PROCESS PLAN OF CONTINUOUS MELTPHASE POLYETHYLENE TEREPHTHALATE

(PET) PRODUCTION PLANT

A Project Report Presented to

Mr. Nasiruddin Shaikh
(Project Instructor)

In Partial Fulfillment of Requirement for the Degree of

Bachelors of Chemical Technology

By
Hassan Niaz
M. Umair Farooque
Madiha Ismail Khan
Surrayya Shafuq Siddiqui
January 2009

DEPARTMENT OF CHEMICAL TECHNOLOGY

UNIVERSITY OF KARACHI

LETTER OF TRANSMITTAL

Plan a system for the Melt-Phase Polyethylene Terephthalate (PET) production, provided
that the viability report has already been specified signifying the suitability of the plan.
The plan report must include the Block Flow Diagram of the production facility,
Generalized Process Description of the system and justification by Energy and Mass
Balance, Process Flow Diagram and Detailed Designing of a single unit (equipment) in
conjunction with the Preliminary Piping and Instrument Diagram. The details must also
present the reaction mechanisms and catalyst selection.
The report is submitted in partial fulfillment of the Degree of Bachelors of Chemical
Technology, as the final year project report. The report is intended to deal with specified
information of a continuous PET manufacturing process. The information of the
variables on the optimum design, which has been used to turn out the aim, had been
provided by the project instructor.

SUMMARY

Synthesized polymers are used increasingly in our daily life, and industrial applications
have contributed to their expansion. They are replacing metals in different walks of life
because of their distinctive properties. Current studies involve new methods of polymer
manufacturing, their reaction mechanism, factors that influence their properties, new
methods to improve the product quality and process cost minimization.
Polyethylene terephthalate (PET) is used for melt-spun polyester fibers, films, injection
molded parts, and a multitude of plastic objects such as soft-drink bottles. As a widely
used and fast growing polymer, economical production of PET is of great importance.
Pursuant to the goal of economical and efficient production of PET, this report models the
PET formation, and its process conditions. The manufacturing process plan is modeled
using two-stage process, i.e. esterification followed by poly condensation to produced PET
by PTA Process (which includes Ethylene Glycol & Pure Terephthalic Acid as raw
materials). The model takes into account the product degree of polymerization (DP) and
diethylene glycol content (DEG). The production unit is designed to produce 100 tonnes /
day Bottle grade Polyethylene Terephtalate (PET).
The processes that form a part of our design are shown in the Block Flow Diagram and
the Process Flow Diagram shows the process scheme to simplify the visualization of
process plant that we design. The design preferred for the project plan is the three reactors
continuous process in series: one esterifier reactor & two polymerization reactors. The
operating temperatures for the three reactors in the series are 258, 270C and 280C,
respectively. The reactor type specifications are CSTR, CSTR and DRR respectively. The
operating pressure for the first reactor is relatively low (0.88barr, guage), for the next two
reactors in series are 15mbarr and 1.5mbarr, absolute, respectively. The volumes of the
first two reactors in the series are relatively large suggesting that large volume reactors
tend to reduce the effect of volume level fluctuations on the product DP. Molar ratio of
EG to TPA is 1.2. The polymerization catalysts, which are incorporated with the EG feed
stream in to the mixer, comprises of a system that includes about: 300ppm of Antimony
Trioxide, Sb3O2, 40ppm of Zinc or Cobalt, and 50ppm of at least one of Magnesium or
Manganese.
The Recovery Unit consists of a multi-stage distillation column, which rectifies the
vapors from the process reactors. The column removes water and other volatile reaction
by-products, including acetaldehyde. Excess ethylene glycol is recovered and recycled to
the plant (usually to the paste tank & esterifier).

Finally, the report furnishes the inclusive sizing calculations, done for the mixing vessel
of EG & PTA and the process and instrumentation plan has also been illustrated for the
same equipment. All the necessary parameters and proportions are designed in
accordance with the specified provisions.

ACKNOWLEDGEMENT

At first, we are highly grateful to ALLAH Almighty, by the grace of Whom,

we have been able to complete this report.
We would like to thank to all those people whose valuable guidance & cooperation made our group enable to complete the assigned task especially to Mr. Zubair
(Sr.deputy manager, NOVATEX pvt.ltd), Mr.Haroon (Sr. deputy NOVATEX pvt.ltd)
and to our respected madam Shagufta Aslam.
We wish to express our sincere gratitude to our Instructor, Mr. Nasiruddin
Shaikh, for his invaluable knowledge, guidance, and support and for many helpful
discussions on this endeavor.
HassanNiaz, Umair Farooque, Madiha Ismail
& Surrayya Siddiqui

TABLE OF CONTENTS

S.N
O.

CONTENT

PAGE

1.

GENERAL INTRODUCTION

1.1
1.2
1.3
1.4
1.5

7
12
13
15

1.6
1.7

HISTORICAL & ECONOMICAL PERSPECTIVE

IMPORTANCE OF PET
REPROCESSING OF PET
PROJECT OBJECTIVES
INDUSTRIAL PRODUCTION OF POLYETHYLENE
TERPHTHALATE
REACTIONS CHEMISTRY
CATALYST & OTHER ADDITIVES FOR PET SYNTHESIS

2.

DISCUSSIONS ON PROJECT

34

2.1

PTA PROCESS FOR PET PRODUCTION

34

3.

FINAL DESIGN CONFIGURATION

43

3.1
3.2
3.3
3.4
3.5
3.6
3.7

PROCESS CONFIGURATION
PROCESS FLOW DIAGRAM
PROCESS EQUIPMENTS
MATERIAL BALANCE FOR THE PET PROCESS DESIGN
ENERGY BALANCE FOR THE PROCESS
SIZING OF MIXER FOR THE FEED
P & ID OF THE SIZED MIXER

43
45
47
51
54
57
66

APPENDICES

67

APPENDIX A
APPENDIX B
APPENDIX C
APPENDIX D
APPENDIX E

68
72
78
92
95

BIBLIOGRAPHY

100

16
25
29

CHAPTER
01
GENERAL
INTRODUCTION

1.1. HISTORICAL & ECONOMICAL PERSPECTIVES

Polymers have changed dramatically many aspects of human life since the launch of their
commercial mass production in the beginning of the last century. 235 million tons of
synthetic polymers were consumed worldwide in 2003 by important economic sectors
such as electro- and electronic industry, packaging industry, building and construction,
and automobile industry among others. They are replacing metals in different walks of
life because of their distinctive properties. Current studies involve new methods of
polymer manufacturing, their reaction mechanism, factors that influence their properties,
new methods to improve the product quality and process cost minimization.
Due to wide range of their uses, the demand of PET bottles is increasing as most of the
food manufactures are converting the packaging of their products to PET bottles. These
7

bottles/containers are mainly used for the packaging of mineral water, carbonated
beverages, edible oil, household food containers, detergents, paints, lubricating oils,
feeding bottles for babies and many other items.
As PET bottles provide better packaging, and have a lower cost than the bottles made
from glass and other materials, different businesses in beverage, food and non-food
industry are gradually shifting towards PET bottles.
The PET resin has superior properties; they are attractive, pure and safe. The low
permeability of PET to oxygen, carbon dioxide and water means that it protects and
maintains the integrity of products giving a good shelf life. It also has good chemical
resistance.
PET bottles have the advantage of being lightweight, one-tenth the weight of an
equivalent glass pack. Thus, PET bottles reduce shipping costs, and because of the
material in the wall is thinner, shelf utilization is improved by 25 per cent on volume as
compared to glass. High strength, low weight PET bottles can be stacked as high as glass.
The other benefits are no leakage, design flexibility; containers can have all shapes, sizes,
neck finish designs and colors and are recyclable. PET is made from the same three
elements (carbon, oxygen, and hydrogen) as paper, and contains no toxic substances.
When burned, it produces carbon dioxide gas and water, leaving no toxic residues. Being
recyclable is the most important factor of success of business of PET bottles. It consumes
less energy and produces less pollution than glass or metal packaging. Due to completely
recyclable material, in many European and Latin American countries, PET bottles are
refilled and used over and over again. In the US, more than 600,000,000 pounds of PET
bottles are recycled annually.

PET BUSINESS IN PAKISTAN

Pakistan, since its independence in 1947, has been able to transform itself to a large
extent, from a completely agrarian economy to a fairly developed techno-industrial base.
Besides textiles, Pakistans exports are largely manufactured items such as consumer
durables and engineering products. However, it is also a fact that Pakistan has not been
able to realize its potential due to internal and external compulsions and thus it lags
behind many developing countries of the world.

Pakistan Plastics Industry Statistics

Statistics For Production

Capacity of Plastics Materials

Gatron Industries

Engro Asahi Chemical

Pak Polymer Industries

Dyno Limited

Total Production

PET 200,000 M.Tons

perYear
PVC 100,000 M.Tons per
Year
PS
36.000 M.Tons per
Year
UF
34,000 M.Tons per
Year
370,000 M.Tons per
years

Status of Plastic Products Industry

Year 2006

Local Consumption of Plastics

Local Production of Plastics
Imports of Plastics
Exports of Plastics
Total Industrial Units
o Organized Sector
o SMEs

470,000 M.Tons per Year

370,000 M.Tons per Year
180,000 M.Tons per Year
58,000 M.Tons per Year
6,000
700
5, 300
475, 000
Water Coolers. Hot Pots etc.

Manpower Engaged

Major Exportable Items

Local Consumption of Recycled Materials 150,000 M. Tons per
No. of Recycled Units
Year.
More than 400.
50,000.
Direct/ indirect Labor

Because of the high demand of PET bottles in Pakistan, there has been an increase in
small manufacturing units of PET bottles in the main cities of Pakistan. Besides the two
major players of the industry, there are around 10 small and medium units working in

Lahore only. These units manufacture a variety of products, ranging from bottles for
mineral water to packaging for pesticides.
To meet the growing demand in future a project with a production capacity of 5.82
million bottles per year can be set up. The estimated cost of the project may be about Rs6
million.
Market size: The majority of the businesses in Pakistan are converting from the bottle
containers of traditional material to plastic substitutes for packaging of their products.
The domestic manufacturing of plastic products is growing at 10 to 15 per cent annually.
Carbonated beverage, edible oil and mineral water industries are good examples for the
increasing demand of PET bottles. Within five years, the share of PET bottles has grown
from 2 to 3 per cent to 18 to 20 per cent in the carbonated beverage market. While with
every passing day, new industries are shifting to PET bottling because of lower cost and
better preservation of their product.
The bottles can be manufactured in the sizes of 0.5, 1.5 and 5litre or according to the
customer specifications. However, the production of 1.5litre bottles may be the highest,
as they are used in the beverage and mineral water industries, which are the two largest
consumers of PET bottles. Along with this, the production of 0.5litre bottles is also
increasing because of the increasing usage in mineral water bottles. The production of
5litre might be lower than the other two because they are mostly used in edible oil
packaging.
Innovations that continuously improve products and processes are the strongest driver of
profitable growth and sustained competitive strength. Because of the enormous
competitive pressure and shorter product lifecycles, it is essential to come up with more
and more new and innovative developments despite declining returns. Nevertheless the
situation on the PET market will, in the medium term, lead to a process of consolidation.
Self-reliance instead of self-sufficiency is the bottom line of Pakistans industrial policy.
Its direction is defined by the twin considerations of import-substitution and exportorientation. Value-addition is a national priority to improve our position on the value
chain. That is why more investment is required in technology transfer. Pakistans
investment space is vast. Imperatives of the investment continuum e.g. economic interest
of the country and the financial interest of the individual investors are the key
considerations. There is a kind of an organic link between the national economic interest
on the one hand and the individuals financial interest on the other. Sustainability of this
linkage is the key to a win-win situation. This is being achieved by completely freeing the
Government from the upfront controls and regulatory overhang, which it had instituted
on investment over the years. Trade and industry is no more being controlled by the
Government. The private sector is now in the drivers seat. The Government is trying to
put it on the high road of development. Approach is fast track. The policy focus is
shifting to the provision of the following requirements; namely:
o Adequate policy framework

10

o
o
o
o
o
o
o
o
o

Simplified operating procedures

Strong support mechanisms
Easy access to capital
Upgrading technologies
Enhanced productivity
Reliable quality control
Enhanced management skills
Well-trained manpower
Improved marketing skills.

Thus a reliable investment environment is being developed. The strategic preference is

massive change instead of marginal one. Value-addition is our national priority for
increasing national wealth. This requires upgrading of technology and capacity building
in design development for improving our position on the value chain. There is therefore
an immense scope of cooperation and technology tie-ups for cost-effective comanufacturing of automotive vehicles in Pakistan for domestic and export requirements.

1.2. IMPORTANCE OF PET

11

The PET resin has superior properties; they are attractive, pure and safe. The low
permeability of PET to oxygen, carbon dioxide and water means that it protects and
maintains the integrity of products giving a good shelf life. It also has good chemical
resistance i.e. it makes a good gas and fair moisture barrier, as well as a good barrier to
alcohol (requires additional "Barrier" treatment) and solvents. And since they are
excellent barrier materials, they are widely used for soft drinks. It is strong and impactresistant. It is naturally colorless with high transparency.
When produced as a thin film (often known by the trade name Mylar), PET is often
coated with aluminium to reduce its permeability, and to make it reflective and opaque.
When filled with glass particles or fibers, it becomes significantly stiffer and more
durable. This glass-filled plastic, in a semi-crystalline formulation, is sold under the
tradename Rynite, Arnite, Hostadur& Crastin. PET use has reduced the size of the
waste stream because it has replaced heavier steel and glass containers. Because, as PET
bottles provide better packaging, and have a lower cost than the bottles made from glass
and other materials, different businesses in beverage, food and non-food industry are
gradually shifting towards PET bottles.
PET can be semi-rigid to rigid, depending on its thickness, and is very lightweight. Due
to wide range of their uses, the demand of PET bottles is increasing as most of the food
manufactures are converting the packaging of their products to PET bottles. These
bottles/containers are mainly used for the packaging of mineral water, carbonated
beverages, edible oil, detergents, paints, lubricating oils, feeding bottles for babies,
household food containers such as in the product of salad dressing, fruit juices, peanut
butter and milk and also used as film in oven trays, sheeting for cups and food trays, oven
trays and many other items.
Moreover, recycled PET can be used for clothing and carpet fiber, and fiberfill for
stuffing articles such as pillows. It can also be used to make new bottles for non-food
products such as cleaning products.

1.3. REPROCESSING OF PET

12

Because PET is an engineered resin, it is more expensive than

commodity resins, such as high-density polyethylene (HDPE). For the
same reason, PET usually is one of the more highly valued plastic
recyclables.
PET is fully recyclable where facilities exist. It is given the recycling code 1. Postconsumer recycled PET (PCR PET) can be used for clothing and carpet fiber, and fiberfill
for stuffing articles such as pillows. Recycled PET can be used to make new bottles for
non-food products such as cleaning products. To make food and beverage containers out
of PCR PET, it must pass through approved processes to ensure it has no contaminants,
and it must retain enough of the original properties to meet the final quality requirements.
At the first sight recycling could minimize the amount of solid waste, and easy solution to
environmental problems. But PET recycling offers a potential to reduce in fossil fuel
consumptions, because to produce the origin PET needs fossil fuel, so that, PET recycling
could assist to solve energy crisis in the future. PET recycling also is to be able to
lengthen the life expectancy of the landfills. The other benefit of PET recycling is to
generate income for unskilled people and labor force.
As the demand for PET in the market exceeded supply of the raw material, and the high
cost of virgin PET (VPET) created a strong demand for RPET. It can be said that the cost
of virgin PET was the driving force behind the development of the recycling industry,
rather than government legislation for waste minimization.
There are three main methods used to recycle PET and they are broken down into
mechanical, thermal and chemical processes. Post consumer bottles are particularly suited
to the mechanical recycling route, producing resins with properties, which approach
virgin resin specifications.
The process of recycling of PET involves the first stage as a combination of mechanical
techniques and washing to remove waste and solid contaminants. The next stage involves
the removal of PVC contamination with X-ray detectors followed by optical detectors for
HDPE and PP. At this stage, the automatic sortation systems should have removed
surface contamination and other polymeric materials and the remaining pure PET stream
would be ground into flake, washed, further purified by sink/float separation and
centrifuges (to eliminate labels and caps) and then be rinsed and dried. This is the type of
recycling process clean and decontaminates post consumer PET bottles to produce RPET
resin. The conventional route taken to convert flake into fibres involves re-granulating
and drying the flake, melt spinning the fibres, directly followed by processing into a yarn
or non-woven fabric.
One drawback, however, to the known recycling techniques is that of being able to
recover what is known as in the industry as clear PET. Instead much-colored PET is
recovered. The colored material contains dark streaks or specs caused by decomposition
of glue and other foreign material upon melting of PET (such as when processed for
13

pellets for further use). The colored PET contains glue, which was employed to adhere
labels and bases to the containers. Colored PET has more limited use than clear PET
that can be refabricated into products, which do not contain dark colors. Clear PET can be
used to make fibers for clothing, insulation fiberfill, fish line, fabrics and other similar
products.

1.4. PROJECT OBJECTIVES

This report intends to deal with specified information of a continuous polymer

manufacturing process, namely polyethylene terephthalate (PET). A production unit to
produce 100 tonnes / day Bottle grade Polyethylene Terephtalate (PET) has been

14

designed using two-stage process, i.e. estrification followed by poly condensation to

produce PET.
The information of the following variables on the optimum design, which has been used
to turn out the aim, had been provided by the project instructor.

Starting Raw Materials available

1. Ethylene Glycol (EG)
2. Purified Terephthalic acid (PTA)

Available Utilities
1. Cooling Water

Supply Temperature = 90F, Return Temperature = 115F, Operating Pressure =60

psig
2. Instrument Air, Operating Temperature = 110F, Operating Pressure = 120 psig,
Dew point = 40F
3. Saturated steam @ 150 psig and 300 psig
4. Superheated steam @ 50 psig and 600F

Product Specifications
1. Density = 86.4 lbs/ft3
2. Water Absorption for 24 hours = 0.10% (max)
3. Specific Gravity = 1.38 gram/cc
4. Tensile Strength at break = 11500 psi (min)
5. Melting point = 490F
6. Glass Temperature = 167F
7. Intrinsic Viscosity > 0.76 dl/g

1.5. INDUSTRIAL PRODUCTION

OF POLYETHYLENE TEREPHTHALATE

15

REVIEW OF PREVIOUS WORK

A considerable amount of research in the area of modeling polymerization reactors and
reactions for the manufacture of polyethylene terephthalate (PET) has been reported in
the open literature. Polyethylene terephthalate (PET) is one of the widely applied
polymers. From annual production viewpoint, PET is in the second rank among synthetic
polymers equally with polypropylene. This is due to its excellent balance of properties
such as impact strength, resistance to creep under pressure, low permeability to carbon
dioxide, high melting point, thermal and hydrolytic stability and high clarity. In view of
the previous classification, PET is a thermoplastic polymer, which is produced by stepgrowth polycondensation polyreaction under evolution of condensates such as water,
methanol or ethylene glycol (EG).
PET is produced in two steps by one of two ways, called the DMT and the PTA
processes, or the transesterfication and direct esterification routes, respectively. Modern
plants are based on the PTA process and further; they incorporate direct product
formation (fibres and filaments, films) by extruding the melt from the final
polycondensation reactor.
Both processes can produce low- and high-viscosity PET. Intrinsic viscosity is
determined by the high polymerizer operating conditions of: (1) vacuum level, (2)
temperature, (3) residence time, and (4) agitation (mechanical design).

Contrasting the DMT & PTA Processes

PET resins are produced commercially from ethylene glycol (EG) and either dimethyl
terephthalate (DMT) or terephthalic acid (TPA). DMT and TPA are solids. DMT has a
melting point of 140C (284F), while TPA sublimes (goes directly from the solid phase
to the gaseous phase). Both processes first produce the intermediate bis-(2hydroxyethyl)-terephthalate (BHET) monomer and either methanol (DMT process) or
water (TPA process). The BHET monomer is then polymerized under reduced pressure
with heat and catalyst to produce PET resins.

DMT Process
First we shall contrast the DMT and the PTA processes. The main difference is the
starting material. The older process used:
o Dimethyl Terephthalate (DMT) and
o Ethylene Glycol (EG)

16

as starting materials. This was because of the non-availability of terephthalic acid of

sufficient purity in the early years of polyester production.
In the DMT process, in the first step, DMT is trans-esterified with ethylene glycol (EG)
to produce an intermediate called diethylene glycol terephthalate (DGT) plus a small
amount of low oligomers. The reaction byproduct is methanol and this is distilled off.

The DGT is alternatively called bis hydroxy ethyl terephthalate or BHET in the literature.
Manganese (II) acetate or zinc (II) acetate is typically used for this transesterification
step, these being the best catalysts for this reaction. In the second step, the DGT is heated
to about 280C under high vacuum to carry out melt-phase polycondensation. The
principal volatile eliminated is EG. For the second step in the DMT route, the catalyst
from the first step (zinc or manganese) is sequestered or deactivated with phosphoric acid
and another catalyst for polycondensation, most commonly antimony triacetate or
antimony trioxide is added. This is because zinc and manganese are considered poor
polycondensation catalysts. The literature indicates that the reactivity of metals for the
polycondensation reaction (second step) follows the trend Ti>Sn>Sb>Ge>Mn>Zn.
Moreover, for the first step, namely the transesterification of DMT with EG, the catalytic
activity trend follows the reverse order, with zinc being amongst the most active. For the
polycondensation reaction, Sb compounds are commercially established (compared with
Sn and Ti) because the resulting polymer has the most favorable balance of properties.
Note, in a usual operation, it is possible to go from step 1 to step 2 without isolating the
DGT. However, if desired, the DGT and oligomers formed in step 1 can be isolated and
used later for melt polycondensation (step 2).
The DMT route is economically unfavorable because of the involvement of methanol and
the additional step needed to produce DMT from terephthalic acid and methanol. The
production of methanol in the DMT process creates the need for methanol recovery and
purification operations. In addition, this methanol can produce major VOC emissions. To
avoid the need to recover and purify the methanol and to eliminate the potential VOC
emissions, newer plants tend to use the TPA process.

PTA Process
The newer industrial method uses:
17

o Purified Terephthalic Acid (PTA) &

o Ethylene Glycol (EG)
PTA is used instead of DMT and so it is called the PTA process. The metal content of the
PTA polymer is less than the DMT polymer, as only one catalyst (for polycondensation)
is used for step 2, and hence the thermal stability of the polymer is higher.
The PTA route to PET is made up of two steps. The first is the esterification of
terephthalic acid with ethylene glycol (EG) to convert to prepolymer that contains
bishydroxyethyl terephthalate (BHET) and short chain oligomers.

The esterification is not complete, and some acid end-groups remain in the prepolymer.
The esterification by-product water is removed via a column system. The second reaction
step is polycondensation, in which mainly the following transesterification reaction.

as well as the following esterification reaction

lead to step-growth polymerization in the melt phase. The reversible nature of the
reactions demands that the condensates ethylene glycol (EG) and water are removed from
the melt efficiently by using high vacuum.
Figure shows a typical continuous process scheme of the melt phase polycondensation of
PET. The first esterification reactor and the second esterification reactors are a series of
stirred tank reactors to convert TPA to BHET and oligomeric PET at temperatures of
18

about 280oC. Because the melt viscosity remains relatively low, the EG and water
condensation products formed during the process can evaporate efficiently. When the
molecular weight increases further, the melt viscosity of PET becomes so high that
bubble formation is hindered even under the applied vacuum, and EG and water have to
diffuse out. Hence it is critical to reduce the diffusion path at the following reaction stage
in order to improve removal of EG and water. This is accomplished by feeding the melt
into a disk ring reactor, that creates thin and renewable film of the polymer melt, thus
significantly increasing the available surface area, and decreasing the diffusion path for
condensate removal. Several reviews have looked at the physical and engineering aspects
of the melt polymerization of PET. At the end of the reaction, the melt is either directly
spun into fibers, or extruded into 2-4 mm thick strands that solidify due to the cooling
and are cut into somewhat cylindrical chips for future processing.

Figure: A typical industrial process for PET production

PTA PROCESS AMENDMENTS

The challenge for production companies has been to increase capacity and to
consequently lower the manufacturing cost per unit of PET. The challenge for

19

engineering companies has been to lower the cost of capital for new plants with higher
capacities required. The more typical PET plant capacity was 240 tonnes per day.

Zimmer AG and Mitsubishi Chemtex used to dominate the Chinese market

with plants in the range of 250 / 300 tonnes per day. In the brief span of six years, China
is now dominated by domestic technologies with 600 tonnes per day lines.

Lurgi Zimmer has eliminated the SSP Process & developed a direct process
for making the PET bottle preforms without the SSP step. It is based on an
integrated process that produces a high viscosity melt from which the chips can be
fed directly to the preform unit.
DuPont, in alliance with Fluor Daniel, has developed the NG3 process
which is claimed to reduce the number of steps from six to four and to lower
capital costs by 40% and overall manufacturing costs by 10-15%. Designed to
produce PET resins for the bottle resin market, the process employs a prepolymerisation step that allows the melt phase to operate under positive pressure,
eliminating the need for a vacuum system. The particle formation steps
simultaneously form and crystallise the low molecular weight intermediate
pellets. The approach used eliminates the finisher in the conventional melt process
and one crystallization stage in the SSP step.
Eastman has developed the IntegRex process which integrates the PX-toPTA and PTA-to-PET processes. Eliminating steps, such as the hydrogenation in
the PTA process and solid stating step, as well as in-process storage stages, save
costs. The process was commercialized in 2007 in a plant in South Carolina that
was claimed to have three times the capacity in half the footprint of conventional
PET technology.
Synetix has developed a new titanium catalyst that can replace antimonybased catalysts and works in both the esterification and polycondensation
processes. In batch systems, the Synetix catalyst is claimed to effectively increase
plant capacity by 15%.
Rather than eliminating the solid-state process, M&G has developed a
completely new process called EasyUPTM, with several splendid returns.
EasyUPTM technology allows solid stating in very large incremental units while
providing better quality due to the very tight control of residence time distribution
and the virtual absence of dust. The horizontal configuration of the reactor
substantially reduces the erection costs.

Solid State Polycondensation

Even with the disk reactors, it is difficult to obtain PET of number average molar mass
Mn greater than 20,000 g/mole (intrinsic viscosity, IV ~ 0.6 dL/g). This is because of the
relatively high viscosity of the melt, which reduces the mass transfer rates for removal of
EG, and water and the chemical degradation accompanying the higher temperature
20

needed to reduce the viscosity and the long residence time needed to obtain the high
molecular weight. The PET produced from melt polymerization is directly used primarily
as textile material for clothing etc. where higher molecular weight is not necessary.
Applications such as bottles and industrial fibers demand higher molecular weight PET,
which is generally achieved by post-polymerization of the PET chips produced by melt
polymerization.
The current industrial practice for post polymerization of PET is the solid state
polymerization (SSP). It is a conventional method used to increase the molecular weight
of poly(ethylene terephthalate) (PET) in order to become more suitable for applications
as carbonated soft drink bottles, etc. The chemical reactions taking place during SSP are
the same as those in the melt polymerization except that the SSP takes place in the solid
state.
Solid -state polymerization of poly (ethylene terephthalate) (PET) is carried out by
heating the low molecular weight prepolymer at temperatures below its melting point but
above its glass transition temperature. Post condensation occurs and the condensation
byproducts can be removed by applying vacuum or inert gas. Polymers obtained usually
have high molecular weight, low carboxyl and acetaldehyde content, and can be used for
beverage bottle or industrial yarns. Chemical reactions involved in the solid-state
polymerization are transesterification, esterification, as well as the diffusion of
byproducts. Overall reaction rate was governed by the molecular weight, carboxyl
content of prepolymer, crystallinity, particle size, reaction temperature, and time.
Prepolymer for solid state polymerization should have intrinsic viscosity 0.4 dL/g or
more, density 1.38 g/mL, and minimum dimension 3 mm or less. The reaction
temperature could be 200-250C. Polycondensation progresses through chain end
reactions in the amorphous phase of the semicrystalline polymer, which in most cases is
in the form of flakes (mean diameter>1.0 mm) or powder (mean diameter<100 m);
reaction by-products are removed by application of vacuum or through convection caused
by passing an inert gas.
Polymerization at 240-245 degree C for 3-5 h can raise the intrinsic viscosity to 0.72 dL/g
and carboxyl content less than 20 meq/kg. Appropriate reaction conditions are subject to
the properties of prepolymers and the design of reactors. Reactor used for solid-state
polymerization could be vacuum dryer type or stationary bed. The former is suitable for a
small capacity and is run batch wise. The latter is a continuous process and is
economically feasible for large -scale production.
The advantages of SSP include low operating temperatures, which restrain side reactions
and thermal degradation of the product, while requiring inexpensive equipment, and
uncomplicated and environmentally sound procedures. Disadvantages of SSP focus on
low reaction rates, compared to melt phase polymerization, and possible solid particle
processability problems arising from sintering.
Technical Information

21

Process: continuous SSP process

Capacities: 10 to 60 metric T/D
Process Environment: Nitrogen Atmosphere
NPU Type: Catalytic Oxidation plus Molecular Sieve Drying
Feed Source: flakes or pellets
Feed IV: 0.50 to 0.80 dl/g
R-PET Product IV: 0.60 to > 1.0 dl/g
R-PET Product [AA]: less than 1 ppm
Applications: fiber, strapping, sheet, engineered resin, industrial yarn, automotive
parts, packaging materials, bottles
o Options: can be used with existing extrusion systems at the plant or provided with
new extrusion system for industrial waste or bottle to bottle recycle applications
o
o
o
o
o
o
o
o
o

Benefits
The SSP-R Process offers a number of benefits to PET producers and PET recyclers:
Highest Product Quality- Chips or flakes are processed in an inert N2 atmosphere to
prevent oxidative degradation of polymer. Product has excellent resin color, low [AA]
and low [COOH]. R-PET product quality is equivalent to virgin PET product.
Flexibility- Both post-consumer and industrial waste can be processed, can be used for
solid stating materials that have been recycled by either physical or chemical means, can
accept chips from various commercially available extrusion systems for bottle to bottle
recycle applications and can also be used to process virgin amorphous PET. There is no
limitation to feed or product IVs because the process is easily adjustable.
Low Cost- Simple three-step processing scheme with minimal equipment results in low
investment and operating costs. Use of patented low nitrogen to solids ratio and NPU
ensures low consumption of utilities. Continuous SSP Process requires less personnel and
utilities vs. batch-type process, also resulting in low operating cost.
Reliability- simple processing scheme and equipment design result in robust, trouble-free
operation. Maintenance is simple and infrequent.
No Environmental Hazards- The patented NPU safely and efficiently converts all
hydrocarbon waste to CO2 and H2O, using efficient catalysts and molecular sieves.
There are no hydrocarbon emissions.

SSP Process Description

22

Solid-state polymerization (SSP) is used to build up the intrinsic viscosity required by

certain applications such as soft drink bottle and tire cord. All unit operations run
between the polymers Tg (glass transition temperature, 69 C) and Tm (melting-point
temperature, 265 C).
Precrystallizer
Amorphous feed chips are introduced into the SSP plant from storage or directly from the
melt phase plant (continuous polymerization process) and subsequently fed to the
precrystallizer (a pair of precrystallizers). The precrystallizer is a high efficiency multizone fluid bed heat exchanger, which heats & de-dusts the incoming PET chips and
increases the crystallinity. The use of nitrogen affords high flexibility in the selection of
process temperature and eliminates the possibility of chip color change.
Crystallizer
The crystallized chips are then fed to the crystallizer, which completes (perfects) the
crystallization, under process conditions optimized to the behavior of the feed polymer.
Crystallization is performed in a moist nitrogen environment, to reduce AA in the
product. The crystallized polymer drops in at the top of the reactor and travels downward.
Nitrogen flows up through the reactor.
SSP Polycondensation Reactor
The crystallized chips are then fed by gravity to the moving-bed polycondensation
reactor. The polycondensation reaction achieves the desired intrinsic viscosity (IV). Byproducts from the post polycondensation (SSP) reaction, such as AA, ethylene glycol,
and oligomers, are removed using a nitrogen carrier gas. The mass flow SSP reactor uses
a patented low gas-to solids ratio for optimum process performance.
Cooling Section
The chips exit the SSP reactor and flow to the cooling section to perform the final cooling
and de-dusting of the polymer chips. Product chips exiting the cooling section are ready
for injection molding, bagging, or spinning.
Nitrogen Purification Unit (NPU)
The entire process is performed in an inert nitrogen atmosphere to ensure production of
the best quality chips. NPU purifies the recirculating nitrogen gas, and a catalytic reactor
converts the organic impurities from the SSP reactor to carbon dioxide and water the
only waste materials from the entire SSP plant. Both the catalyst and molecular sieves are
designed to minimize consumption of utilities and promote optimum process conditions.
The purified nitrogen contains <30ppm ethylene glycol, <6ppm water, and <100ppm
oxygen.

Amorphous Chips

23

Feed

Pre-crystallization
in Fluidized Bed

Closed N2
Loop

Crystallization
In Plug Flow
Crystallizer

Nitrogen
Purification Unit
(NPU)

Reactor

Cooling

Upgraded Chips
Product

SSP Process
With chips flowing via gravity through the system,
flow scheme has very low operating costs.

NOTE: Solid State Polymerization Process is merely defined here just to furnish the
entire process of production of bottle grade PET chips. Otherwise this process designing
is not built-in in the subsequent sections.

1.6. REACTIONS CHEMISTRY

SIDE REACTIONS

24

Apart from the main reactions involved in the PET manufacturing process, several side
reactions occur leading to the formation of undesired byproducts, the presence of which
may adversely affect the final product properties.
The important reactions involved in the manufacture of PET are polycondensation,
esterification, ester interchange, diethylene glycol formation, acetaldehyde formation and
vinyl end group formation. The components produced due to side reactions include acid
ends, diethylene glycol (DEG) in free and associated form, acetaldehyde and vinyl end
groups. The rate of formation of these side products depends on the operating conditions
in the PET manufacturing process. The presence of DEG in the polymer chain disturbs
the regularity of the polymer chain and influences the rate and level of crystallization and
the properties of the polymers. The melting point of PET decreases if DEG is
incorporated in the polymer. It is therefore important' to keep DEG formation during PET
manufacture within certain limits. Another important side reaction in PET synthesis is
degradation of the repeat units, which may lead to a drop in the molecular weight of the
polymer and an accumulation of acid and vinyl end groups. Acetaldehyde is another
component, which is not desirable in the final polymer product. It is generated in melt
processing (over 260oC), which can be produced by the degradation of ethylene glycol or
by the degradation of the PET polymer chain. In addition, cyclic oligomers, e.g., trimer
and tetramers of terephthalic acid and ethylene glycol, also may occur in minor amounts.
The continued removal of ethylene glycol as it forms in the polycondensation reaction
will generally reduce the formation of these by-products.

MAIN PROCESS REACTIONS & SPECIES

To produce PET, the direct reaction method of a diacid with a diol is by and large utilized
(i.e., terephthalic acid is reacted with ethylene glycol as shown below).

REACTION STAGES

The reaction takes place in two main stages: a pre-polymerization stage and the actual
polymerization.
In the first stage, before polymerization happens, you get a fairly simple ester formed
between the acid and two molecules of ethane-1,2-diol.

25

In the polymerisation stage, this is heated to a temperature of about 260C and at a low
pressure. A catalyst is needed - there are several possibilities, discussed in the next
section, including antimony compounds like antimony(III) oxide.
The polyester forms and half of the ethane-1,2-diol is regenerated. This is removed and
recycled.

It has been assumed that the reactivity of the functional groups is not dependent on the
length of the polymer chain. The functional groups, which are modeled here, are hydroxy
ethyl ethoxy ester end group (EO), acid end group (Ee), internal ethyl diester group (ZG),
internal ethyl ethoxy diester group (ZD) and hydroxy ethyl ethoxy diester group (ED). A
detailed description of all the reactions, species involved, can be found in Appendix A.
Figure gives details of the different components involved and their chemical formulas.

26

The list of the reactions which are considered are:

Poly-condensation
1) EG + EO ZG + FG
2) EG + ED ZO + FD
3) ED + EO ZD + FG
4) ED + ED ZD + FD
Esterification
5) EC + FG EG + FC
6) EC + FDED + FC
7) EC + EOZG + FC
27

8) EC + ED ZD + FC

Ester interchange
9) ED + FGEO + FD
Side reactions
10) EG + EGED + EC
11) EG + FGFD + EC
12) EG + ZGZD + EC
13) ZG + FGED + EC

1.7. CATALYST & OTHER ADDITIVES

FOR PET SYNTHESIS

28

The polymerization catalyst employed in the continuous process is generally added prior
to, at the start of, or during the polycondensation stage as long as it is provided
sufficiently early in the polycondensation stage to facilitate polycondensation of the
monomer to yield polyethylene terephthalate. The preferred catalyst system is generally
employed and supplied in a form that is soluble in the polymer melt to enable the catalyst
to be uniformly distributed throughout the polymer melt.
It is aimed to substantially increase the polymerization rate while producing a
polyethylene terephthalate polymer, which has high clarity (if dulling agents are not
added) and is virtually colorless. So, such a catalyst system is created, which are effective
in producing colorless PET having high clarity and that can be added at anytime before
the beginning of or during the polycondensation step.
In both the batch and the continuous processes, a high activity catalyst is often employed
to increase the rate of polymerization thus increasing the throughput of the resulting PET
polyester. The high activity catalysts, which are used in the polymerization of PET
polyester, can be basic, neutral or acidic, and are often metal catalysts.
The polymerization catalysts that are preferably used in the polycondensation reaction are
metals. Specific examples of appropriate polyester catalysts include germanium
compounds, titanium compounds, antimony compounds, zinc compounds, cadmium
compounds, manganese compounds, magnesium compounds, cobalt compounds, silicon
compounds, tin compounds, lead compounds, aluminum compounds, and other similar
compounds. Preferred catalysts for polyester bottle resin, for example, include
germanium compounds such as germanium dioxide, antimony compounds such as
antimony trioxide, cobalt compounds such as cobalt acetate, titanium compounds such as
titanium tetrachloride, zinc compounds such as zinc acetate, manganese compounds such
as manganese acetate and silicon compounds such as methyl silicate and other organic
silicates.
Primarily, the traditional polymerization catalysts used in the formation of PET from both
TA and DMT contains Antimony which have the best all-round properties amongst PET
catalysts during melt polymerization, leading to high productivity and polymers with
good thermal stability.
The most common of the Antimony-containing catalysts is Antimony Trioxide, Sb2O3.
However, a catalyst system specific for producing PET by the TA process includes:
(1) Antimony,
(2) Cobalt and/or Zinc, and
(3) At least one of Zinc, Magnesium, Manganese or Calcium.

29

The preferred catalyst systems include manganese, cobalt, and antimony; or zinc, cobalt,
and antimony; or manganese, zinc, and antimony. These catalyst systems, when used in
the most effective amounts, increase the polymerization rate thereby reducing the
polymerization time by approximately at least one-third, and in some cases up to one-half
of the time otherwise required under control conditions.
The system comprises PET having from about:
o 150 ppm to about 650 ppm Antimony,
o 5 ppm to about 60 ppm of at least one of Zinc and Cobalt, &
o 10 ppm to about 150 ppm of at least one of Zinc, Magnesium, Manganese or
Calcium.
The first metal catalyst is employed in a range of from 5 ppm to about 60 ppm, preferably
from 10 ppm to 40 ppm based on the theoretical polymer yield (100 percent conversion).
The second metal catalyst is employed in a range of from 10 ppm to about 150 ppm,
preferably from 20 ppm to 50 ppm based on the theoretical polymer yield. Antimony is
employed in the range of from about 150 ppm to about 650 ppm, preferably from 250
ppm to 400 ppm based on the theoretical yield of the polymer. The amounts of catalysts
added are generally the same as what generally carries through to the product produced.
Some of the catalysts may volatilize and escape with the off gas from the reaction. The
actual polymer yield may be less than the theoretical polymer yield.
When stating that the catalyst system can be added at any time before or prior to
polycondensation, it is intended to include the addition of one or more of the catalyst
metals in the terephthalic acid, glycol or other feedstock materials. For example, all the
catalyst metals could be added into the terephthalic acid feedstream in a continuous
process, or some of the catalyst metals in the terephthalic acid feedstream and the
remainder in the glycol feedstream, or the catalyst system could be added in with other
additives like coloring agents. Accordingly, as the terephthalic acid and ethylene glycol
are reacted at least some of the catalyst system could already be present.
Generally, in continuous process, no catalyst system is employed in the direct
esterification step. However, the polycondensation catalyst, generally an antimony
catalyst as in the batch process, may be introduced into the first vessel with the raw
materials (i.e., present during the direct esterification stage) or into a vessel further along
in the process prior to or during polycondensation but after the direct esterification stage
is completed.
The metallic catalyst system, in addition to antimony, includes a first metallic catalyst of
cobalt, zinc, or a mixture of these, and a second metallic catalyst of at least one of
manganese, zinc, calcium and magnesium. It is theorized that cobalt, which is not a
particularly effective metallic catalyst when combined with antimony, may make any of
zinc, manganese, calcium, or magnesium more active when employed therewith.
Likewise, it is theorized that zinc, as a substitute for the cobalt may also make

30

manganese, calcium or magnesium more active, if combined with any of them. The
simplest catalyst system comprises zinc and antimony.
The amount of catalyst added refers to the "amount of metal in the catalyst itself". Thus,
if 300ppm of antimony were employed, for example, it would not matter if antimony
trioxide or antimony acetate were employed, so long as the actual amount of antimony
metal present is 300ppm.
It appears that the overall increase in rate provided by the catalyst system is the additive
effect of two catalytic mechanisms. The first mechanism is the effect of antimony as a
coordination catalyst for the oligomers and polymers formed during the direct
esterification of terephthalic acid and ethylene glycol. The second mechanism appears to
be the effect of a metallic catalyst upon the acid catalyzed polymerization of the
oligomers and polymers.
Alternative to Antimony Catalyst---Titanium
The vast majority of PET produced today is made with antimony. However, it would
seem that the tide is beginning to change and more and more companies are realizing the
benefits of titanium as a catalyst for the production of PET bottles, fibres and films.
At the recent PET Strategies 2006 conference in Atlanta, Jim Bruening of Wellman Inc.
presented a paper on the production of polyester resin for bottles using titanium catalysts.
Wellman is a world leader in the production of PET resin for bottles. Mr. Bruening stated
that Wellman have chosen to make titanium catalysts their chosen strategic technology
platform, and he believes other companies in the market will follow suit. Wellman also
launched their new grade of resin specifically for carbonated soft drinks and bottled
water, Ti842, at the conference. This grade will compliment their existing offering for
hot-fill beverage bottles, the titanium catalyzed PET resin, Ti818.
Traditional reluctance to use titanium was due in part to colour issues and a lower activity
in the solid-state polymerization (SSP) process step. However, Mr Bruening presented
data showing that Wellman had surmounted these problems and were thus able to achieve
the full benefits of the titanium catalyst. In hot-fill applications, titanium PET was more
resistant to shrinkage than the antimony-catalyzed bottle and Mr Bruening said that the
titanium catalyst opened the door to light-weighing hot-fill bottles because of superior
strength. Titanium also gives a higher clarity bottle and this has seen the adoption of the
titanium-catalyzed resin for critical applications such as white grape juice bottles.
In carbonated soft drink (CSD) applications, Wellman's new resin grade Ti842, also
demonstrated significant advantages over the traditional antimony catalyzed resin. It
showed reduction in cycle times of 5% to 10% during the injection moulding process.
This corresponds to an increase in output and efficiency for the producers of bottle preforms. A 25%-30% drop in acetaldehyde content was also observed in the Ti842.

31

STABILIZER
Although polymerization catalysts such as antimony trioxide result in the increased
production of PET, these same polymerization catalysts will eventually begin to catalyze
or encourage the degradation of the polymer formed in the condensation reaction. Such
degradation of the PET polymer results in the formation of acetaldehyde and the
discoloration or yellowing of the PET polyester. Acetaldehyde formation is an
objectionable result of degradation, especially in the food and beverage industry, because
it can adversely affect the taste of the bottled product, even when present in very small
amounts.
That is, once the polycondensation reaction essentially reaches completion, the
polymerization catalyst begins to degrade the polymer forming acetaldehyde and causing
discoloration or yellowing of the polyethylene terephthalate.
In an attempt to reduce the degradation and discoloration of the PET polyester, stabilizing
compounds are used to sequester ("cool") the catalyst thus reducing its effectiveness. A
stabilizer containing phosphorous, is therefore added to the polymer melt to deactivate
and stabilize the polymerization catalyst to prevent degradation and discoloration of the
polyester. The stabilizer is added to the substantially entirely polymerized polymer melt
at or after the end of the polycondensation reaction but prior to polymer processing, i.e.,
chipping, fiber spinning, film extrusion, and the like.
The preferred method of introducing the stabilizer into the polymer melt at the end of
polymerization is to inject or pump the stabilizer into the polymer melt at or after the end
of the polycondensation reaction. The stabilizer is preferably added in liquid form.
Accordingly; liquid stabilizers can be added directly, and solid stabilizers such as
ULTRANOX 626 are typically either melted or suspended in an inert liquid carrier prior
to their addition to the polymer melt.
Because the stabilizer is added at the end of the polymerization process, it can be added
in its pure form without negatively affecting the properties of the polymer melt. In
addition, uniform blending of the stabilizer and the polymer melt can be accomplished by
mechanical blending such as passing the melt through pumps, conventional static mixers,
and passing the melt through filtration elements to quickly deactivate the polymerization
catalyst and thus prevent degradation and discoloration of the PET polyester. The
stabilizer may also be added after polymerization when the polymer melt is extruded by
using a screw extruder or similar means.
The late addition of the stabilizer to the polymer melt prevents the stabilizer from
inhibiting ("cooling") the polymerization catalyst during the polycondensation reaction
thus increasing the productivity or throughput of the continuous polyethylene
terephthalate process. Furthermore, because the stabilizer is added prior to polymer
processing, the stabilizer can adequately prevent discoloration and degradation of the
PET polyester. Alternatively, late addition of the stabilizer can increase the thermal

32

stability of the polyester without adversely affecting the throughput or productivity of the
polyester.
Although adding a stabilizer to the polymer melt in a batch reactor is a relatively simple
process, numerous problems arise if the stabilizers are added in the continuous
production of polyethylene terephthalate.
For instance, while early addition of the stabilizer prevents discoloration and degradation
of the polyester, it also causes reduced production throughput (i.e., decreases
polycondensation reaction rates). Moreover, such stabilizer is typically dissolved in
ethylene glycol, the addition of which further slows the polymerization process.
Consequently, early addition of the stabilizer in the polymerization process requires an
undesirable choice between production throughput and thermal stability of the polymer.
As used herein, "thermal stability" refers to a low rate of acetaldehyde generation, low
discoloration, and retention of molecular weight following subsequent heat treatment or
other processing.
Late addition of the stabilizer (e. g., after the polymerization process during polymer
processing) may provide insufficient opportunity for the stabilizer to fully blend with the
polymer. Consequently, the stabilizer may not prevent degradation and discoloration of
the polyester. In addition, adding stabilizer during polymer processing is inconvenient
and does not provide economies of scale.
Generally, a thermal stabilizer which is nonreactive with the polymer and which
possesses low residual moisture will be used to deactivate the polymerization catalyst.
The most commonly used stabilizers contain phosphorous, typically in the form of
phosphates and phosphites. The phosphorous-containing stabilizers were first employed
in batch processes to prevent degradation and discoloration of the PET polyester. The
step of adding the phosphorous-containing stabilizer, with a phosphorous content of from
about 25 to about 150 ppm, comprises adding a stabilizer selected from the group
consisting of phosphorous, polyphosphoric acid; phosphoric acid; organophosphorus
compounds,
organophosphates,
organophosphites,
and
organophosphonates;
orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid,
phosphorous acid, hypophosphorous acid, phosphorous-containing aliphatic organic
carboxylic acid salts; bismuth phosphate; monoammonium phosphate, diammonium
phosphate, monammonium phosphorite; salts of phosphoric acid esters having at least
one free alcoholic hydroxyl group, sodium beta-glycerophosphate, calcium betaglycerophosphate; phosphotungstic acid, ammonium phosphotungstate, sodium
phosphotungstate; tertiary phosphines, tripropylphosphine, triphenylphosphine,
ethylphenyltolylphosphine;
quaternary
phosphonium
compounds,
triphenylmethylphosphonium iodide, triphenylbenzylphosphonium chloride, and
quaternary phosphonium compounds.

CHAPTER
33

02

DISCUSSIONS
ON
PROJECT

2.1. PTA PROCESS FOR PET PRODUCTION

As stated in the previous chapter, this report intends to deal with specified information of
a continuous PET manufacturing process and a production unit to produce 100 tonnes /
day Bottle grade Polyethylene Terephtalate (PET) has been designed using two-stage
process, i.e. estrification followed by poly condensation to produce PET. (The
information of the variables on the optimum design, which has been used to turn out the
aim, had been provided by the project instructor).
Polymerization plants are made up of four main process units:
Paste preparation unit
Reaction unit
Vacuum generation unit
Distillation unit
Several modifications have been made to the cost model in order to more accurately
reflect actual plant costs. Although many process configurations are found in the
polyester industry for polyethylene terephthalate production, they all involve a series of
34

three or more reactors. The most efficient melt-phase method employed is a typical fivecontinuous reactor process in series: two esterification reactors, two pre-polymerization
reactors, and one high-viscosity reactor, which is also called finisher.

However, the trend is nowadays to reduce the number of reactors in the process as this
saves in terms of investment to throughput ratio and maintenance cost. In addition, the
compactness of the design allows savings in civil works and steel structures. Several
plant-engineering companies have claimed new technologies with reduced number of
reactors like Zimmer AG (3 reactors), ESPREE (2 reactors).

35

The design preferred for this project plan is the three reactors continuous process in
series: one esterifier reactor & two polymerization reactors. The operating temperatures
for the three reactors in the series are 258, 270C and 280C, respectively. The reactor
type specifications are CSTR, CSTR and DRR respectively. The operating pressure for
the first reactor is relatively low (0.88barr, guage), for the next two reactors in series are
15mbarr and 1.5mbarr, absolute, respectively. The volumes of the first two reactors in the
series are relatively large suggesting that large volume reactors tend to reduce the effect
of volume level fluctuations on the product DP. Molar ratio of EG to TPA is 1.2.

PASTE PREPARATION

Raw materials are brought on site and stored. Terephthalic acid, in powder form, may be
stored in silos. The ethylene glycol is stored in tanks. The terephthalic acid and ethylene
glycol, containing catalysts, are mixed in a tank to form a paste. Combining these
materials into a paste is a simple means of introducing them to the process, allowing
more accurate control of the feed rates to the esterification vessels (a portion of the paste
is, sometimes, recycled to the mix tank. This recycled paste and feed rates of TPA and
ethylene glycol are used to maintain an optimum paste density or weight percent of
terephthalic acid).

36

Vacuum System

EG Recovery Unit

EG
PTA
Mixing (Paste)
Tank

ESTERIFICATION
REACTORS

POLYCONDENSATION
REACTORS

Additives

Amorphous PET
Chips

Cooling or
Quenching

SSP Process Unit

NPU

Precrystallizer

Crystallizer

Crystalline PET
Chips

Reactor

Chip
Cooling

BLOCK FLOW DIAGRAM FOR THE PROCESS

37

The polymerization catalysts that are incorporated with the EG feed stream in to the
mixer comprises of a system that includes about:
o 300ppm of Antimony Trioxide, Sb3O2,
o 40ppm of Zinc or Cobalt, and
o 50ppm of at least one of Magnesium or Manganese.
(NOTE: These values are selected simply for the concern project plan)
Different additives (like a color toner e.g. Blue or Red Toner) are also added along with
the catalysts, depending upon the polymer product requirements or specifications.

ESTERIFICATION REACTORS:

The paste from the mix tanks is fed to an esterification vessel (referred to as esterifier, or
ester exchange reactor). In the esterification stage, the terephthalic acid and the ethylene
glycol react to form low molecular weight oligomers and water. In general, a continuous
feed of raw materials is used employing a molar ratio of ethylene glycol to terephthalic
acid of from 1 to 1.6 (in the present case, sustained at 1.2). The resulting paste is fed to
the CSTR, which is known as an esterification reactor. Typically, the estrifier is operated
at a pressure of 1-8bar and a temperature of 240-290 degree C for 1 to 5 hours; but the
reactor is maintained at a pressure of 0.88barr & a temperature of 258 degree C for the
specified designing presently. The reaction is typically un-catalyzed and forms low
molecular weight oligomers and water.
The vapor from esterification reactor is rectified in a multi-stage distillation column. The
column removes water and other volatile reaction by-products, including acetaldehyde.
Excess ethylene glycol is recovered and returned to the paste tank and the esterification
reactor. The recycle rate to esterification reactor can be manipulated to control the local
monomer ratio.
One thing which is worth mentioning here is that since esterification reaction occurs from
the beginning to the end of PET synthesis, it is an equilibrium reaction and, thus removal
of the condensed water is necessary to minimize the hydrolysis of the formed ester
groups.
Phosphoric acid stabilizer is also introduced into the esterification reactor or prior to the
pre-polymerization, to about 5-100ppm, to reduce the degradation and discoloration of
the PET polyester and to cool the catalyst, which encourages the degradation of the
polymer formed in the condensation reaction.

38

POLYMERIZATION REACTORS:

The third reactor, or low polymerizer (LP), is typically composed of a simple CSTR. The
low polymerizer (LP) operates at a medium vacuum pressure (50-500 Torr), it is
maintained at 15mbarr gauge pressure for the scheme plan. This stage strips off most of
the excess ethylene glycol and water remaining in the polymer. In most plants, the
polymer intrinsic viscosity in the low polymerizer is below 0.2 dl/g, and the LP behaves
ideally. At higher viscosity levels, the low polymerizer becomes increasing mass-transfer
limited. As the polymer melt is fed into successive vessels, the molecular weight and thus
the intrinsic viscosity of the polymer melt increases. The temperature of each vessel is
generally increased and the pressure decreased to allow greater polymerization in each
successive vessel. The final DRR (disk-ring reactor) reactor, known as the high
polymerizer (HP), is operated at lower absolute pressures, often as low as 1.5mbarr. As
with the low polymerizer, each of the polymerization vessels communicates with a flash
vessel and is typically agitated to facilitate the removal of ethylene glycol, as EG removal
is the rate-determining step of the polycondensation reaction, thus enabling the
polycondensation reaction to go to completion. Therefore, these reactors are stirred tank
reactors with unusual ratio of diameter/height to provide a large gas-liquid interface.
Disk-ring reactor contains a number of annular disks attached to a rotating shaft. Polymer
flows through holes cut into the disks. As the disks rotate they generate a surface film,
which enhances the evaporation rate. Due to the high viscosity of the polymer, the
performance of the finishing reactors is limited by the liquid-vapor mass transfer rate.
This makes the reactor performance a function of the shaft rotation rate, as well as the
temperature, pressure, and throughput.

A side view of a rotating disc reactor (left), and a cross-section of one perforated disc (right)

39

The number of DRRs typically does not exceed two. All reactors have a vacuum system,
which condenses each reactor's vapor product. The purpose of the vacuum system is to
remove the volatile byproducts of the polymerization reaction.
The retention time in the polymerization vessels and the feed rate of the ethylene glycol
and terephthalic acid into the continuous process are determined in part based on the
target molecular weight of the PET polyester. Because the molecular weight can be
readily determined based on the intrinsic viscosity of the polymer melt, the intrinsic
viscosity of the polymer melt is generally used to determine the feed rate of the reactants
and the retention time in the polymerization vessels. Long residence times lead to thermal
degradation of the polymer and cause black spots in the transparent final products.
Equipment for each reactor includes the vessel, agitator, agitator motor, heating jacket,
heat exchanger and pump (CSTR only), gear pump, and a vacuum system. Figure
provides a schematic of a CSTR with auxiliary equipment. The CSTR heat exchanger is
necessary to provide sufficient heat for the process feed (which enters at a lower
temperature) and the vaporization of the volatile components. With the DRRs, the vapor
outlet flows are much less than with the CSTRs. The vacuum system consists of jets and
a spray condenser with a heat exchanger and recirculating pump.

The vapor product from each reactor enters the spray condenser. Condensate is
continuously replaced with ethylene glycol to reduce the volatility of the spray fluid. The

40

vapor product of the spray condenser feeds into the jet ejectors. The product of the jets
combines with the liquid product from the condenser and enters the refining system.
All reactors share a single refining system. It usually consists of a ten-stage distillation
column with a feed heat exchanger, reboiler, and condenser. A single Dowtherm heating
system provides for each reactor's heating duty. Further depiction on the vapor recovery
process is described in the following paragraphs.

COOLING & CHIPS FORMATION

Although this selective report case do not covers the overall process of bottle grade PET
chips formation, since it only takes account of the production to the melt polymer
making, it would be helpful to be acquainted with the succeeding progression stages of
Melt Phase PET.
Thus, once the polymer melt exits the polycondensation stage, typically from the high
polymerizer, it is generally filtered and then extruded into polyester sheets, filaments, or
pellets. Preferably, the polymer melt 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. The solidified PET
polyester is formed into pellets or cut into chips for storage and handling purposes. The
pellets or chips may be subjected to solid-state polymerization (SSP) to increase the
molecular weight of the polyester. The polyester chips are then re-melted and re-extruded
to form items such as bottles, filaments, or other applications. It should be noted that
because the melting and extruding steps in the formation of the PET polyester are
performed at elevated temperatures of at least greater than 260C, it is important that the
PET polyester is thermally stable and does not degrade or discolor as a result of
temperature increases. Therefore, it is crucial that the stabilizer adequately blend with the
polymer melt to deactivate the polymerization catalyst.

EG RECOVERY
Spent glycol from the PET process typically contains 90-99% EG, 1-5% DEG, 1-10%
low molecular weight terephthalate oligomers, .01-.5% antimony, 2-5% water, a trace of
other metallic cations, and a trace of phosphates, acetates and other anions as well as
other contaminants.
Glycol released in the polymerization process and any excess or unreacted glycol is
drawn into a contact spray condenser (scrubber) countercurrent to a spent ethylene glycol
spray. (At one facility, both the low and high polymerizer spray condensers have four
spray nozzles, with rods to clear blockage by solidified polymer. Care is taken to ensure

41

that the spray pattern and flow are maintained.) Recovered glycol is pumped to a central
glycol recovery unit, a distillation column. Vacuum on the reactors is maintained by a
series of jets with barometric intercondensers. A three-stage ejector system is used
selectively for the evacuation of both the polymerizers.
Generally, at some plants, a two-stage ejector system with a barometric intercondenser is
used to evacuate the low polymerizer. The condensate from the intercondensers and the
last jets is discharged to an open recirculating water system, which includes an open
trough (referred to as a "hot well") and cooling tower. The recirculation system supplies
cooling water to the intercondensers.
Vapors from the spray condenser off the high polymerizers are also drawn through a jet
ejector system. One facility uses a five-jet system. After the first three ejectors, there is a
barometric intercondenser. Another barometric intercondenser is located between the
fourth and fifth ejectors. The ejectors discharge to the cooling water hot well. The stream
exiting the vacuum system is sent either to a cooling tower where the water is
recirculated through the vacuum system, or to a wastewater treatment plant (once-through
system).
Vacuum pumps can be installed as an alternative to the last two ejectors. These pumps are
installed as part of an energy conservation program and are used at the operators
discretion. But if vacuum is lost, or is insufficient in the low or high polymerizers, offspecification product results. So, each process line must have a dual vacuum system. One
five-stage ejector/vacuum pump system must be maintained as a standby for each
industrial filament (high-viscosity) process line. The staple (low-viscosity) lines can have
a standby ejector system, but with only one vacuum pump per process line. Nevertheless,
steam ejectors recover faster from a slug of liquid carryover than do vacuum pumps, but
the spare system must be used in the production of either high- or low-viscosity PET.

42

CHAPTER
03
FINAL
DESIGN
CONFIGURATIONS

3.1. PROCESS CONFIGURATION

The preferred model of the process consists of series of continuous stirred tank reactors
(CSTR) and disc ring reactors (DRR) with accessories attached to each reactor to handle
the downstream products. The selection of the type of reactor (CSTR/DRR) is made
depending upon the degree of polymerization of the product coming out of the reactor.
43

A DRR is selected if the product degree of polymerization is greater then 25. The feed to
the first reactor consists of TPA and ethylene glycol. The molar ratio of TPA to ethylene
glycol in the feed to the first reactor is 1:2. Overheads from reactors are sent to individual
spray condensers. The condensate from the spray condensers is combined and refined. A
multistage jet ejector is used to create vacuum in the reactor. A heat exchanger is used to
cool the circulating fluids of the condenser. Ethylene glycol is added as fresh feed to the
spray condenser to lower the vapor pressure of the condensables. A single distillation
column is used for all the reactors in the process to separate the products leaving the jets
and the spray condenser. Figure given below shows a brief description of the reactor and
the accessories.

Key for the figure

Identifier
1
2
3
4
5
6
7
8
9

Description
Feed
Reactor
Spray Condenser
Jet Ejector
Heat Exchanger
To Distillation Column (Recovery Unit)
Make Up Feed of EG
EG Feed to Ejector System
Product to next Reactor in series

44

3.2. PROCESS FLOW DIAGRAM

The flow diagram, to show the sequence of equipments and unit operations in the overall
process, and to simplify visualization of the manufacturing procedures, is represented and
illustrated in the subsequent pages.

PT A

M EG
S t a b iliz e r

A d d it iv e s
C a t a ly s t

II

II I

V es s e l A t 8 0 o C

M EG

M EG

M o th e r V e s s e l
(SEG)
PRO D U CT ST REA M
SPEN T ETH YLEN E GLYCO L
VA PO RS ET H YLEN E GLYCO L
W A T ER
R A W M A T E R IA L

M ELT PHASE PET

45

This design relates to a process for the continuous production of

polyethylene terephthalate (PET), wherein pure terephthalic acid is
esterified with ethylene glycol, then pre-polycondensated and
subsequently polycondensated, the vapors formed being rectified, the
liquid phase substantially consisting of ethylene glycol being
recirculated to the production process, and the vapor phase containing
EG and water (lower boiling components are neglected) being
condensed.
In detail, terephthalic acid is mixed with ethylene glycol, with the mole ratio of 1.2, and a
catalyst (together with the additives like color toner, stabilizer or preservative), to obtain
a paste and is then supplied to the esterification vessel by way of a pump. Esterification is
effected at 0.88bar pressure (via removing water) & at temperature of 258 degree C. The
esterified liquid mixture is then passed to the pre-polycondensation, which is affected
under a vacuum, at 15mbarr gauge pressure. The product is next pumped through a filter
to the DRR. Polycondensation is performed in DRR at an elevated temperature and under
an increased vacuum, at 1.5mbarr. The produced PET polymer melt is finally cleaned by
means of a filter and then sent for additional processing of pellet formation.
Here, the vacuum system consists of jets and a spray condenser with a heat exchanger
and recirculating pump. The vapors are rectified, the ethylene glycol obtained as bottom
product is re-circulated to the esterification stage (and the lower-boiling components, if
exists, are discharged as top product and condensed).
The vapor product from polymerization reactors enters the spray condensers. Condensate
is continuously replaced with ethylene glycol to reduce the volatility of the spray fluid.
The vapor product of the spray condenser feeds into the jet ejectors whose condensate
product goes into the mother vessel.
The liquid product from the condenser gets refined in a ten-stage distillation column
recovery system that consists of a feed heat exchanger, and a condenser. The ethylene
glycol obtained as bottom product is sent to the mother vessel from where it is
recirculated to the esterifier and the mixing vessel.

46

3.3. PROCESS EQUIPMENTS

The chief equipments used for the projected plan of PET production,
shown in the process flow diagram, are enlisted underneath.

LIST OF EQUIPMENTS

Paste preparation tank-- Continuous Stirred Tank

Esterification reactor-- Continuous Stirred Tank
Column
Poly-condensation reactor-I-- Continuous Stirred Tank
Final Poly-condensation reactor-- Disc Ring Reactor
Vacuum system
Pre-polymer filter--Candle Type Filter
Polymer filter-- Candle Type Filter
Mother vessel of spent Ethylene Glycol
Different types of condensers

LIST OF PUMPS

The selection of pumps, used in the process, is mentioned in the chart given below and
their general working descriptions are briefly defined in the subsequent paragraphs.
Screw pump (type of positive displacement The pump after paste preparation tank and
pumps)
in front of esterification tank is screw
pump.
Gear pumps (type of positive displacement Gear pumps are installed before and after
pumps)
the DRR.
Centrifugal pumps
Rests of the pumps in the diagram are
centrifugal pumps.
A power pump is a positive displacement machine consisting of one or
more cylinders, each containing a piston or plunger. The pistons or
plungers are driven through slider-crank mechanisms and a crankshaft
from an external source. The capacity of a given pump is governed by
the rotational speed of the crankshaft. Unlike a centrifugal pump, a
power pump does not develop pressure; it only produces a flow of fluid.

47

The downstream process or piping system produces a resistance to this

flow, thereby generating pressure in the piping system and discharge
portion of the pump. The flow fluctuates at a rate proportional to the
pump speed and number of cylinders. The amplitude of the
fluctuations is a function of the number of cylinders. In general, the
greater the number of cylinders, the lower the amplitude of the flow
variations at a specific rpm. All power pumps are capable of operating
over a wide range of speeds, thereby making it possible to produce a
variable capacity when coupled to a variable speed drive. Each pump
has maximum suction and discharge pressure limits that, when
combined with its maximum speed, determine the pumps power
rating. The pump can be applied to power conditions that are less than
its maximum rating but at a slight decrease in mechanical efficiency.
The power pump is a positive displacement device. When operating, it
will continue to deliver flow independent of the pressure in the
discharge piping system. Unlike a centrifugal pump, a power pump will
not deadhead or go back on its curve in response to increasing
discharge pressure. When this pressure exceeds the design limits of
the pump, mechanical failureoften catastrophicwill result. For this
reason, all piping systems incorporating power pumps must have
discharge pressure relief devices to limit the pressure in the piping
system and avoid pump failure. These devices must be located
between the discharge connection on the pump and the first isolation
valve in the piping system. It is recognized that the proper pump
metallurgy for the pumped fluid must be used, but due to the vast
number of possible fluids, selection of pump metallurgy is outside the
scope of this section. For basic power pump selection, it is only
necessary to understand that the NPSH available from the suction
system must be sufficiently above the NPSH required by the pump to
operate properly.
The pump after paste preparation tank and in front of esterification tank is screw pump.
Introduction, advantages and disadvantages are given below:
SCREW PUMPS
Screw pumps are a special type of rotary positive displacement pump in which the flow
through the pumping elements is truly axial. The liquid is carried between screw threads
on one or more rotors and is displaced axially as the screws rotate and mesh. In all other
rotary pumps, the liquid is forced to travel circumferentially, thus giving the screw pump
with its unique axial flow pattern and low internal velocities a number of advantages in
many applications where liquid agitation or churning is objectionable. The applications of
screw pumps cover a diversified range of markets including navy, marine, and utilities
fuel oil services; marine cargo; industrial oil burners; lubricating oil services; chemical
processes; petroleum and crude oil industries; power hydraulics for navy and machine
tools; and many others. The screw pump can handle liquids in a range of viscosities, from
48

molasses to gasoline, as well as synthetic liquids in a pressure range from 50 to 5000

lb/in2 (3.5 to 350 bar) and flows up to 8000 gal/min (1820 m3/h). Because of the
relatively low inertia of their rotating parts, screw pumps are capable of operating at
higher speeds than other rotary or reciprocating pumps of comparable displacement.
Some turbine-attached lubricating oil pumps operate at 10,000 rpm and even higher.
Screw pumps, like other rotary positive displacement pumps, are self-priming and have a
delivery flow characteristic, which is essentially independent of pressure, provided there
is sufficient viscosity in the liquid being pumped.
Screw pumps are generally classified into single- or multiple-rotor types. The latter is
further divided into timed and un-timed categories.
The single-screw or progressive cavity pump has a rotor thread that is eccentric to the
axis of rotation and meshes with internal threads of the stator (rotor housing or body).
Alternatively, the stator is made to wobble along the pump centerline. Multiple-screw
pumps are available in a variety of configurations and designs. All employ one driven
rotor in a mesh and one or more sealing rotors. Several manufacturers have two basic
configurations available: single-end and double-end construction, of which the latter is
the better known.
ADVANTAGES OF SCREW PUMP:

As with every pump type, certain advantages and disadvantages can be found in a screw
pump design. These should be recognized when selecting the best pump for a particular
application. The advantages of a screw pump design are as follows:
A wide range of flows and pressures
A wide range of liquids and viscosities
High speed capability, allowing the freedom of driver selection
Low internal velocities
Self-priming, with good suction characteristics
A high tolerance for entrained air and other gases
Multiple-screw double-end arrangement.
Low velocities for minimum churning or foaming
Low mechanical vibration, pulsation-free flow, and quiet operation
A rugged, compact design that is easy to install and maintain
High tolerance to contamination in comparison with other rotary pumps
DISADVANTAGES OF SCREW PUMP:

A relatively high cost because of close tolerances and running clearances

Performance characteristics sensitive to viscosity changes
High pressure capability requires long pumping elements

49

GEAR PUMPS
Gear pumps are installed before and after the DRR. Gear pump are positive displacement
rotary pumps. The Hydraulic Institute defines them as mechanisms consisting of a casing
with closely fitted gears that provide a means for conveying a fluid. Their principle
motion is rotating, rather than reciprocating, and they displace a finite volume of fluid
with each shaft revolution. When describing them, the general term fluid is used, rather
than the more restrictive liquid. Fluid, in this case, is understood to include not only true
liquids, but mixtures of liquids, gases, vapors, slurries, and solids in suspension as well.
CENTRIFUGAL PUMPS
A centrifugal pump is a rotating machine in which flow and pressure are generated
dynamically. The inlet is not walled off from the outlet, as is the case with positive
displacement pumps, whether they are reciprocating or rotary in configuration. Rather, a
centrifugal pump delivers useful energy to the fluid or pumpage largely through
velocity changes that occur as this fluid flows through the impeller and the associated
fixed passageways of the pump; that is, it is a roto-dynamic pump. All impeller pumps
are roto-dynamic, including those with radial-flow, mixed-flow, and axial-flow impellers:
the term centrifugal pump tends to encompass all roto-dynamic pumps. Although the
actual flow patterns within a centrifugal pump are three-dimensional and unsteady in
varying degrees, it is fairly easy, on a one-dimensional, steady-flow basis, to make the
connection between the basic energy transfer and performance relationships and the
geometry or what is commonly termed the hydraulic design (more properly the fluid
dynamical design) of impellers and stators or stationary passageways of these machines.
In fact, disciplined one-dimensional thinking and analysis enables one to deduce pump
operational characteristics (for example, power and head versus flow rate) at both the
optimum or design conditions and off-design conditions. This enables the designer and
the user to judge whether a pump and the fluid system in which it is installed will operate
smoothly or with instabilities. The user should then be able to understand the offerings of
a pump manufacturer, and the designer should be able to provide a machine that
optimally fits the users requirements.
The complexities of the flow in a centrifugal pump command attention when the energy
level or power input for a given size becomes relatively large. Fluid phenomena such as
recirculation, cavitation, and pressure pulsations become important; hydraulic and
mechanical interactionsinvolving stress, vibration, rotor dynamics, and the associated
design approaches, as well as the materials usedbecome critical; and operational limits
must be understood and respected.

50

3.4. MATERIAL BALANCE

FOR THE PET PROCESS DESIGN

SPECIFIED INFORMATION:
o PRODUCTION RATE----100 tonnes / day Bottle grade Polyethylene
Terephtalate (PET)
o RAW MATERIALS:
1. Ethylene Glycol (EG), in liquid.
2. Purified Terephthalic acid (PTA), in powder form.

OVERALL MASS BALANCE FOR 100TPD PRODUCTION PLANT

Table, represented below, shows the overall material balance of the selected PET process
unit. The comprehensive calculations are worked out in Appendix B.

INPUT

OUTPUT

Kg/hr

Kg/hr

SPECIES

51

MIXER
PTA
EG

3587.06
1607.694

5194.754

TOTAL

5194.754

5194.754

836.0011
2443.695
-

4855.465
413.8032
73.31086
688.1762

TOTAL
PRE-POLYCONDENSATION

6030.755

6030.755

PTA
BHET (produced)
TOTAL BHET
EG CONSUMED
H2O (produced)
PET
BHET (un-reacted)
EG (produced)
TOTAL EG
EG left
PET
BHET

413.8032
633.1688
5488.634
309.106
89.74046
3966.993
240.6327
1281.008
996.8378
-

19.93676
3966.993
240.6327

TOTAL

5294.204

4227.563

CONDENSER:
EG VAPORS
H2O VAPORS
EG CONDENSATE
H2O CONDENSATE

976.9011
89.74046
-

195.3802
781.5209
89.74046

TOTAL

1066.642

1066.642

240.6327
19.93676
3966.993

72.85181
4093.82

4227.563

4166.671

60.89114

59.67332

ESTERIFICATION
MAKE UP EG (SEG)
TOTAL EG IN
BHET
PTA
EG (un-reacted)
WATER

POLYCONDENSATION
BHET (to be reacted)
EG
TOTAL PET
TOTAL
CONDENSER:
EG

52

JET SYSTEM
EG

196.598

EG RECOVERY COLUMN
LIQUID FEED
EG
H2O

871.2613
781.5209
89.74046

VAPOR FEED
EG EVAPORATED
H2O

736.5514
48.3752
688.1762

TOTAL H2O
TOTAL EG

777.9166
829.896

TOTAL

196.598

1607.813

DISTILLATE & REFLUX

H2O
EG

777.9166
27.06556

BOTTOM
EG

802.8305
TOTAL

1607.813

MOTHER VESSEL
COLUMN
JET SYSTEM
DRR CONDENSER
TOTAL EG

802.8305
196.598
59.67332
1059.102

836.0011

53

3.5. ENERGY BALANCE

OF THE PROCESS

SPECIES

INPUT
KJ/hr

OUTPUT
KJ/hr

EG
PTA

2.46E+05
3.84E+04

1.64E+05
1.99E+05

TOTAL

2.84E+05

3.63E+05

SEG
EG
PTA
BHET
H2O

2.26E+05
1.64E+05
1.99E+05
-

1.14E+05
2.90E+05
3.31E+06
2.02E+06

TOTAL

5.88E+05

5.74E+06

2.81E+04
2.90E+05
3.31E+06
3.63E+06

1.80E+06
1.74E+05
2.66E+05
4.96E+06
7.21E+06

BHET
PET
EG

1.74E+05
4.96E+06
2.38E+04

5.52E+04
5.38E+06
1.13E+05

TOTAL

5.16E+06

5.55E+06

MIXER

ESTERIFICATION

PRE-POLYCONDENSATION
EG
PTA
BHET
H2O
PET
TOTAL
POLYCONDENSATION

54

COLUMN

Liquid

Vapor

TOP

BOTTOM

H2O
EG
REFLUX H2O

4.74E+04
2.02E+06
5.80E+03
8.63E+04
1.47E+05

2.02E+06
-

5.89E+05

TOTAL

2.31E+06

2.61E+06

MOTHER VESSEL
EG (JET) at 100oC

6.32E+04

EG (DRR) at 33oC

1.91E+03

EG (COLUMN) at 180oC

5.70E+05

TOTAL

6.35E+05

3.40E+05

55

HEAT EXCHANGERS

cooling water
Distillate

cooling water
PP Cond

cooling water
DRR Cond

Temperature
o
C
32
46
100
70
32
46
95
40
10
46
150
33

COLUMN CONDENSER
Temperature
Cp
K
305.15
75.4
319.15
75.49
373.15
75.9
343.15
75.55
PP HEAT EXCHANGER
305.15
75.4
319.15
75.49
368.15
144.1
313.15
131.7
DRR HEAT EXCHANGER
283.15
74
319.15
75.49
423.15
187.0
306.15
151.7

1084.323

m*1084.3

42397.1

3664601

1084.3

m*1084.3

11794.46

1669978

3139.534

m*3139.5

32695.17

77487.55

1084.323

m*1084.3

9508.3

34214.51

1084.3

m*1084.3

12560.6

351318.7

1084.3

m*1084.3

4208.0

47424.3

m
(Kmol/hr)
3379.6

1540.1

24.7

MIXER HEAT EXCHANGER

cooling water
SEG

32
46
100
62

305.15
319.15
373.15
335.15

75.4
75.49
172.78
164

31.6

JET HEAT EXCHANGER 1

cooling water
EG

32
46
100
54

305.15
319.15
373.15
327.15

75.4
75.5
172.6
158.4

324.0

JET HEAT EXCHANGER 2

cooling water
EG

32
46
100
85

305.15
319.15
373.15
358.15

75.4
75.5
172.6
168.1

43.7

56

3.6. SIZING OF THE MIXER FOR FEED

PASTE FORMATION

As described in the preceding chapters that a slurry of EG and TPA are mixed in a stirred
tank vessel equipped with a stirrer for viscous fluids (e.g. intermig) to prepare a paste
with molar ratio of EG & TPA of 1:2.
When considering any mixing application it is important to realize that the optimum
solution will depend on a variety of different factors. And it is crucial to specify precisely
the right system configuration to best serve the total needs of a particular mixing
operation.
Mixing Mechanisms
Mixing is achieved by a number of different mechanisms, as summarized in the following
table. The most important mechanism will vary for any given application, and a given
process may rely on any or all of these mechanisms.
In order to arrive at an optimum mixer design a detailed understanding of the various
mechanisms involved and their importance in achieving the process result is required.

Convection

Macro-mixing

Induced by pumping action of the impeller, Fluid moves through the

different parts of vessel, preventing stratification.

Caused by turbulent flow a wide range of vortices. Smallest in the

impeller region where dissipation is the highest. Separates bulk of
fluid into smaller elements

Laminar shear

Below the scale of macro mixing fluid elements are further

dispersed by laminar shearing. Elements are stretched, distorted and
folded.

Micro-mixing

Final smallest scale mixing. Diffusion of reactants takes place and is

driven only by concentration gradient. Takes place on scale smaller
than any eddy size.

57

By far the most common of mixing applications are those which rely upon flow to
achieve the required process result. These applications are often referred to as, 'Flow
Controlled Applications', and include such applications as Blending, Solids Suspension
and Heat Transfer. For the reason that polymerization is one of the typical blending
applications thus only this function is considered here.

Blending / Homogenization of Miscible Liquids

Blending involves the mixing of two or more miscible liquids to achieve a uniform
mixture throughout the entire volume of the tank, usually within a specified period of
time. It is important to note that the blending of liquids having widely varying density
and/or viscosity, as in the case of EG & TPA, requires special attention and may require
longer blend times to ensure the liquids are mixed.

Information Required for Mixer Selection

o
o
o
o
o
o

Viscosity
Density
Pressure & Temperature
Blend Time
Volume (s)
Any specific process requirement

Optimum Mixer Selection Criteria

A full and accurate specification of the mixing vessel, the process
parameters, and the required mixer performance is the first crucial
step to arrive at an optimum mixing operation. Some of the many
other variables that can affect mixer performance and so need to be
considered in arriving at the optimum mixer design are noted on these
pages.

IMPELLERS

Impeller Type
The function of any mixing impeller is to convert the rotational energy of the mixer shaft
into the correct combination of flow, shear and turbulence to achieve the required process
result.

58

As no one-impeller design is capable of providing optimum performance under every

process condition, optimum process performance is dependent upon selecting an impeller
design that has the specific characteristics required by a given process.
Number of Impellers
The use of a single impeller is the usual preferred option on the basis of cost. However,
changes in the ratio of liquid level (Z) to vessel diameter (T) can have an adverse effect
on the flow patterns generated within the vessel. This can result in the need to consider
the use of multiple impellers in order to achieve an economic solution.
Z/T ratio alone is not the only consideration when determining the number of impellers
required. Multiple impellers may also need to be considered for other reasons including,
when high viscosity fluids are involved, for mixing at low level during filling and
emptying or where draw down from the liquid surface is a requirement.
Impeller Positioning
Whether utilizing a single or a multiple impeller configuration, the positioning of the
impellers within the process fluid can have a significant effect on the overall process
performance. Incorrect positioning can lead to staged flow patterns, poor dispersion of
additives and impellers being out of the liquid at crucial stages of the process.
D/T Ratio
The ratio of mixing impeller diameter (D) to vessel diameter (T) has a very significant
effect on the performance of most fluid mixers and the optimum D/T is a function of both
process conditions and process requirements.
Normally the optimum D/T will be in the range 0.2 < D/T < 0.5. Some special
applications however, sometimes operate outside this range.
Bottom Clearance
The impeller bottom clearance (C/T ratio) can also have a very significant effect on the
overall performance of a mixer, affecting both power draw and pumping efficiency. The
optimum C/T ratio is essentially dependent upon impeller type but can also be affected by
process conditions.
Normally, the optimum C/T will be in the range: 0.1 < C/T < 0.3. Hydrofoils however can
operate at much higher levels, up to C/T = 0.5 or more.

VESSEL DESIGN

59

Vessel Geometry
When designing a vessel for mixer duty it is important to understand the role that tank
geometry plays in determining the final mixer design. Poor aspect ratios and or
inappropriate bottom shapes can both result in increase mixer cost and in certain
circumstances make it impossible to optimize the mixer design.
Aspect Ratio
It is generally accepted that the ideal aspect ratio for most mixing tanks is one where the
liquid depth (Z) is equal to the tank diameter (T) as this allows for the optimum number
of impellers, optimum power input and optimum power distribution.
In practice, the optimum Z/T will be in the range 0.9 < Z/T ^ 1.2 as this does not
significantly effect mixer design.
Bottom Shape
Tank bottom shape can have a significant effect on the flow patterns generated within the
mixing vessel and hence the mixers ability to achieve optimum process performance.
Normally a dish-bottom tank is the preferred bottom shape. However, flat-bottoms and
shallow cones (less than 15) can be used for many processes without any particular
problem. In the case of flat-bottomed tanks mixer performance can often be significantly
improved by the introduction of corner fillets.
In general deep cones should be avoided especially where the requirement is solids
suspension.
Baffles
The importance of proper tank baffling in obtaining optimum mixer performance should
not be underestimated. In a correctly baffled tank the mixer develops the fluid regime
required to achieve the optimum process result.
An incorrectly baffled tank on the other hand can lead to poor mixer performance and
may even result in the mixer not being able to achieve the process result for which it was
designed.
It is normally desirable to set the baffles off the wall and off the bottom of the tank to
prevent solids or fluids from stagnating at those points. The optimum baffling
arrangement however, will vary from process to process and is dependant upon a variety
of factors including, vessel geometry, vessel internals, specific power, the required
surface effects, and viscosity.
Mixing Intensity

60

Within the process industries in general it has become convenient to characterize the level
of mixing required for a given application in terms of agitation intensity. This practice has
led to the introduction of terms like mild or vigorous agitation. Whilst such general terms
are convenient they can mean different things to different people and so need quantifying
if they are to be of any practical use.
The following table gives a general overview of the various degrees of agitation in
common use throughout the industry.

61

MIXING EQUIPMENT SPECIFICATIONS

The proposed designing specifications of the tank meant for preparing the paste of
ethylene glycol and pure terephthalic acid of the desired consistency, with the mole ratio
of 1.2, are evaluated below. The inclusive calculations are worked out in Appendix D.

ENTITY
Mixing Temperature:
Mixing Time:
Viscosity of Paste:
(EG & PTA)
Density of Paste:
Mixer Capacity:
Vessel Height:
Vessel Diameter:
Liquid Level:
Level above agitator:
Selected Impeller:
Impeller Diameter:
No. of baffles:
Baffle width:
Baffle Clearance:
Impeller bottom clearance:
Impeller Blade width:
Blade length:
Impeller rotational speed:
(Gear drive)
Power consumption by Impeller:

PROJECTED
DIMENSIONS
50oC
2hr
4.8827 * 10-3 Pa.S
(or 6.88224 cP)
1217.553 kg/m3
15m3
4.24m
2.12m
2.417m
1.57m
6 pitched-blade turbine
type
0.707m
4
0.212m
0.0212m
0.707m
0.1413m
0.1768m
5 rps (300rpm)
46.882 hp

62

Nomenclature:
Where,
D = Impeller Diameter
C = Impeller off Bottom Clearance
N = Impeller speed
Z = liquid Depth
T = Vessel Diameter

As tabulated in the table, in the mixing vessel, 6 pitched-blade turbine type axial flow
impeller is selected as an agitator (impeller in which the blade makes an angle of less
than 90 with the plane of rotation). Pitched-blade turbines are used on top-entering
agitator shafts instead of propellers when a high axial circulation rate is desired, that is
the cause it is chosen in the case of EG & TPA paste formation. Another reason is that it
is effective for rapid submergence of floating particulate solids, near the upper surface of
liquid in a vessel.

63

PITCHED-BLADE TURBINE

If further efficient mixing is required then two impellers can be mounted on the same
shaft as shown in figure given below, having the same dimensions as mentioned above,
with the distance (S) equal to the diameter of the impeller between them. But in such
condition, it will be required to ensure that the upper impeller remain immersed, at all
time, in the paste during agitation.

DUAL IMPELLER MIXER & DRIVE

64

FLOW PATTERN IN MIXER

In fluid agitation, the direction as well as the magnitude of the velocity is essential. The
directions of the velocity vectors throughout an agitated vessel are referred to as the flow
pattern. Since the velocity distribution is constant in the viscous and turbulent ranges, the
flow pattern in an agitated vessel is fixed.
The use of vertical sidewall baffles destroys the rotary and swirling motion in the tank
(reduces the vortex formation). The axial-flow turbine (shown in figure) actually gives a
flow coming off the impeller of approximately 45, and therefore has a re-circulation
pattern coming back into the impeller at the hub region of the blades.

Typical flow pattern in a baffled tank

65

3.7. PROCESS & INSTRUMENTATION DIAGRAM

OF THE MIXER

We are basically concerned with the level of the mixer and it can be lowered then
specified level so it can be controlled by the flow rate of ethylene glycol. Since flow rate
of spent ethylene glycol cant be maintained therefore the mole fraction of ethylene
glycol is maintained by fresh one. The process and instrumentation plan, for the mixer
sized, is illustrated underneath showing all the crucial appliances.

FY
F IC

FT
M

LT

L IC

P&ID OF THE EG & PTA MIXER

66

APPENDICES

67

APPENDIX A

Reactions and Species

The following section details the reactions and components involved in

the PET manufacturing process. For this study, PET formation is
modeled with a system of second order reactions. The model includes
eight components. Table A.l lists the component's name, type,
molecular weight, and the component's symbol.
Table A.I: Species Notation and Molecular Weights

68

Each reaction has the following form

A + B C + D.
Although most of the reactions are reversible, all are treated as forward
reactions (reversible reactions are treated as two forward reactions
with the second reaction's component list inverted).

Polymerization Reactions
In the polycondensation reaction, two hydroxy ethyl ester end groups react to yield an
internal ethyl diester and a free glycol.
1) EG + EG ZG + FG
If one of the hydroxy ethyl ester end groups is replaced by a hydroxy ethyl ethoxy ester
end group, the reaction yields an internal ethyl diester and a free diethylene glycol or a
free glycol and an internal ethyl ethoxy diester.

69

2) EG + ED ZG + FD
3) ED + EG ZD + FG
If both of the reactants are hydroxy ethyl ethoxy ester end groups, the reaction yields an
internal ethyl ethoxy diester and a free diethylene glycol.
4) ED + ED ZD + FD
The kinetic parameters involved in reactions (1), (2), (3) and (4) are assumed to be
identical since the functional groups where the reaction occurs are the sarne.
In the esterification reaction a hydroxy ethyl ester group or a free glycol reacts with an
acid end. The primary example of this type of reaction is an acid end reacting with free
ethylene glycol yielding a
hydroxy ethyl ester end group and water.
5) EC + FG EG + FC
If the free glycol from the above reaction is replaced by a free diethylene glycol the
reaction produces water and a hydroxy ethyl ethoxy ester end group.
6) EC + FD ED + FC
The kinetic parameters of this reaction are the same as for reaction (5) since the
functional groups involved in the reaction are the same. The esterification reaction
between an acid end and a hydroxy ethyl ester end yields an internal ethyl diester and
water.
7) EC + EG ZG + FC
If a hydroxy ethyl ethoxy ester replaces the hydroxy ethyl ester in the above reaction it
results in formation of an internal ethyl ethoxy diester and water.
8) EC + ED ZD + FC
Reactions (7) and (8) can be assumed to have same kinetic parameters since the
functional groups involved are the same. If a hydroxy ethyl ethoxy end reacts with a free
glycol, a hydroxy ethyl ester end and a free diethylene glycol are formed.
9) ED + FG EG + FD
The most important side reactions involved in PET manufacturing are DEG formation,
both in the free and associated forms. The following reactions come under this category.
10) EG + EG ED + EC

70

If one EG group is substituted by a free glycol the following reaction is observed.

11 ) EG + FG FD + EC
Diethylene glycol contained species can also be formed by the following reactions.
12) EG + ZG ZD + EC
13) ZG + FG ED + EC
It should be noted here that reactions (11) and (12) have the same kinetic parameters as
reaction (10), but since free glycol has a functionality of two, the rate constant is
multiplied by a factor of two. The rate constant for reaction (13) is the same as that for
reaction (10). To account for the number of sites available for the occurrence of the
reaction, the rate constant is Inultiplied by a factor of four.

71

APPENDIX B

Material Balance
MIXER:
By the help of following Equation we may calculate the amount of Raw
Materials required to produce 100 TPD of Poly (ethylene Terephthalate)
which is taken as the basis for calculation:

By the stoichiometry, for the production of 100TPD PET we are required 21.6088
Kmol/hr (3587.06 Kg/hr) of PTA and since 1.2-mol ratio of EG: PTA is maintained so
25.9305 Kmol/hr (1607.694 Kg/hr) of EG is required. It forms 70:30 wt% of PTA: EG.
ESTERIFICATION REATOR:
It taken as bases that 52% of Ethylene Glycol is added so as to
maintain 1.8-mol ratio of EG. So the amount of EG is 39.41 Kmol/hr
(2443 Kg/hr). From the equation it is shown that 2 moles of EG is
required to produce 1 mol of PET but we are taken 1.8-mol ratio and
hence EG is Limiting reactant. It is also taken as the basis that 97%
conversion is taken place in the Esterifier reactor.
BHET Produced

PTA remains un-reacted

= 0.0888 21.61 + 0.912 21.61 0.03

= 2.49Kmol/hr

Kmol/hr

(4855 Kg/hr)

(414Kg/hr)

72

39.41 = 1.18 Kmol/hr

EG remains un-reacted

= 0.03

H2O Produced

= 0.97 39.41 = 38.23 Kmol/hr

TOTAL EG OUT

= 1.18 - 0.78 = 0.402 Kmol/hr

(73.31 Kg/hr)
(688 Kg/hr)
(25 Kg/hr)

To Column:
Since at high temperature all of the H 2O and assumed to be 2mol % of EG is evaporated
as Esterifier is operating at 258oC.

EG evaporated

Kmol/hr (48.37 Kg/hr)

H2O

= 38.23 Kmol/hr (688 Kg/hr)

PRE-POLYCONDENSATION REACTOR:
It is required to calculate first the amount of conversion of BHET into PET. It is assumed
that about 0.27 IV (intrinsic viscosity) is maintained after Pre-Polycondensation unit. By
the help of formula:

It is obtained by calculation that the conversion is 96 %. Since BHET converts into PET
with the production of EG and this product EG is used to convert PTA. Both of these
reactions are simultaneously occurring thus it is difficult to calculate them, so we first
assumed the production of BHET and then conversion of BHET into PET is presumed. It
is also assumed that conversion of PTA is 100% with no PTA left un-reacted.

BHET Produced
TOTAL BHET

= PTA converted
= 2.493+19.116

=2.493 kmol/hr
= 21.6 Kmol/hr

EG Produced

= 0.96 21.608

= 20.66 Kmol/hr (1281 Kg/hr)

(633 Kg/hr)
(5489 Kg/hr)

73

EG Consumed

= 2 2.49

= 4.98 Kmol/hr

TOTAL EG
PET produced
H2O Produced
EG OUT

= 20.66-4.98
= EG produced
= EG consumed
= 16.07-15.76

= 16.07 Kmol/hr (996 Kg/hr)

= 20.66 Kmol/hr (3966 Kg/hr)
= 4.98 Kmol/hr
(90 Kg/hr)
= 0.32 Kmol/hr (19.94 Kg/hr)

(309 Kg/hr)

To Condenser:
It is assumed that at high vacuum about 98% of EG and 100% of H 2O has been removed
by evaporation, it is needed to remove as high as we could to prevent the probability of
reversible reaction.
EG evaporated

= 0.98

16.07

= 15.756 Kmol/hr (976 Kg/hr)

= 4.98 Kmol/hr

H2O

(90 Kg/hr)

POLYCONDENSATION REACTOR (D.R.R):

It is a special type of horizontal reactor, supplied with disc ring that provides the
maximum surface area that helps in termination and growth of chain.
It is required to calculate first the amount of conversion of BHET into PET. It is assumed
that about 0.61 IV (intrinsic viscosity) is maintained after Pre-Polycondensation unit. By
the help of formula:

It is obtained by calculation that the conversion is 98.7 %.

BHET to be reacted

= (0.9867-0.96) 21.6088 = 0.66 Kmol/hr (168 Kg/hr)

EG Produced
TOTAL EG
BHET un-reacted

= BHET reacted
= 0.66 + 0.32
= 0.947 0.66

= 0.66 Kmol/hr (41 Kg/hr)

= 0.98 Kmol/hr (61 Kg/hr)
= 0.286 Kmol/hr
(72.85 Kg/hr)

74

TOTAL PET
TOTAL PRODUCT
PRODUCED

= 20.66 + 0.66

= 21.32 Kmol/hr
(4094 Kg/hr)

= PET+BHET un-reacted =73 + 4094

= 4167 Kg/hr

In Tons per Day:

PRODUCT =

= 100 TPD

To Condenser:
It is assumed that at high vacuum about 100% of EG has been removed by evaporation; it
is needed to remove as high as we could to prevent the probability of reversible reaction.
EG evaporated = 0.98 Kmol/hr (61 Kg/hr)
DRR CONDENSER:
It is assumed that 98% of EG is evaporated.
EG Condensed

= 0.98

0.98

EG Uncondensed

= 0.98 - 0.96

= 0.96 Kmol/hr

(60 Kg/hr)

= 0.02 Kmol/hr (1.22 Kg/hr)

PP CONDENSER:
It is assumed that 80% of total vapors are condensed, which constitutes 80% of EG
condensed vapors whereas 100% of H2O condensed vapors.
Vapor Condensed:
EG

= 0.8

15.76

= 12.61 Kmol/hr (781 Kg/hr)

= 4.98 Kmol/hr (89.7 Kg/hr)

H2O
Uncondensed Vapor:
EG

= 15.76 - 12.61

3.15 Kmol/hr

(195 Kg/hr)

75

JET SYSTEM:
Since three-stage jet system has been used, along with vacuum pump
so as to condense the uncondensed vapors from both PP and DRR
condensers. It is assumed to be 100% efficient and all the vapors has
been condensed.
Uncondensed EG = 0.02 + 3.15 = 3.17 Kmol/hr (196 Kg/hr)

DISTILLATION COLUMN:
FEED IN:
Feed enters into the column at different flash points as a mixture of vapors and liquid.
Liquid feed is used to manipulate the temperature of column and throttle accordingly.
LIQUID FEED:
All of the Liquid feed is taken from PP Condenser, therefore
EG = 12.6 Kmol/hr (781 Kg/hr)
H2O = 4.98 Kmol/hr (89.74 Kg/hr)
VAPOR FEED:
All of the Vapor feed is taken from Esterifier reactor, therefore
EG = 0.78 Kmol/hr (48.37 Kg/hr)
H2O = 38.23 Kmol/hr (688 Kg/hr)
TOP OUT:
It is assumed that 99 mol% of H2O is obtained as the top product.
H2O

= 38.23 + 4.98

= 43.22 kmol/hr (778 Kg/hr)

EG

= 0.44 Kmol/hr (27 Kg/hr)

TOTAL TOP OUT

= 778+27

= 804 Kg/hr

REFLUX:

76

Reflux ratio is taken to be 1.

H2O

= 21.61 Kmol/hr (389 Kg/hr)

EG

= 0.22 Kmol/hr(13.53 Kg/hr)

DISTILLATE:

H2O

= 21.61 Kmol/hr (389 Kg/hr)

EG

= 0.22 Kmol/hr(13.53 Kg/hr)

BOTTOM:
100% of EG is taken as Bottom Product.
EG
= 13.38 - 0.436

= 12.95 Kmol/hr (803 Kg/hr)

MOTHER VESSEL:

Column EG
Jet System EG
DRR Condenser EG
TOTAL EG IN
EG to Esterifier
EG to Mixer

= 12.95 + 3.17 + 0.96

= 17.08 - 13.48

= 12.95 Kmol/hr (803 Kg/hr)

= 3.17 Kmol/hr (196 Kg/hr)
= 0.96 Kmol/hr
(60 Kg/hr)
= 17.08 Kmol/hr(1060 Kg/hr)
= 13.48 Kmol/hr (836 Kg/hr)
= 3.6 Kmol/hr
(223 Kg/hr)

77

APPENDIX C

Energy Balance
HEAT CAPACITIES:
The heat capacity is the amount of heat required to raise the temperature of an object or
substance one degree.
The basic equations used for the calculation of Heat Capacities are
1. FOR LIQUID:

2. FOR GASES:

The values of A, B, C, D and E are obtained from several sources and graphs including
DIPPR 8.0 for liquid and gases except monomers and polymer (PET).

78

Cp at 25
o
C
(KJ/Kmol)

ENTITY

Ethylene Glycol Liquid

Ethylene Glycol Vapor
Water Liquid
Water Vapor
Terephthalic Acid
Poly(ethylene
Terephthalate)
BHET

3.55E+04
8.20E+04
2.76E+05
3.34E+04
-2.60E+04

4.36E+02
1.27E+05
-2.09E+03
2.68E+04
6.34E+02

-1.84E-01
1.69E+03
8.13E+00
2.61E+03
0.00E+00

0.00E+00
9.29E+04
-1.41E-02
8.89E+03
0.00E+00

0.00E+00
-7.54E+02
9.37E-06
1.17E+03
0.00E+00

1.49E+02

9.00E-01

5.00E-03

0.00E+00

0.00E+00

0.00E+00

4.59E+02

Cp = 454.3 KJ/KmolK

7.53E+01
1.63E+02

Cp=454*(0.64+0.0012*T)

4.53E+02

HEAT OF VAPORIZATION:
The enthalpy of vaporization, (symbol vH), also known as the heat of vaporization or
heat of evaporation, is the energy required to transform a given quantity of a substance
into a gas.
It is often measured at the normal boiling point of a substance, although tabulated values
are usually corrected to 298 K: the correction is small, and is often smaller than the
uncertainty in the measured value.

By using the formula;

ENTITY
Ethylene Glycol
Water

Hla
1.95E+04
1.35E+04

Hlb
6.45E+02
6.47E+02

H (KJ/Kmol)
4.97E+04
4.08E+04

ALL Heat of Vaporization calculated at their boiling point.

BASIS:
Reference temperature is considered to be 25 oC (298.15 K)

Heat capacities for the saturated vapor is calculated by adding heat capacities of
liquid, latent heat of vaporization and heat capacities at particular temperature.

H can be calculated by using following formula;

TEMPERATURES:
ENTITY
ESTERIFICATION
PREPOLYCONDENSATION

TEMPERATURE (oC)

TEMPERATURE (K)

258
270

531.15
543.15

79

POLYCONDENSATION DRR
Reference
Boiling point EG
Boiling point Water
PTA IN
EG IN
OUT
SEG
Liquid feed
Vapor feed
Reflux
Top out
Bottom out
Q recycle
Q cond
Q uncond
Q recycle
Q cond
Q uncond

280
25
197.6
100
MIXER
30
62
50
ESTERIFICATION
100
COLUMN
40
258
70
100
180
PP CONDENSER
40
95
210
DRR CONDENSER
33
150
210

553.15
298.15
470.75
373.15
303.15
335.15
323.15
373.15
313.15
531.15
343.15
373.15
453.15
313.15
368.15
483.15
306.15
423.15
483.15

MIXER:
FEED IN:
ETHYLENE GLYCOL:

PURE TEREPHTHALIC ACID:

TOTAL IN =

= 2.84

105 KJ/hr

MIXER OUT:
ETHYLENE GLYCOL:

80

PURE TEREPHTHALIC ACID:

= 3.63

TOTAL OUT =

105 KJ/hr

ESTERIFICATION REACTOR:
FEED IN:
SPENT ETHYLENE GLYCOL(SEG):

= 5.88

TOTAL IN =

105 KJ/hr

ESTERIFICATION OUT:
To Pre-Polycondensation:
ETHYLENE GLYCOL:

PURE TEREPHTHALIC ACID:

BHET:

TOTAL OUT =

KJ/hr

To Column:
ETHYLENE GLYCOL:

81

WATER:

TOTAL OUT = 2.02 106+8.63 104 = 2.11

TOTAL OUT OF ESTERIFIER =

106 KJ/hr
= 5.74

106 KJ/hr

HEAT OF REACTION:
AMOUNT OF HEAT REQUIRED:
= TOTAL OUT TOTAL IN HEAT OF REACTION
= 5.74 106-5.88 105-(-2.87 105)= 5.43

106KJ/hr

It is assumed that 30% of heat is supplied by the liquid dowtherm while 70% of heat
is supplied by vapor dowtherm.
Mass Flow of Liquid DOWTHERM:

Mass Flow of Vapor DOWTHERM:

82

PRE-POLYMERIZATION:
FEED IN:
ESTERIFIER PRODUCT =

KJ/hr

PRODUCT OUT:
To DRR:
Poly(ethylene Terephthalate):

BHET:

ETHYLENE GLYCOL:

TOTAL OUT=

= 5.16

106 KJ/hr

To Condenser:
ETHYLENE GLYCOL:

WATER:

83

TOTAL OUT = 1.78 106+2.66 105 = 2.04

106 KJ/hr

TOTAL OUT OF PP =

= 7.21

106 KJ/hr

HEAT OF REACTION:
AMOUNT OF HEAT REQUIRED:
= TOTAL OUT TOTAL IN HEAT OF REACTION
HEAT OF POLYMERIZATION
=7.21 106 -3.63 106-(-3.74 104)-0= 3.62

106KJ/hr

Mass Flow of Vapor DOWTHERM:

POLYCONDENSATION (DRR):
FEED IN:
PRE-POLYMERIZER PRODUCT = 5.16

106 KJ/hr

MELT PHASE PRODUCT:

Poly(ethylene Terephthalate):

84

BHET:

= 5.44

TOTAL OUT =

106 KJ/hr

To Condenser:
ETHYLENE GLYCOL:

= 5.55

TOTAL OUT OF DRR =

106 KJ/hr

AMOUNT OF HEAT REQUIRED:

= TOTAL OUT TOTAL IN HEAT OF
POLYMERIZATION
=5.55 106 -5.16 106-0= 3.90

105KJ/hr

Mass Flow of Vapor DOWTHERM:

COLUMN:
LIQUID FEED:
ETHYLENE GLYCOL:

85

WATER:

TOTAL IN =

= 5.32

104KJ/hr

VAPOR FEED:
ETHYLENE GLYCOL:

WATER:

TOTAL IN = 2.02 106+8.63 104 = 2.11

106 KJ/hr

REFLUX:
WATER:

86

TOTAL IN = 2.11 106+5.32 104+7.36 104 = 2.31

106KJ/hr

TOP OUT:
It is assumed to be 100% water and neglecting ethylene glycol in the top product.
WATER:

BOTTOM OUT:
ETHYLENE GLYCOL:

TOTAL OUT = 2.02 106+5.89 105 = 2.61

106KJ/hr

AMOUNT OF HEAT REQUIRED:

= TOTAL OUT TOTAL IN
=2.61 106 -2.31 106= 2.99

105KJ/hr

Mass Flow of Liquid DOWTHERM:

PRE-POLYMERIZATION CONDENSER:

Q recycle:
ETHYLENE GLYCOL:

WATER:

87

Q cond:
ETHYLENE GLYCOL:

WATER:

Q uncond:
ETHYLENE GLYCOL:

By the equation:

POLYMERIZATION CONDENSER:

Q recycle:
ETHYLENE GLYCOL:

88

Q cond:
ETHYLENE GLYCOL:

Q uncond:
ETHYLENE GLYCOL:

By the equation:

MOTHER VESSEL:
EHTYLENE GLYCOL IN:
From JET SYSTEM:

From DRR VESSEL:

From COLUMN:

89

TOTAL IN =

= 6.35

105KJ/hr

EXIT TEMPERATURE:

ETHYLENE GLYCOL OUT:

JET SYSTEM:
ENTITY
Qf
Qcond
Quncond
Qrecycle
Qf
Qcond
Quncond
Qrecycle
Qf
Qcond
Quncond
Qrecycle

TEMPERATURE
(oC)
STAGE 1st
210
80
210
54
STAGE 2nd
210
100
210
85
STAGE 3rd
210
120
210
100

TEMPERATURE
(K)
483.15
353.15
483.15
327.15
483.15
373.15
483.15
358.15
483.15
393.15
483.15
373.15

STAGE 1st:

Q recycle:
ETHYLENE GLYCOL:

90

Q cond:
ETHYLENE GLYCOL:

Q uncond:
ETHYLENE GLYCOL:
By the equation:

STAGE 2nd:

Q recycle:
ETHYLENE GLYCOL:

Q cond:
ETHYLENE GLYCOL:

Q uncond:
ETHYLENE GLYCOL:
By the equation:

STAGE 3rd:

91

Q recycle:
ETHYLENE GLYCOL:

Q cond:
ETHYLENE GLYCOL:

Q uncond:
ETHYLENE GLYCOL:
By the equation:

APPENDIX D
Balances on Heat Exchangers
COLUMN CONDENSER:

92

TEMPERATURES:
COOLING WATER
DISTILLATE

IN
32
100

OUT
46
70

COOLING WATER:
IN:
OUT:

DISTILLATE:
IN:
OUT:

SINCE,
ENERGY IN = ENERGY OUT

PREPOLYMERIZATION HEAT EXCHANGER:

TEMPERATURES:
COOLING WATER
PP COND

IN
32
95

OUT
46
40

COOLING WATER:
IN:
OUT:

93

PP COND:
IN:
ETHYLENE GLYCOL:
WATER:

OUT:
ETHYLENE GLYCOL:
WATER:

SINCE,
ENERGY IN = ENERGY OUT

DRR HEAT EXCHANGER:

TEMPERATURES:
COOLING WATER
DRR COND

IN
10
150

OUT
46
33

COOLING WATER:
IN:
OUT:

DRR COND:
IN:
OUT:

94

SINCE,
ENERGY IN = ENERGY OUT

MIXER HEAT EXCHANGER:

TEMPERATURES:
COOLING WATER
SPENT ETHYLENE
GLYCOL

IN
32
100

OUT
46
62

COOLING WATER:
IN:
OUT:

SPENT ETHYLENE GLYCOL:

IN:
OUT:

SINCE,
ENERGY IN = ENERGY OUT

NOTE: By the specification, it is defined that the supply water is available at 32 oC and
return water having the temperature of 46 oC.

APPENDIX E

Mixing Equipment Sizing

95

Information Required for Mixer Selection

1. Mixer Feed Data

o Mixing Temperature: 50oC
o Mixing Time: 2hr

COMPONENT

MOLE FRACTIONS
x

DENSITY,
Kg/m3

VISCOSITY,
Pa. S

EG

0.70

1092.218

0.0069724

TPA

0.30

1509.9995

6.6733*10-6

2. Paste Properties at 50 oC
o Paste Density:
T = (x x )EG + (x x )PTA
= 0.70 x 1092.218 + 0.30 x 1509.9995
= 12.17.553 kg/m3
o Paste Viscosity:
T = (x x )EG + (x x )PTA
= 0.70 x 0.0069724 + 0.30 x 6.6733E-6)
= 4.8827E-3 Pa.S

3. Fluid Characteristics in Mixing Vessel:

o Flow Rates:
Total Mass Flow Rate (out) = m

= 5194.74 kg/hr

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 Volumetric Flow Rate

= Q = m/ T = 5194.74 / 1217.553
= 4.2665 m3/hr

o Fluid Volume:
V = Q x t = 4.2665 x 2
= 8.5331 m3
or 2275.49 gallons

1 m3 = 266.667 gallons

Sizing Calculations

1. Vessel Dimensions:
o Total Mixer Capacity:
Since, 60% of the total vessel volume is filled with the fluid so the total volume of the
vessel will be estimated as:
Total Mixer Capacity = 8.5331 / 0.6 = 14.22 m3
15 m3
o Vessel Height, Diameter & Volume:

REALTIONS

HEIGHT (m)

DIAMETER (m)

VOLUME (m3)

H=3D

5.56

1.853

15.00

H=2D

4.24

2.12

14.97

H=D

2.67

2.67

14.95

Selected Dimensions:
- Height, H = 4.24 m
- Diameter, D = 2.12m

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2. Liquid Levels in the Vessel:

o Height of the Liquid in Vessel:
As, 60% of total volume is paste filled having volume = 8.5331 m3
So, the height of the liquid in vessel is:
Height / Level of Liquid = h = Volume/r2
= 8.5331 / (3.142x2.122/4)
= 2.417m
Since, 65% of paste is above agitator & 35% is below it.
Level above agitator
= 0.65 x 2.417
= 1.57m
Level below agitator
= 0.35 x 8.5331
= 2.987m3
3. Impeller Selection:
6 pitched-blade turbine type axial flow impeller is selected as an agitator (impeller in
which the blade makes an angle of less than 90 with the plane of rotation), as a topentering agitator shafts. Four baffles are estimated as optimum along with the turbine
type impeller for effective mixing (also because the Reynolds number of the paste is
greater then 2000).
4. Proportions of Tank:
At H = 4.24m & D = 2.12m.
o Impeller Diameter:
Da/D = 1/3
or, Da = 1/3 x 2.12 = 0.707m
o Baffle Width:
(10% of Tank diameter)
J/D = 1/10
or, J = 2.12 /10 = 0.212m
o Clearance between Baffles & Vessel wall:
(0.1-0.15J)
Ca = 0.1 J = 0.1x 0.212
Ca
= 0.0212m
o Impeller Height from Bottom:
C/Da = 1
or, C = Da = 0.707m

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o Impeller Blade Width:

W = D/15
or, W = 2.12/15 = 0.1413m
o Blade Length:
L/Da = 1/4
L = Da/4 = 0.707 / 4
= 0.1768m
5. Fluid Flow Characteristics:
o Velocity of Fluid in Tank:
V = Q / A = 4.2665 / 3.5304
Area = r2 = 3.5304 m2
= 1.20852 m/sec
o Reynold Number:
Re = D x v x T / T
= (2.12 x 1.20852 x 1217.553) / 4.8227E-3
= 6.4683E5
6. Impeller Rotational Speed:
Re = ( Da2 n T )/ T
or,
n = (Re T)/ (Da2 T)
= (6.4683E5 x 4.8227E-3)/(0.7072 x 1217.553)
= 5.13 rps 5rps (300rpm)
7. Power Consumption by Impeller:
Estimating the power consumption for any agitator is essential for design. The power
consumed by an agitator depends on fluid density, viscosity, vessel dimensions, internal
attachments, position of the impeller, its shape, rotational speed, and impeller diameter by
plots of power number (gcP/n3Da5) versus Reynolds number (Da2n/). Typical
correlation lines for frequently used impellers operating in Newtonian liquids in baffled
cylindrical vessels are presented in the Figure A.

99

Figure A : Impeller power correlations: curve 1, six-blade turbine,

Da /Wi = 5, with six blades, four baffles, each DT /12; curve 2, vertical
blade, open turbine with six straight blades, Da /Wi = 8, four baffles each
DT /12 curve 3, 45 pitched-blade turbine with six blades, Da /Wi = 8 four
baffles, each DT/12; curve 4, propeller, pitch equal to 2Da, four baffles,
each 0.1DT, also same propeller in angular off-center position with no
baffles; curve 5, propeller, pitch equal to Da, four baffles each 0.1DT,
also same propeller in angular off-center position with no baffles. Da =
impeller diameter, DT = tank diameter, gc = gravitational conversion
factor, N = impeller rotational speed, P = power transmitted by impeller
shaft, Wi = impeller blade height, = viscosity of stirred liquid, and =
density of stirred mixture. Any set of consistent units may be used, but N
must be rotations (rather than radians per unit time. In the SI system, gc
is dimensionless and unity. [Curves 4 and 5 from Rushton, Costich, and
Everett, Chem. Eng. Prog., 46, 395, 467 (1950), by permission; curves 2
and 3 from Bates, Fondy, and Corpstein, Ind. Eng. Chem Process Des.
Dev., 2, 310 (1963), by permission of the copyright owner, the American
Chemical Society.]

Thus, the empirical relation for calculating power consumption by an

impeller can be written as:
P = Np T n3 Da5
The value of Power number (Np) is taken is 1.3 for 6-pitched blade turbine, from the
graph of impeller power correlations. So, the power consumed by the selected turbine is:
P = 1.3 x 1217.553 x 53 x 0.7075
= 34.95 kWatt or 46.882 hp

1 hp = 745.48 Watt

100

BIBLIOGRAPHY

o Robert H. Perry & Don W. Green, Perrys Chemical Engineering Handbook, 7th
Edition, Volume 2, Mc-Graw Hill International Edition.
o Pattalachinti, R.K., Modeling and Optimization of Continuous Melt-Phase
Polyethylene Terephthalate Process. Ohio University Master's Thesis, 1994.
o Timothy J. Calmeyn, Optimization of Melt-Phase Polyethylene Terephthalate
Manufacturing Process. Ohio University Master's Thesis, 1995.
o Faissal-Ali El-Toufaili, Catalytic and Mechanistic Studies of Polyethylene
Terephthalate Synthesis. Project Report, 2006.
o UOP Sincos SSP English Brochure, Solid State Polycondensation Process, 2005.
o David A. Tremblay, Using Simulation Technology to Improve Profitability In the
Polymer Industry, Aspen Technology Inc., 1999.
o PET Facts, National Association for PET Container
www.napcor.com/toolbox/funfacts.html accessed July 2000.

Resources.

o United States Patents: 5008230, 5898058, 5166311, & 6864345.

www.uspatent.com
o Other References:
-

International Search Reports and Written Opinions.

http://en.wikipedia.org/wiki/Polymer

http://www.designboom.com/contemporary/petbottles.html

http://www.kenplas.com/

http://www.plasticsinfo.org/beveragebottles/faq.html

http://www.petresin.org/pet_facts.asp

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