencing of separators in a separation system, the following heuristics were applied:

i) The most difficult separations will be done at the end of the process.

ii) Direct sequence is usually favored in this case. Sequences that remove the lightest
components alone one by one in column overheads should be favored.

iii) A component making up a large fraction of the feed should be removed first

Before entering the esterification reactor, the EG fed will be purify using distillation column
to remove the water content in the fresh feed. The same distillation column is use to purify
the EG recycled from the formation of by-product from polycondensation reactions.
Purification of EG fresh feed is important to overcome the accumulation of unwanted
impurities, in this case is water, which might affect the esterification reactions.

66
After entering the reactor, most of the products formed will be in two phase mixture. This
mixture can be separated by two-phase separator. The rules of thumb apply in heterogeneous
mixture separation:

i) Separation of heterogeneous mixture is easier than for homogeneous mixture

ii) Separation of heterogeneous mixture should be carried out before homogeneous


mixture separation

For this process, the use of separator is crucial especially in removing the water that has been
produced during the esterification reaction and removing EG in the polycondensation
reactions. This is to ensure that the reaction does not proceed to form the reactants since they
are reversible reactions. The vapor separated from the two-phase separator contains high
fraction of EG and water, thus both of this mixture need to be further separated using
distillation column. This vapor mixtures are cooled down to change the phase from vapor
phase to liquid phase in order to further separated using distillation column.

Besides using the distillation column for purifying of EG, it can also be used to separate
water from EG and at the same time, recycled back the EG into esterification reactor. The
advantages of using distillation column in separation of liquid mixtures:

i) Distillation columns offer the most economical way for liquid mixture separation,
as the operating cost is mainly on the utility (cooling water and steam) used within
the condenser and reboiler.

ii) Distillation are able to separate mixtures of wide range of liquid mixtures and
feed concentration, as other homogenous mixture separation are limited to feed
with low throughput and relatively pure.

iii) The ability of distillation to produce high-purity products, without involving any
extra components being introduced into the separation system like liquid-liquid
extractions.

67
4.2.3 Operating Conditions for Separators

The table below summarizes the operating conditions for separating unit in the process:

Unit Mixtures Operating Conditions


Reboiler
Inlet = EG & Water
T = 207ºC P = 140 kPa
Distillation Column Outlet (liquid) = EG
Condenser
Outlet (vapor) = Water
T = 107.2ºC P = 130 kPa
Separator 1
T = 280ºC P = 141.7 kPa
Inlet = TPA, EG, Water & BHET
Separator Separator 2
Outlet (liquid) = TPA, BHET, EG
(esterification) T = 190º P = 131.7 kPa
Outlet (vapor) = Water & EG
Separator 3
T = 265ºC P = 101.3 kPa
Separator 1
Inlet = PET & EG
Separator T = 280ºC P = 6.67 kPa
Outlet (liquid) = PET
(polycondensation) Separator 2
Outlet (vapor) = EG
T = 270º P = 1.33 kPa

Table 16: Separators with Types of Mixtures and Operating Conditions

68
4.3 Economic Potential (EP)

4.3.1 Economy Analysis

It is crucial for plant designers and engineers to take economic feasibility into
consideration when planning a plant. Beside direct costs, there are also different types of cost
involved for the plant operation and establishment. The EPCIC (Engineering, Procurement,
Construction, Installation and Commissioning) has significant affect on plant economics.
Other factors that might affect economic are as shown below:

• Raw materials price fluctuation


• Company policies
• Governmental policies

Our economic analysis is based on assumptions stated below:

• The calculation made follows the Douglas’s approach method


• Prices for raw materials are valid till August 2010
• The interest rate for plant operation is 10% per annum
• Project life-cycle will be 20 years
• Plant operates at normal annual operation period which is 330 days

4.3.2 Total Capital Investment

Capital investment by is the total amount need to be invested in the early stages of
pant design.There are two parts for capital investment which are fixed capital investment and
working capital investment.

69
4.3.3 Fixed Capital Investment

Purchasing of necessary equipments plus the installation is crucial as it will be the


core investment that will determine the operatibility of the plant as well as piping installation,
land, instrumentation, services and the land where the plant is going to be established

Equipment Purchase Cost (RM)


Reactor 595,586.05
Separator 2,337,540.25
Compressor 535,223.00
Distillation column 7,032,410.00
Pump 801,888.17
Heater 1,266,312.00
Cooler 1,953,401.60
Mixer 2,421,233.00
Splitter 1,824,382.00
Total Equipment Cost 18,767,976.07
Source : MATCHES (www.matche.com)

Table 11 : Equipment Required and Estimated cost for PET Plant

70
From the fixed capital costs, we could split it into two costs which are direct cost and
indirect cost. The components of the direct and indirect cost are shown below:

COMPO E T ESTIMATIO COST (RM)


Direct Cost
Total Equipments Costs 18,767,976.07
Equipment Installation
(includes insulation and 40% of total equipment cost 8,699,596.16
painting)
Piping System Installation 50% of total equipment cost 10,874,495.20
Instrumentation and Control 20% of total equipment cost 4,349,798.08
Electrical System Installation 15% of total equipment cost 3,262,348.56
Service facilities 50% of total equipment cost 10,874,495.20
Building, process and
40% of total equipment cost 8,699,596.16
auxiliary
Land 6% of total equipment cost 1,304,939.42
Yard Improvement 12% of total equipment cost 2,609,878.85
Total 69,443,123.68
Indirect Costs
Engineering and supervision 10% of total direct cost 6,944,312.368
Construction expenses
Legal expenses 10% of total direct cost 6,944,312.368
Contractors fee 5% of total direct cost 3,472,156.184
Contingencies 12% of total direct cost 8,333,17.842
Total 18194098.03
Fixed Capital Investment Direct Costs + Indirect Costs 87,637,221.71

Table 12 : Fixed Capital Investment for PET Production Plant

71
4.3.4 Working Capital Investment

Working capital represents costs necessary to operate the plant. Listed below are the
components of the working capital that need to be taken account.

1. Raw materials for one-month supply.


2. Finished products in stock and semi finished products.
3. Accounts receivable.
4. Cash on hand to meet the operating expenses.
5. Accounts payable and taxes payable

Typically, Douglas proposes that the estimated value of working capital investment is simply
15% of the fixed capital investment (III).

Working capital investment = 0.15 x fixed capital investment


= 0.15 x RM 87,637,221.71
= RM 13,145,583.26

4.3.5 Start Up Cost

Costs allocated for starting up the plant operation are start-up costs. Some of the examples of
start-up costs are process modifications, start-up labor and loss in production.

From Douglas method, the startup cost will be 10% out of fixed capital investment.

Start-up Costs = 0.10 x fixed capital investment


= 0.10 x RM 87,637,221.71
= RM 8,763,722.171

72
4.3.6 Total Capital Investment

The total for total capital investment is addition from fixed capital investment and working
capital. But we add up the start-up costs as added values.

Total capital investment = Fixed capital investment + Working capital investment


+ Start-up costs
= RM 87,637,221.71 + RM 13,145,583.26 + RM 8,763,722.171
= RM 97,715,527.14

4.3.7 Utilities

Plant uses both hot utility and cold utility. Both of the utilities tariff are take from
latest Tenaga Nasional Berhad as this industry falls under the category of industrial
consumer.

We assume that we will be using the high voltage industry tariff. Below shown the tariff for
high voltage industry:

Figure 9: Tariff for High Voltage Industries

73
UTILITIES USAGE TOTAL COST
RM549.45 /h (Peak period)
Cold 2,065.6 kW/h
RM330.496 /h (Off-Peak Period)
RM 965.64 /h (Peak period)
Hot 3714 kW/h
RM 594.24 /h (Off-peak period)
RM 1515.09/h (Peak period)
TOTAL
RM 924.736 /h (Off- Peak period)

Table 13 : Plant Utilities

Assume Peak period 8AM-5PM Off-Peak Period 7PM-8AM


= RM1515.09 X 8 Hours = RM 924.736 X 16 Hours
= RM12, 120.72 = RM 14,795.776

Total for a day = RM 26,916.496


= RM 26916.496 X 330 days
= RM 8,882,443.68 /year

Economy Potential 1:

Economic Potential 1 (EP 1) = (Product value) – (Raw material cost)

Mass flow for main chemicals:

Ethylene Glycol (EG) = 11973.19 kg/hr


Terepthalic Acid (TPA) = 26760 kg/hr
PET = 30450.7 kg/hr

74
Pricing :

Substance Pricing (August 2010)


Ethylene Glycol $1006 / ton
Terepthalic Acid $895 / ton
PET $1 350 /ton
(Source: www.icis.com)

Calculations :

TPA =

= $718.39 /hr

EG =

= $ 2007/hr

PET =

= $34104.784/hr

Gross Profit

Profit = Product-Reactant
= $34104.784/hr – ($ 2007/hr + 718.39 /hr)
= $31379.394 /hr
= RM 97739.0804/hr

Gross Profit for a year (330 days)

75
Profit per day = RM97739.0804 /hr X 24 hours/Day
= RM 2,345,737.93/day

Profit per annum = RM 2,345,737.93/day X 330days/year


= RM 774,093,516.8 / year

76
4.4 Mass Balance by Manual Calculation & iCO Simulation

Below is the mass balance performed by theoretical manual calculation compared to iCON
Simulation. Several assumptions have been made in order to have an accurate result.

a) Mass balance around esterification reactor 1 ( )

Manual
I LET OUTLET
Molecular
Component
Weight
mol mass mol mass
(kmol/hr) (kg/hr) (kmol/hr) (kg/hr)
TPA 166.14 161.27 26793.39 8.06 1339.08
EG 62.08 628.45 39014.17 322.04 19992.24
BHET 254.26 0 0 153.21 38955.17
WATER 18.02 0 0 306.41 5521.50
Total 789.72 65808.01 789.72 65808.01

iCON
I LET OUTLET
Molecular
Component
Weight
mol mass mol mass
(kmol/hr) (kg/hr) (kmol/hr) (kg/hr)
TPA 166.14 161.26 26790.78 8.06 1339.54
EG 62.08 628.59 39173.97 322.18 20156.39
BHET 254.26 0.33 53.66 153.53 39003.22
WATER 18.02 0.02 0.04 306.42 5520.28
Total 790.2 66018.45 790.2 66019.43

b) Mass balance around esterification reactor 2 ( )

77
Manual

Molecular I LET OUTLET


Component
Weight
mol mass mol mass
(kmol/hr) (kg/hr) (kmol/hr) (kg/hr)
TPA 166.14 8.06 1339.08 3.23 536.63
EG 62.08 322.04 19992.24 312.37 19391.93
BHET 254.26 153.21 38955.17 158.05 40185.79
WATER 18.02 0 0 9.67 174.25
Total 483.31 60286.51 483.31 60286.51

iCON

Molecular I LET OUTLET


Component
Weight
mol mass mol mass
(kmol/hr) (kg/hr) (kmol/hr) (kg/hr)
TPA 166.14 8.06 1339.08 3.23 536.63
EG 62.08 322.04 19992.24 312.37 19391.93
BHET 254.26 153.21 38955.17 158.05 40185.79
WATER 18.02 0 0 9.67 174.25
Total 483.31 60286.51 483.31 60288.61

c) Mass balance around pre-polycondensation reactor


( )

78
Manual

I LET OUTLET
Molecular
Component
Weight mol mass mol mass
(kmol/hr) (kg/hr) (kmol/hr) (kg/hr)
BHET 254.26 158.05 40185.79 0 0
PET30 5824.46 0 0 5.268 30683.26
EG 62.08 0 0 152.78 9484.58
Total 158.05 40189.79 158.05 40167.83

iCON

I LET OUTLET
Molecular
Component
Weight mol mass mol mass
(kmol/hr) (kg/hr) (kmol/hr) (kg/hr)
BHET 254.26 158.01 40176.72 0 0
PET30 5824.46 0 0 5.27 30690.95
EG 62.08 10.85 673.51 163.65 10159.41
Total 168.86 40850.21 168.92 40850.36

d) Mass balance around final polycondensation reactor


( )

Manual

I LET OUTLET
Molecular
Component
Weight mol mass mol mass
(kmol/hr) (kg/hr) (kmol/hr) (kg/hr)
PET30 5824.46 5.268 30683.26 0 0
PET112 21575.02 0 0 1.411 30442.3
EG 62.08 0 0 3.857 239.55
Total 5.268 30683.26 5.268 30681.74

79
iCON

I LET OUTLET
Molecular
Component
Weight mol mass mol mass
(kmol/hr) (kg/hr) (kmol/hr) (kg/hr)
PET30 5824.46 5.27 30690.91 0 0
PET112 21575.02 0.001 18.45 1.41 30450.71
EG 62.08 0.05 3.10 3.91 242.45
Total 5.321 30712.46 5.32 30712.66

a) Mass balance around distillation column ( )

80
Manual

I LET OUTLET TOP (V) OUTLETTOP (D) OUTLET BOTTOM


Molecular
Component
Weight mol mass mol mass mol mass mol mass
(kmol/hr) (kg/hr) (kmol/hr) (kg/hr) (kmol/hr) (kg/hr) (kmol/hr) (kg/hr)
EG 62.08 628 38986.24 0 0 0 0 628 38986.24
WATER 18.02 315.71 5689.09 315.71 5689.09 0 0 0 0
Total 943.71 44675.33 315.71 5689.09 0 0 628 38986.24

iCON

I LET OUTLET TOP (V) OUTLETTOP (D) OUTLET BOTTOM


Molecular
Component
Weight mol mass mol mass mol mass mol mass
(kmol/hr) (kg/hr) (kmol/hr) (kg/hr) (kmol/hr) (kg/hr) (kmol/hr) (kg/hr)
TPA 166.14 0.19 31.57 0 0 0 0 0.19 31.57
EG 62.08 628.45 39014.18 0 0 0.78 48.42 628.45 39014.18
BHET 254.26 0.33 83.91 0 0 0 0 0.33 83.91
WATER 18.02 300.91 5422.40 300.12 5408.16 0 0 0.02 0.3604
Total 929.88 44552.06 300.12 5408.16 0.78 48.42 628.99 39130.03
4.4.1 Block Diagram for Production of PET Process

Figure 13: Block Diagram of The Process

82
CHAPTER 5 : HEAT I TEGRATIO

5.1 Pinch Analysis

Pinch analysis is a well establish synthesis and analysis tool for exchange of heat
within a network of heat exchangers. Some of its capabilities are:

i) Setting pre-design targets for utility consumption


ii) Setting pre-design target for the installed cost of heat exchanger network
iii) Designing heat exchanger network
iv) Optimizing the trade-off between energy costs and capital cost, optimizing the
selection of utility source

5.5.1 Pre-design Target for Utility Consumption

Problem Table Algorithm method is used to design heat cascade, composite curve and
grand composite curve. In problem table, the energy balance within the each segment of the
temperature interval connecting the hot and cold streams. The actual temperatures have to be
adjusted according to:

Cold stream = T + (∆Tmin/2)


Hot stream = T - (∆Tmin/2)

In this case, ∆Tmin = 10ºC. Below are the shifted temperature (TT*, TS*) for temperature
target (TT) and temperature supply (TS) together with the heat capacity.

Stream TT (ºC) TS (ºC) TT* (ºC) TS* (ºC) Cp (kJ/ºC.hr) H (kJ/hr)


H1 170 290 165 285 781.82 93818.4
H2 190 280 185 275 53959.49 4856354
C1 250 173.3 255 178.3 186103 14274100
C2 280 251.4 285 256.4 110576.9 3162499
C3 280 265 285 270 58248.9 873733.5
Table 17: Data from iCon Simulation
The figure below shows the heat transfer between each interval of temperature. The expression that is used to calculate the heat transfer between
each interval is:
Qi = [∑ ( FCP ) hot,i − ∑ ( FC p ) cold,i ]∆Ti

ΣCpc - ∆H
∆T (ºC) Deficit/Surplus
T(ºC) ΣCphot (kJ/hr)
285
10 168,043.98 1680440 Deficit
275
5 114084.49 570422.5 Deficit
270
13.6 55,835.59 759364 Deficit
256.4
1.4 -54,741.31 -76637.8 Surplus
255
70 131,361.69 9195318 Deficit
185
H2
6.7 185,321.18 1241652 Deficit
178.3
13.3 -781.82 -10398.2 Surplus
165

Figure 14: Heat Balance By Manual Calculation


Performing heat cascade of surplus heat from high temperature interval to low temperature interval

T (ºC) 0 T (ºC) Qh = 13370558.7


285 285
∆H = 1680440 ∆H = 1680440

275 -1680440 275 11690119

∆H = 570422.5 ∆H = 570422.5

270 -2250862.5 270 11119696


Adjust heat cascade from
∆H = 759364 the highest negative value ∆H = 759364

256.4 -3010226.5 accumulated 256.4 10360332

∆H = -76637.8 ∆H = -76637.8

255 -2933588.7 255 10436970

∆H = 9195318 ∆H = 9195318

185 -12128906.7 185 1241652

∆H = 1241652 ∆H = 1241652

178.3 -13370558.7 178.3 0

∆H = -10398.2 ∆H = -10398.2

165 -13360160.5 165 Qc = 10398.2


Figure 15 : Problem table Algorithm By manual Calculation
85
The manual calculation was compared using Aspen HX-Net 2006 software.

Qh = 3.196x106 kcal/hr
(1.337x107 kJ/hr)

QC =2485 kcal/hr
(1.04x104 kJ/hr)

86
Composite curve generated by using Aspen HX-Net 2006 software

Figure 16 : Composite Curve generated by using Aspen HX- et 2006 software

87
Grand composite curve generated by using Aspen HX-Net 2006 software

Figure 17 : Grand Composite Curve generated by using Aspen HX- et 2006 software

88
Heat exchanger network generated by manual calculation

∆H T(ºC) 183.3 Cp
(kJ/hr) 83420.19 10398.21 (kJ/hr) ∆H (kJ/hr)
83420.19 290 170 781.82 10398.206

4856354 280 190 53959.49

250 200ºC 174ºC


14274100 186103
9334325.8 4856354 83420.19
3162499 280 251.44 110576.9
3162499
873733.5 280 265 58248.9
873733.5 173.3

Figure 18 : Heat Exchanger etwork

Total Hot Utility = 9334325.8 + 3162499 + 873733.5 = 13,370,558.3kJ/hr

Total Cold Utility = 10,398.206 kJ/hr

89
5.2 Difference in Heat Exchanger Duty Requirement Before and After Heat
Integration (HI)

i) Hot utility
Duty before HI = 18,310,332.5 kJ/hr
Duty after HI = 13,370,558.3kJ/hr

ii) Cold utility


Utility excluded in HI = 7,425,733.81 kJ/hr
Duty before HI = 7,425,733.81 + 4,950,172.4 = 12,375,906.21 kJ/hr
Duty after HI = 7,425,733.81 + 10,398.206 = 7,432,132.016 kJ/hr

Duty before HI
Type of Utility Duty after HI (kJ/hr) % Saving
(kJ/hr)

Hot 18,310,332.5 13,370,558.3 26.98

Cold 4,950,172.4 10,398.206 39.95

Table 18 : Summary Of % Saving After Heat Integration

From the heat integration analysis table, the plant can reduce the amount of cold utility and
hot utility up to 29.95% and 26.98% respectively. Thus, it can be concluded that heat
integration in beneficial as it reduce the operating cost.
CHAPTER 6 : PROCESS DESCRIPTIO

6.1 Process Description

Polyethylene Terephtalate (PET) is a type of thermoplastic polymer at which it is


produced by step-growth polycondensation polymerization under evolution of condensates
that is water during the esterification process and also ethylene glycol (EG) during the
polycondensation process.

Figure 19: Reaction flow of PET production.

91
6.2 Feed Raw Material

The first step in producing Polyethylene Terephtalate is the esterification process


whereby in this process, Terephthalic Acid (TPA) is reacted with Ethylene Glycol (EG) in a
direct esterification reaction, producing bis-(2-hydroxyethyl) terephthalate (BHET) and
water.
At the plant, the recycled Ethylene Glycol (EG) produced from the previous poly
condensation process are mixed with raw EG from supplier. Mixture of raw Ethylene Glycol
(EG) with the recycled one contained some impurities, thus they are fed to the distillation
column for the impurities to be removed first. Then purified Ethylene Glycol (EG) is fed to
another mixer to be mix with Terephtalate Acid (TPA) to form a paste at atm pressure and
room temperature. In the case of plant PET production, both raw reactants that is Ethylene
Glycol and Terephtalate Acid (TPA) are stored in two different storage facilities at which
Ethylene Glycol (EG) is stored in tank while Terephtalate Acid (TPA) is stored in the silos
since it is in powdered form compared to the Ethylene Glycol (EG) that initially is in liquid
form.

6.3 Reactions Involved

6.31 Esterification Process

As for the industrial production of PET, the ratio between feed Ethylene Glycol (EG)
to Terephtalate Acid (TPA) fed to the esterification reactor are in the range of 1.2:1 in order
to maximise the reaction between these two reactants since Terephtalate Acid (TPA) acts as
the limiting reactant in this reaction.
The mixtures of these two reactants are then being heated up to temperature of 250oC
and pressure of 265kPa in the first esterification reactor. The temperatures is further increased
in the second esterification reactor up to 265oC while the pressure is decreased to the atm
pressure since most of the water vapour formed from the eterification process has been
removed earlier in the first eserification reactor. This esterification reaction is reversible,

92
hence the water formed during the reaction has to be removed in order to convert the starting
materials completely into the monomer.

Figure 20 : Esterification process

Figure21: Series of esterification reactor

6.32 Separation Process

Water vapour that has been removed from the first reactor during the esterification
process is separated from the remaining unreacted Ethylene Glycol (EG) and Terephtalate
Acid (TPA) by using separator. The bottom product of this separator that mostly contains the
remaining Ethylene Glycol (EG) and Terephtalate Acid will further reacts to form BHET
monomer thus increase the total reaction conversion.

As shown in figure 6.3, for each of the rector, there is at least one separator to
separate the resulted water vapour produced from the esterification process. The top product

93
from these separators is fed to the Ehtylene Glycol (EG) recovery system at which Ethylene
Glycol (EG) will be recovered using distillation column.

There are two (2) flash tanks acted as separator attached to the output or the first
esterification reactor. These flash tanks operated to separate water vapour produced from the
esterification process from the mixtures. High input temperature to the flash tank causes
more water vapour to evaporates that induced some of the Ethylene Glycol (EG) to vaporize
as well. Thus the second flash tank meant to reduce the losses of Ethylene Glycol (EG) and to
increase degree of separation water vapour as well.
The bottom product of the second flash tank is then fed back to the second
esterification reactor. This at the same time could minimized the losses of Ethylene Glycol
(EG) from the system itself.

Figure 22: Ethylene Glycol recovery system

A distillation column involved in the Ethylene Glycol (EG) recovery system at which
all the recycled streams from top product of flash tanks connected with the reactor in the
esterification and polycondensation process are fed to the distillation column. These recycled
streams are cooled first by the cooler since most of the top product of the flash tanks are in
the form of gas phase thus by lowering the temperature, it could liquefied these gasses before

94
being fed into a mixer (M1) and then to the distillation column to separate between used
Ethylene Glycol and water vapour moisture.

The bottom product of this distillation column that contains minimum impurities mix
back with added raw Terepthalate Acid (TPA) for the continuous of PET process. The top
products of the distillation column that mostly contained water went to the water treatment
system for further treatment process before being released to nearby natural water system.

6.33 Purging system

Figure 23: Purging system

As for the purging system, it is crucial to have it as small amount from the
combination of two (2) streams that is the recycled system and raw input of Ethylene Glycol
(EG) will be purged into the Ethylene Glycol (EG) Recovery tank. The main reason for the
plant to have this purging system is to avoid any over accumulated of Ethylene Glycol (EG)
in the recycled stream that later will disturb the ratio of Ethylene Glycol (EG) to Terephtalate
Acid (TPA) used as feeds in the overall process.

95
6.34 Polycondensation Process

Previously, Ethylene Glycol (EG) and Terapthalate Acid (TPA) did not fully react in
the esterification process thus some acid end-groups from Terepthalate Acid (TPA) remain in
the prepolymer further react to form oligomer of PET.

These oligomers of PET and bis-(2-hydroxyethyl) terephthalate (BHET) will proceeds


to the next reactor to form PET with desired degree of polymerization (DP) in the
polycondensation process.

Unlike esterification process, polycondesation process of BHET to produce PET


requires the addition of catalyst to induce the rate of reaction in the step-growth
polycondensation. The catalyst most frequently employed in the polycondensation reaction is
a catalyst based on antimony such as antimony acetate or antimony trioxide.

The product (BHET) from this esterification process will acts as the monomer to
undergo to the next polycondensation process to form the PET. Monomer BHET is lead to
step-growth polymerization in the form of melt phase to polycondensation reactor. For the
purpose of polycondensation process, two(2) reactors are used to produced PET with desired
degree of polymerization (DP). In the first reactor, monomer react at high temperature of
280oC and vacuum pressure of 6 kPa to induce the removal of Ethylene Glycol (EG) formed
during the polycondensation process.

As for the second reactor (high polymerizer) the short polymer chains formed in the
previous reactor lengthened. In this second reactor , temperature is maintained while the
pressure is further reduced to 1.3kPa at vacuum condition to forced more Ethylene Glycol
(EG) removed out from the mixtures in the bubble forms since the mixtures are now become
more viscous.

96
Figure 24: Series of Polycondensation process.

The polycondensation processes proceeds until the desired PET product with certain
degree of polycondensation (DP) are produced. This degree of polymerization (DP) of the
final product of PET in the form of resins determines its physical and chemical properties at
which it signify the suitability of that resins to be used in the production of various grades
and types of products. As for the production of PET bottles, one need to produce degree of
polycondensation of PET resins between the ranges of 112-125.

Throughout the reactions of both esterification and polycondensation process, there


were some side reactions that occurred and produced some by-products together along with
the main products. During the evaporation of condensed byproducts, EG and W, is also
promoted by lower vacuum pressures, 6.666kPa in the first polycondensation reactor section
and 1.333 kPa in the second polycondensation reactor section, in order to favor the
lengthening of polymer chains. To overcome the high polymer viscosity, a high power to the
agitator of propeler and a high temperature, are required, but if the temperature is too high, i
leads to an undesired degradation due to side reactions, especially through the formation of
Aceteldehyde and Diethylene glycol (DEG) Then the product resulted from this second
polycondensation reactor should be in the form of viscous fluid with degree of
polymerization of n=112 that is required by bottle grade-PET.

Finally this polymer melt is generally filtered and then extruded into pellets.It is
extruded shortly after exiting the polycondensation stage and typically is extruded
immediately after exiting the polycondensation stage. Once the PET polyester is extruded it is
quenched, preferably in a water trough, to quickly decrease its temperature thus solidifying it.

97
The solidified PET polyester is formed into pellets or cut into chips for storage and handling
purposes

As for the formation of by-products during both of the process esterification and
polycondensation such as Aceteldehyde, it is resulted from degradation of BHET as the cause
of too high temperature in both of the process:

 +
BHET TPA Aceteldehyde

While for the formation of Diethylene Glycol (DEG), it is aby-products resulted from
reaction of BHET with unreacted Ethylene Glycol (EG) in the reactor.

+ OHCH2CH2OH  +
BHET EG TPA DEG

Other formation s of byproducts from the resulted side reactions are summarized as shown in
the figure below.

Figure 25: Reactions of functional group in stages of PET formation

98
CHAPTER 7 : CO CLUSIO S

Since the demand of Polyethylene Terephtalate (PET) is increasing throughout the


year, the production of PET through esterification and polycondensation process is viable and
economical as well. We could see that the rate of increasing for Polyethylene Tereplhtalate
demands is at constant and promising level each year thus provides a strong basis for one to
build a new plant producing this PET. This could be seen from the evaluation of Economic
Potential 1 (EP1) and Economic Potential 2 (EP2) that shown a high profit value since the
price of PET products is quite high as the reason of high demands from the consumers. Since
products made from Polyethylene Terephtalate is recyclable, it also could minimize the
emiisions of hazardous chemicals to the environments and at the same time could reduce the
consumption of oil petroleum products as well.

The main objective of this study that is to produced a flowsheet with a proper material
balance for a plant to produced Polyethylene Terephtalate (PET) in an industrial-scale
amount with all related preliminary crucial information to build a plant is achieved. This
includes the consideration of health, safety and environment (HSE) in the construction of the
plant so that its production is not only profitable but environment friendly as well. All
techniques and software related to construct the material and energy balance of the process
for producing this PET are stated in the report and each of the comparision values of
manually calculated and saftware calculated are at satisfied level since the error are at a low
value that not exceeded 0.05% as what has been practised by normal industrial practicioners.

All aspects of completing this project were partially completed and thus it is
preferrable for us to complete this project into the next semester.

99
REFERE CES

• Hassan Niaz et. al, January 2009, PROCESS PLAN OF CONTINUOUS MELT-
PHASE POLYETHYLENE TEREPHTHALATE (PET) PRODUCTION PLANT

• S.M Aharoni, Industrial-Scale Production of Polysters, especially Polyethylene


Terephtalate (PET)

• Kevin C. Seavey, Step-Growth Polymerization Process Modelling and Product


Design

• Joonho Shin1,a, Yunghyo Leeb, Sunwon Park, 1999, Optimization of the pre-
polymerization step of polyethylene terephthalate (PET)

• Flavio Manenti, 2008, Integrated Multilevel Optimization in Large-Scale


Poly(Ethylene Terephthalate) Plants

• Yunqian Ma, 2005, Post Polymerization of Polyester for Fiber Formation

• Organic Chemical Process Industry

• JOHN SCHEIRS, 2003, Modern Polyesters: Chemistry and Technology of Polyesters


and Copolyesters

• Fatemeh Ahmadnian, 2008, Kinetic and Catalytic Studies of Polyethylene


Terephthalate Synthesis

• Robert H. Perry & Don W. Green, “Perry’s Chemical Engineering Handbook”, 7th
Edition, Volume 2, Mc-Graw Hill International Edition

• Pattalachinti, R.K., Modeling and Optimization of Continuous Melt-Phase


Polyethylene Terephthalate Process. Ohio University Master's Thesis, 1994

100
• Timothy J. Calmeyn, Optimization of Melt-Phase Polyethylene Terephthalate
Manufacturing Process. Ohio University Master's Thesis, 1995

• Faissal-Ali El-Toufaili, Catalytic and Mechanistic Studies of Polyethylene


Terephthalate Synthesis.Project Report, 2006

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102