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Download265 Tons Per Day Production of Terephthalic Acid by Amoco Process 1 PDF Free - HTML
Download265 Tons Per Day Production of Terephthalic Acid by Amoco Process 1 PDF Free - HTML
Download265 Tons Per Day Production of Terephthalic Acid by Amoco Process 1 PDF Free - HTML
PROJECT ADVISOR
SESSION
2015 - 2019
Approved On
Thesis Supervisor
Signature
External Examiner
Name
Signature
Signature
Acknowledgment
All praise to Almighty ALLAH, who provided us with the strength to accomplish this project
report. All respects are for His HOLY PROPHET (Peace Be Upon Him), whose teachings are
true source of knowledge & guidance for whole mankind.
Before anybody else, we would like to thank our Parents who have always been a source of
moral support, driving force behind whatever we do. We are indebted to our project advisor
Dr. Waqas Aleem for his worthy discussions, encouragement, technical discussions, inspiring
guidance, remarkable suggestions, keen interest, constructive criticism & friendly discussions
that enabled us to complete this report.
We are thankful to the Head of Department and Project In-charge Dr. Asim Umer for
providing facilities and guidance. We are also thankful to all of our teachers for their keen and
sincere efforts and suggestions that proved to be very helpful in achieving our goal.
Abstract
Terephthalic acid (TPA) is the building block of plastic production industries. It is a very
important for the production of Poly-Ethylene Terephthalate. TPA is produced by the high
pressure, high temperature catalytic oxidation of para xylene. Pakistan is currently in a lot of
need of TPA as the demand of plastic industry for TPA is much greater. The objective of this
project report is to deal with design calculations of 265 metric tons per day production rate of
purified TPA along with their manufacturing aspects such as Material and Energy Balance,
Equipment Design, Instrumentation, cost Estimation, HAZOP study and Environmental
Aspects. Keeping these points in Mind. This report is divided in to different sections;
introduction of TPA, literature review, process description, material and energy balance,
equipment design, cost Estimation, HAZOP study, instrumentation and environmental aspects
of Terephthalic Acid Production Plant.
Our project ensures the purity of final product to be 99.99%. The selection of this project was
based on the increasing need of TPA in the Plastic industry of Pakistan. Our project employs
The only
sole producer of TPA in bulk in Pa t is
implemented, our plant will be able to complete the remaining need of TPA for Pakistani plastic
industry.
Undertaking
I certify that thesis work titled 265 MTPD Production of Purified Terephthalic Acid by Amoco
Process is our own work. The work has not been presented elsewhere for assessment. Where
material has been used from other sources it has been properly acknowledged / referred.
List of Figures
Figure 1- 1 Purified Terephthalic acid/PX price trend, 2017[2] _______________________ 28
Figure 4- 3 Lumped kinetic scheme for the oxidation of p-xylene to terephthalic acid _____ 94
Figure 7- 1 Feedback Control loop on Shell and tube Heat Exchanger 147
List of Charts
List of Tables
Table 1- 1 Physical properties_________________________________________________ 27
Table of Contents
1 INTRODUCTION _______________________________________________________ 26
2-15 Henkel Process (Rearrangement of Benzoic acid and Phthalic anhydride) __________ 47
4 EQUIPMENT DESIGN___________________________________________________ 82
4-1-4-5 Assumption_______________________________________________________ 85
4-2-7-14 Specification Sheet for Continuous Stirred Tank Reactors ________________ 105
4-3-19 Calculation for Volumetric heat transfer coefficient (Ua) ____________________ 114
4-3-21 Calculation for log mean of drying gas wet bulb depression at inlet & exit end of dryer
( Tm) __________________________________________________________________ 114
Introduction
PRODUCTION OF PURIFIED TPA CHAPTER 01
1 Introduction
The Group of a senior class of Chemical Engineering has been assign to design a Purified
Terephthalic Acid (TPA) plant using oxidation of para xylene as the raw material. The team
needs to incorporate safety aspects, site selection, conceptual design, material and energy
balance, heat integration and preliminary economic evaluation in the design of plant.
Terephthalic acid, a raw material for polyethylene terephthalate production, is one of the most
important chemicals in petrochemicals industry. Crude Terephthalic acid commonly produced
by homogeneous liquid phase of Para xylene oxidation, contains impurities such as 4-CBA
(carboxybenzaldehyde) and several colored poly aromatics that should be removed to obtain
purified Terephthalic acid.
Terephthalic acid is usually obtain by the catalytic oxidation of p-xylene in air, in the presence
of acetic acid as solvent. Once the synthesis is complete, the solvent is to be recycled and reused
back to the chemical reaction media.
Purified Terephthalic acid manufacturing process consists of two steps, namely, oxidation and
purification. During oxidation step, the p-xylene oxidation reaction takes place in the liquid
phase and is catalyzed by a Co-Mn-Br at the (150-
Terephthalic acid[1].
26
PRODUCTION OF PURIFIED TPA CHAPTER 01
Color White
The aromatic ring of PTA imparts excellent hardness, corrosion and stain resistance to coatings
reins. Such other industrial application of PTA are given as[1]
Adhesives
Architectural coating
Automotive
Coil coating
Graphics arts
Intermediates
Paints & coatings
Protective coating
Water packing
Pharmaceutical industry
Polyester coating resins
27
PRODUCTION OF PURIFIED TPA CHAPTER 01
The purified Terephthalic acid market is likely to observe a noticeable growth in the
approaching years owing to a high demand for polyester resin. Poly Ethylene Terephthalate
demand is also anticipated to have a positive impact on the purified Terephthalic acid market.
The rising per capita consumption and the growing disposable income in the developing
economics such as India and China along with a significant growth of the textile, coating and
packing industries in these region is predicted to fuel the demand for the purified Terephthalic
acid market.
Industries such as the beer industry and the household product containers industry are still
dominated by the glass industry, which is an unexplored market for purified Terephthalic acid
consumption, offering new opportunities for the growth of purified Terephthalic acid market[2].
The PTA price crossed the US$ 700/MT mark in November. The average price of PTA in
spot market was US$ 655/MT.
28
PRODUCTION OF PURIFIED TPA CHAPTER 01
1%
10%
19%
48%
22%
In 2016 the production capacity for PTA reached 80 million tons from 70 million tons in
2014
13%
21%
55%
11%
29
PRODUCTION OF PURIFIED TPA CHAPTER 01
4%
6%
22%
68%
Asia pacific export PTA 62%, western Europe 20%, japan and middle east export PTA 5% &
4% respectively
1%
4%
18%
77%
30
PRODUCTION OF PURIFIED TPA CHAPTER 01
1-5 Feedstock
Feedstock for the production of Purified TPA consist of oxidation of Para xylene[1]
1-5-2 Uses
31
PRODUCTION OF PURIFIED TPA CHAPTER 01
Purified Terephthalic acid is a raw material, which is use in the production of high performance
multipurpose plastics like poly butylene terephthalate (PBT), polyethylene terephthalate
(PET). Purified Terephthalic acid is also use in automotive, intermediate and paint & coating
industry. The main feedstock for purified Terephthalic acid industry are Para xylene and fresh
air. However, due to its increasing cost of Para xylene. The team is assigned the task of
designing a purified Terephthalic acid production plant using a pre-specified composition of
Para-xylene as the raw material. Purified Terephthalic acid is produced by bromine promoted
catalytic oxidation of Para xylene and then is purified by the process of hydrogenation
(AMOCO PROCESS).
1-7 Objectives
The objective of this project is to develop a purified Terephthalic acid production plant. The
plant must be cost effective, considers all of the desired criteria in addition to dealing with
relevant issue. The team needs to recommend the best possible design, which will ultimately
convince panel of juries to verify the new plant. The objectives of this design project include
the following:
To generate cost effective process options while maintaining operability, safety and
environment friendly of the design.
32
CHAPTER 2
Literature Review
&
Process Description
PRODUCTION OF PURIFIED TPA CHAPTER 02
Nowadays, Two PET grades dominate the global market fiber-grade PET and bottle-grade
PET. They differ mainly in the product properties such as optical appearance and production
technologies where these properties can be controlled by molecular weight, intrinsic viscosity,
and additives specific to each process. Other uses include film production and specialty nylons.
Terephthalic acid is the main raw material in PET manufacturing industries [3].
During the period 1942-1944 Whinfield, Dickson and Hardy made Terephthalic Acid (TPA)
by dehydrogenating dipentene with sulfur to form P-cymene (P-isopropyl toluene), which they
oxidized in two stages, where in the first with dilute nitric acid ,and then with alkaline
permanganate. The first commercial route for forming the PET fiber was through oxidation of
p-xylene under pressure using dilute nitric acid. This method had some problems as the
product contained color, and color forming impurities that could not be removed. This required
the replacement of this method by another that gives better product purity; this is why the
method of esterification with methanol to form Dimethyl Terephthalate (DMT) was employed.
Later it was discovered that some DMT production routes are hazardous, so researches were
made to produce TPA from p-xylene directly via air oxidation. Another problem was found
then, which was the high oxidation resistance of the intermediate p-toluic acid. Using acetic
acid as a solvent and oxygen as an oxidant instead of air solved this problem
enabling the use of TPA in polymerization directly.
With the development of the process, the separation equipment also developed. This
development opened the way for the production of PET as a beverages container. Because the
bottle-grade PET needed higher molecular weight and intrinsic viscosity, the need for a more
purification of TPA was essential. Now the production of TPA with the needed purity is
applicable with considerable ease [3].
34
PRODUCTION OF PURIFIED TPA CHAPTER 02
The importance of PET comes from the fact that it is widely used in many products either alone
or as a co-monomer. Also the PET pre-polymerization intermediate (TPA) can be used to
produce other products. The following part shade light on the importance of PET and its
monomers, through stating the most important uses in which they are used [3].
TPA properties, as a PET production intermediate, are shown in the table below mentioning
some physical and chemical properties.
35
PRODUCTION OF PURIFIED TPA CHAPTER 02
TPA can be manufactured from different raw materials and through several routes. Several
technologies have been developed to achieve the most economical way of production. The
following part explains different processes with flow sheets and technical description [3].
TPA is produced by oxidation of p-xylene. There are different technologies to produce TPA
according to oxidation process as follow:
36
PRODUCTION OF PURIFIED TPA CHAPTER 02
P-xylene is the feedstock for most of TPA processes while acetic acid in water is the reaction
solvent. Air is compressed to supply oxygen to the reaction and is added in excess to minimize
formation of by-products, achieve high p-xylene conversion and provide measurable oxygen
partial pressure.
TPA is produce by catalytic liquid-phase reaction. The reaction is highly exothermic, releasing
5.3×107 kJ per hour p-xylene reacted, that is removed by allowing the acetic acid solvent to
boil and rest of heat is removed through external jacket. Oxidation of the methyl groups occurs
in three steps. Two intermediates are formed through the reaction, p-toluic acid and 4-
formylbenzoic acid and finally TPA is produce.
Detail of the above listed processes are mention below. It includes their respective operating
temperature pressure conditions and choice of catalyst as well.
Toray process, which developed in the late 60s, is considered as a modification on Amoco
process. It was established in two main factories all over the world; one of them in
37
PRODUCTION OF PURIFIED TPA CHAPTER 02
The problem that led to the discontinuing of licensing this process is the huge amount of acetic
acid by product obtained, usually 0.5 - 1.1 ton acetic acid per ton TPA, which makes it suitable
only for high market demand of acetic acid as a requirement[3].
In mid-1970, Mitsubishi Kasei developed an oxidation process to obtain high yield pure forms
of TPA without a separate purification step in which these products are called medium purity
TPAs. This process is used to reduce the 4- formyl benzoic acid concentration to 200 - 300
ppm in order to obtain suitable feed stock of TPA for polyester industry. This is done by very
intensive oxidation and the separation step is eliminated as the high purity of feedstock is not
critical. The product is often called medium purity TPA and accounts for about 11% of the
TPA produced all over the world. The oxidation process is the same as of Amoco oxidation
where p-xylene, acetic acid, and catalyst are the reaction mixture to form the TPA. It differs
from Amoco in number of oxidation reactors (two vessels), conditions and residence time
(more than 2.5 hrs.) [3].
The second oxidation vessel operates at higher temperature than the first one in order to oxidize
p-xylene - acetic acid mixture in presence of catalyst to TPA. Where the solubility of TPA is
increased with heating, the crystals dissolved with heating. Also at higher temperature acetic
acid tends to be oxidized largely to carbon oxides and water.
Although the TPA is not completely soluble at the higher temperature, the crystals are digested.
So the amount of the released 4-formylbenzoic acid decreases into solution and this means that
the oxidation is completed so the need for a separate purification process is eliminated. The
rest of the Mitsubishi process consists of solid liquid separation and drying to obtain the
powdered product and acetic acid recycled to the process after dehydration [3].
This process is proven suitable for the production of all kinds of fiber and bottle PET without
limitations at international first grade quality specs. P-xylene is the feedstock with air as
oxidizing agent and acetic acid as a solvent. The reaction is catalyzed by Co +2, Mn+2 and
bromide. The solvent to hydrocarbon weight ratio in the oxidation reactor is in the range of 3 -
5. The catalyst is usually 0.1-0.2 wt % of the solvent used. The temperature and pressure inside
the reactor are in the range of 185 204 °C and 1200 1750 kPa. The maximum recovery
exceeds 95%.
38
PRODUCTION OF PURIFIED TPA CHAPTER 02
The residence time is less than 1 hr to accomplish complete conversion and about 98.3% yield
is achieved. In addition to that, power generation from the process may reach 10,000 kW.
Wash acid tank serves as the acetic acid reservoir that supplies acid deficiency in the feed
stream to the oxidizer reflux tank and the filtrate tank. The filtrate tank collects the prepared
catalyst solution, hydrogen bromides as well as filtrate from the filtrate treatment. The filtrate
is used to control catalyst and acid concentrations. These all and p-xylene are fed together into
the oxidizer. The weak acid stream from the oxidizer reflux tank is sprayed into the top of the
oxidizer in order to prevent solid formation. The oxidizer is a bubble column reactor. A
centrifuge is used to remove impurities from the CTA by the lean solvent that is obtained as
the bottoms of the water removal column. This lean solvent consists of mixture of the oxidizer's
overhead vapor (water, acetic acid and nitrogen) and solvent. Only impurities soluble in this
solvent can be removed from CTA. Then CTA is purified to obtain Eastman Purified
Terephthalic Acid (EPTA) in a post oxidation step done in two oxidizers. This process requires
increasing the temperature to increase the conversion of the CTA impurities oxidation. TPA
(TA) with lower impurity content is obtained from this oxidation. Finally, TPA is directed to
crystallizer. Then separated in vacuum flash drum and the solvent is recovered to the oxidizer
reflux tank. EPTA is finally directed to rotary vacuum filter then dryer to get the final product.
The outlet from centrifuge passes to overflow flash drum then to catalyst recovery and filtrate
treatment unit where it is separated to get soluble impurities, insoluble impurities and the CTA
residue. Both insoluble impurities and the CTA residue are burnt in the fluidized bed or buried
in a landfill. The catalyst is recovered to a filtrate tank. The top stream of the water removal
column enters WRC condensers. Then vent gas is separated from waste water in WRC reflux
drum then directed to regeneration thermal oxidizer/ scrubber. The waste water got is directed
to water treatment station [3].
Methyl p-toluate is isolated and returned back to the oxidation reactor in which it is oxidized
to MMT, which is esterified to DMT to be purified.
39
PRODUCTION OF PURIFIED TPA CHAPTER 02
Then finally the DMT passes through a hydrolysis stage which consists of two reaction steps,
where first the DMT turns into MMT, and then the MMT turns into TPA to enter
polymerization [3].
Purified TPA became commercially available from Amoco Chemical Co. in 1965. Amoco
process involves purification of crude TPA by a separate step to attain the high product purity
required for PET manufacture. This technology is the most used worldwide, but other
processes have been developed and are operating commercially. The feed passes to the
oxidation reactor at which oxidation occurs. Most of TPA precipitates, because of its low
solubility in the solvent. This yields a two- phase system; TPA slurry; solvent with some
dissolved TPA; and vapor consisting of nitrogen, acetic acid, water, and a small amount of
oxygen. The overhead vapors from the reactor are condensed in heat exchangers, and the
condensate is refluxed to the reactor. Steam, which is generated by condensation, used as
heating source in other parts of the process. Oxygen depleted gas from the condensers is
scrubbed to remove most uncondensed vapors.
Oxidation reactor operates at 175 - 225 C and 1500 - 3000 kPa, at residence time about 2.5
hours.The pressure of hydrogenation reactor is held above the vapor pressure of water to
maintain a liquid phase. Catalyst used in oxidation reactor is multivalent heavy metal [3].
40
PRODUCTION OF PURIFIED TPA CHAPTER 02
Mostly, cobalt and manganese are the multivalent heavy-metal catalysts and bromine is the
renewable source for the free radicals. A soluble cobalt manganese bromine catalyst
system is the heart of the process.
This yields nearly quantitative oxidation of the p-xylene methyl groups with small xylene
losses. Various salts of cobalt and manganese can be used, and the bromine source can be
HBr, NaBr, or tetrabromo ethane.
The effluent stream from the reactor contains TPA as slurry. This slurry passes through a
surge vessel that operates at a lower pressure than the reactor. More TPA crystallizes and the
cooled slurry is then ready to be processed at close to atmospheric conditions. The slurry is
fed to a centrifugation unit at which most of water removed from the product. After
centrifugation, one stream is fed to the recovery unit and the other to a rotary drier. Preheated
air is sent to the drier to remove the moisture present in the final product. TPA crystals are
obtained from the drier by 99% purity, then conveyed to storage, from which they are in turn
fed to the purification step [3].
Water formed and some undesirable by-products must be removed from acetic acid solvent.
Mother liquor from the centrifuge is purified in a solvent recovery tower to purify acetic acid.
The purified acetic acid from the top of the tower is recycled to the reactor and combined
with fresh acetic acid and the bottom product can be processed for catalyst recovery and
regeneration. Vents from the oxidation process, are sent to a gas scrubbing tower then to
water removal tower to remove the water formed as the overhead stream which sent to waste
water treatment. Amoco process involves a purification unit to achieve the required purity
before entering the polymerization step. The main impurity in the crude TPA is 4-
formylbenzoic acid (up to 5000 ppm). There are also yellow impurities and residual amounts
of catalyst metals and bromine.
TPA crystals are dissolved in a hot process water to increase its solubility. The slurry formed
contains at least 15 wt. % TPA and the rest are impurities accessible to the purification reaction.
The solution flows through a hydrogenation reactor. Hydrogen is added to the reactor, where
it dissolves in the feed solution.
41
PRODUCTION OF PURIFIED TPA CHAPTER 02
Various colored impurities are hydrogenated to colorless products. The catalyst is highly
selective; the loss of TPA by carboxylic acid reduction or ring hydrogenation is less than 1%.
The more soluble p-toluic acid formed in the reactor, and other impurities, remain in the mother
liquor. After leaving the final crystallizer, the slurry undergoes centrifugation to yield a wet
cake, and the cake is dried to give the product TPA as a free-flowing powder [3] .
TPA is the main product. More than 98% of the p-xylene is converted with a minimum yield
of 95 mole %. Further, this is on a once-through basis. TPA from oxidation process is called
technical or crude grade of phthalic acid, but the purity is typically greater than 99%. It is not,
however, pure enough for the PET production to reach the required degree of polymerization.
In the purification unit over 98 wt. % of the incoming TPA is recovered as purified product.
The purified TPA as a white powder is called polymer grade TPA which is suitable to be used
in the production of PET[3].
The process feedstock is p-xylene dissolved in acetic acid with the inclusion of bromide,
manganese and cobalt salts as catalysts[5].
2-6-2 Oxidation
groups produces crude terephthalic acid (CTA). The CTA is largely insoluble, and
consequently the reactors contain significant amounts of solid product crystals. The main
impurity of the CTA relative to PTA is determined
content[5].
Flash cooling further crystallizes product from the slurry. The solid CTA is then separated and
dried, before being re-slurried in water in preparation for purification[5].
42
PRODUCTION OF PURIFIED TPA CHAPTER 02
hydrogen initiates the following reaction. The p-toluic acid is much more soluble in water than
terephthalic acid, allowing the PTA to crystallize from solution by flash cooling while the p-
toluic acid remains dissolved. Filtration, washing and drying follow to give solid PTA[5].
PET is one of the major polymers produced worldwide representing about 18 % of world
polymer production and comes in third after polyethylene and polypropylene. PET production
profitability study is overviewed based on both local and global market.
Global production of PET in 2008 was approximately 50 million MTA. The main downstream
industries based on PET are production of polyester fibers, accounting for around 65% of
global consumption, and PET bottle resins consuming around 30%. Other applications occupy
the remaining fraction containing polyester film and polyester engineering resin[3].
Major producers are China Petrochemical Corporation (Sinopec), Reliance Industries, Formosa
Plastics Group, Gruppo Mossi & Ghisolfi, Far Eastern Textile and Alfa Group, and Eastman
chemicals in America[3].
43
PRODUCTION OF PURIFIED TPA CHAPTER 02
Global demand is predicted to grow up to 17.3 million MTA in 2011. Strong growth in demand
combined with low entry barriers has attracted far too much capacity, especially in Asia.
It was estimated that production in the last five years has grown at an average of 10.5% per
year to reach 15.8 million MTA in 2006. However, the forecast capacity growth is 4.5% per
year, in the next five years it will be lower than demand growth, improving operating rates.
Capacity is expected to reach 19.6 million MTA in 2011. Most of the capacity growth has
occurred in Asia with the majority of plants being built in China. According to market forecast
Asia will continue to produce the greatest capacity for the next few years and will be a major
exporter as it takes advantage of its low cost position[3].
Production of PET is mainly divided into two stages; the first stage is PTA production using
p-xylene as a raw material in presence of acetic acid as a solvent. The second stage is the
reaction between PTA and MEG forming PET. Hence the feedstock for PET production is p-
xylene, acetic acid, and MEG[3].
2-11-1 P-xylene
Isolation of p-xylene accounted for 82% of 41.6 million MTA in 2008 of global mixed xylenes
consumption.
44
PRODUCTION OF PURIFIED TPA CHAPTER 02
Asia is the largest p-xylene producing region, with 64% of capacity; North America produces
20% and Western Europe 9%. Global production of p-xylene in 2008 was approximately 28
million metric tons. -
xylene isomer[3].
BP is another major producer of mixed xylenes and the second-largest producer of p-xylene
and a major producer of its derivative, TPA. China Petrochemical Corporation and its affiliates
have become the second largest producer of mixed xylenes[3].
The largest use of acetic acid is the manufacture of vinyl acetate monomer which represents
33% of the total production; the second largest derivative is the production of PTA which
represents 22% of the total production which is used to produce PET bottle resins and polyester
fiber. Consultants to grow at 3-4% per year forecast global demand for acetic acid. Growth is
much higher in Asia, pulled by strong demand in China. India is also seen as a country where
there could be strong acetic acid demand growth in the future.
The two biggest producers of virgin acetic acid are Celanese and BP Chemicals. Other major
producers include Millennium Chemicals, Sterling Chemicals, Samsung, Eastman, and Svensk
Etanolkemi[3].
A fractional kinetic model for the liquid-phase oxidation of p-xylene to terephthalic acid
catalyzed by cobalt acetate and manganese acetate and promoted by hydrogen bromide.
Cincotti studied the kinetic scheme at low temperature and assumed that all the reactions were
zeroth order with respect to gaseous reactants under the condition that the oxygen partial
pressure was higher than a minimum value and first order with respect to liquid reactants. Yan
studied the oxidation kinetics at high temperature and assumed that all the reactions were 0.65th
order with respect to PX and first order with respect to the other liquid reactants, and the effect
of oxygen partial pressure on the reaction rate was neglected[6].
Virtually the entire world's supply of terephthalic acid and dimethyl terephthalate are consumed
as precursors to polyethylene terephthalate (PET). World production in 1970 was around 1.75
million tons[3].
45
PRODUCTION OF PURIFIED TPA CHAPTER 02
By 2006, global purified terephthalic acid (PTA) demand had exceeded 30 million tons. A
smaller, but nevertheless significant, demand for terephthalic acid exists in the production of
polybutylene terephthalate and several other engineering polymers[7, 8].
Polyester fibers based on PTA provide easy fabric care, both alone and in blends with
natural and other synthetic fibers. Polyester films are used widely in audio and video
recording tapes, data storage tapes, photographic films, labels and other sheet material
requiring both dimensional stability and toughness.
In addition to these end uses, Terephthalic acid based polyesters and polyamides are
also used in hot melt adhesives.
PTA is an important raw material for lower molecular weight saturated polyesters for
powder and water-soluble coatings.
In the research laboratory, terephthalic acid has been popularized as a component for
the synthesis of metal-organic frameworks.
The analgesic drug oxycodone occasionally comes as a terephthalate salt; however, the
more usual salt of oxycodone is the hydrochloride. Pharmacologically, one milligram
of terephthalas oxycodonae is equivalent to 1.13 mg of hydrochloridum oxycodonae.
Terephthalic acid is used as a filler in some military smoke grenades, most notably the
American M83 smoke grenade and M90 vehicle-employed smoke grenade, producing
a thick white smoke that acts as an obscurant in the visual and near-infrared spectrum
when burned.
46
PRODUCTION OF PURIFIED TPA CHAPTER 02
This process is considered as a different route for production of TPA starting with phthalic
anhydride or its precursor, o-xylene or naphthalene vapors, as the raw material. According to
this process phthalic anhydride, which is mainly produced through vapor phase catalyzed
oxidation of o-xylene or naphthalene in presence of V2O5 as a catalyst, is converted
sequentially to mono-potassium and then dipotassium o-phthalate by aqueous recycle of mono-
potassium and dipotassium terephthalate.
Then, dipotassium p-phthalate is converted into TPA by two methods. In the first one TPA
may be formed in two steps as shown in the following equations:
47
PRODUCTION OF PURIFIED TPA CHAPTER 02
The aqueous solution of the acid potassium phthalate obtained by second step reaction is
recycled for use in first step reaction, and the aqueous solution of potassium phthalate obtained
in 1st step reaction is recycled for use as the starting material of thermal rearrangement reaction
after being dried by evaporation or by spraying. TPA produced may be purified by dissolving
it in alkalis and precipitating it from alkaline solution with acids.
The other method for producing TPA is by blowing carbon dioxide into an aqueous solution of
potassium terephthalate to produce acid potassium salt of TPA (precipitate) and potassium
carbonate (in mother liquor), and then the acid potassium salt of TPA is reacted with phthalic
acid or anhydride in an aqueous phase so as to produce TPA (precipitate) and an acid potassium
salt of phthalic acid (in mother liquor). A solution, of which main component is potassium
phthalate, can be obtained by mixing the two mother liquor and boiling to expel carbon dioxide.
The resultant solution can be recycled and reused for preparation of the aqueous solution
containing crude potassium terephthalate and potassium phthalate, which is to be subsequently
concentrated.
48
PRODUCTION OF PURIFIED TPA CHAPTER 02
This process is done by first reacting p-xylene with ammonia on a catalyst producing TPN, and
then the intermediate TPN goes through a hydrolysis reaction where it produces TPA and
ammonia.
At first TPN is produced from p-xylene which is passed with ammonia and oxygen over a
catalyst, oxygen is used to regenerate the catalyst in place. The catalyst used in Lummus
process can be Vanadium, molybdenum or other metals while the catalyst used in Esso process
is chromia and vanadia supported on alumina, which is the mostly used catalyst for this process.
Then TPA is produced from TPN by aqueous hydrolysis in the presence of Silica gel or silica
alumina supported on phosphoric acid as a catalyst. The produced acid is produced in the
gaseous phase.
Purified TPA became commercially available from Amoco Chemical Co. in 1965. Amoco
process involves purification of crude TPA by a separate step to attain the high product purity
required for PET manufacture. This technology is the most used worldwide, but other processes
have been developed and are operating commercially.
Most of TPA precipitates, because of its low solubility in the solvent. This yields a three phase
system; solid TPA crystals; solvent with some dissolved TPA; and vapor consisting of nitrogen,
acetic acid, water, and a small amount of oxygen. The overhead vapors from the reactor are
condensed in heat exchangers, and the condensate is refluxed to the reactor. Steam, which is
generated by condensation, used as heating source in other parts of the process. Oxygen
depleted gas from the condensers is scrubbed to remove most uncondensed vapors[11].
Oxidation reactor operates at 175 - - 3000 kPa, at residence time about 2.5
hours. Reactor is lined with titanium to withstand the highly corrosive bromine and acetic acid.
49
PRODUCTION OF PURIFIED TPA CHAPTER 02
The pressure of hydrogenation reactor is held above the vapor pressure of water to maintain a
liquid phase.
Catalyst used in oxidation reactor is multivalent heavy metal. Mostly, cobalt and manganese
are the multivalent heavy-metal catalysts and bromine is the renewable source for the free
radicals. A soluble cobalt manganese bromine catalyst system is the heart of the process.
This yields nearly quantitative oxidation of the p-xylene methyl groups with small xylene
losses. Various salts of cobalt and manganese can be used, and the bromine source can be HBr,
NaBr, or tetra-bromoethane. This catalyst system is used in about 70% of the p-xylene
oxidation processes, and this percentage increases as new plants employ it.
The effluent stream from the reactor contains TPA as slurry. This slurry passes through a surge
vessel that operates at a lower pressure than the reactor. More TPA crystallizes and the cooled
slurry is then ready to be processed at close to atmospheric conditions. The slurry is fed to a
centrifugation unit at which most of water removed from the product.
After centrifugation, one stream is fed to the recovery unit and the other to a rotary drier.
Preheated air is sent to the drier to remove the moisture present in the final product. TPA
crystals are obtained from the drier by 99% purity, then conveyed to storage, from which they
are in turn fed to the purification step.
Water formed and some undesirable by-products must be removed from acetic acid solvent.
Mother liquor from the centrifuge is purified in a solvent recovery tower to purify acetic acid.
The purified acetic acid from the top of the tower is recycled to the reactor and combined with
fresh acetic acid and the bottom product can be processed for catalyst recovery and
regeneration. Vents from the oxidation process, are sent to a gas scrubbing tower then to water
removal tower to remove the water formed as the overhead stream which sent to waste water
treatment.
Amoco process involves a purification unit to achieve the required purity before entering the
polymerization step. The main impurity in the crude TPA is 4-formylbenzoic acid (up to 5000
ppm). There are also yellow impurities and residual amounts of catalyst metals and bromine.
TPA crystals are dissolved in a hot process water to increase its solubility. The slurry formed
contains at least 15 wt% TPA and the rest are impurities accessible to the purification reaction.
The solution flows through a hydrogenation reactor. Hydrogen is added to the reactor, where
it dissolves in the feed solution.
50
PRODUCTION OF PURIFIED TPA CHAPTER 02
Various colored impurities are hydrogenated to colorless products. The catalyst is highly
selective; the loss of TPA by carboxylic acid reduction or ring hydrogenation is less than 1%.
After reaction, the solution passes to a series of crystallizers where the pressure is sequentially
decreased. This results in temperature reduction, and crystallization of the TPA.
The more soluble p-toluic acid formed in the reactor, and other impurities, remain in the mother
liquor. After leaving the final crystallizer, the slurry undergoes centrifugation to yield a wet
cake, and the cake is dried to give the product TPA as a free-flowing powder. TPA is the main
product. More than 98% of the p-xylene is converted with a minimum yield of 95 mol%.
Further, this is on a once-through basis. TPA from oxidation process is called technical or crude
grade of phthalic acid, but the purity is typically greater than 99%. It is not, however, pure
enough for the PET production to reach the required degree of polymerization.
In the purification unit over 99.99 wt% of the incoming TPA is recovered as purified product.
The purified TPA as a white powder is called polymer grade TPA which is suitable to be used
in the production of PET[10].
It was the first industrial process to manufacture TPA. This process was industrialized by Du
Pont which employs the liquid phase oxidation of p-xylene by nitric acid at 165 °C and 1000
kPa, by the following overall reaction:
The TPA formed is separated by precipitation and centrifuging. After drying it is esterified by
methanol at 150 °C in the presence of sulfuric acid catalyst. Although the total yield is 90
molar%, the presence of nitrogen compounds makes purification difficult and nitrogen oxides
recovery encumbers the economics of the system [10, 12-14].
51
PRODUCTION OF PURIFIED TPA CHAPTER 02
A brief comparison of the discussed processes will help us understand that why we selected
the respective process as our production process. The comparison is done in tabular form in
order to fully understand the selection (side by side comparison).
Cobalt
Amoco process >99% 200oC Manganese
16 bars &
HBr promotor
Vanadium pentoxide
Lummus process* 90% 400-450 oC supported on
Aluminum oxide
Product contains
Du pont process impurities as 148- Auto Catalytic
nitrogenous 8.6-13.7 bar
compounds
Amoco Process
the following factors:
52
PRODUCTION OF PURIFIED TPA CHAPTER 02
Para xylene, acetic acid and the CMB catalyst (Cobalt acetate, Manganese acetate and
Hydrogen bromide acid) are all mixed together at an ambient temperature of 25oC. The mixture
is then introduced into the reactor by passing it through a pump and a pre-heater which raises
its pressure and temperature to 200oC and 16 bar respectively. Moreover, pre-treated air is
compressed to 16 bars, then cooled to 200oC and is introduced into the reactor. The reaction
occurs at 200oC and 16 bar pressure producing TPA, 4-CBA* (as impurity) and water. Due to
the exothermic heat of reaction, the acetic acid is vaporized and it is purged out with unreacted
air. The acetic acid is then condensed and recycled into the reactor.
The product stream flows to a crystallizer where it throttled to atmospheric pressure and some
flash to vapor phase. The product stream is crystallized by creating super-
saturation through evaporation. The flash acetic acid, water and p-xylene are also condensed
and are sent to the recovery section. The slurry from crystallizer is further passed through a
centrifuge and a drier to remove remaining acetic acid, p-xylene and water. Finally, a 99%
product is obtained at the end of the crude TPA production section. The product majorly
contains TPA and minor amounts of 4-CBA as impurity.
The Crude TPA is further treated to remove the remaining 4-CBA impurity in the purification
section. In this section, the Crude TPA is mixed with water again to make a diluted slurry. It is
then motivated to 40 bar and heated to 235oC and introduced into the reactor. The other reactant
is pure Hydrogen gas which also compressed to 40 bar, cooled to 235oC and then it is also
introduced into the reactor. The reaction occurs and the maximum amount of 4-CBA is
converted into p-toulic acid. The p-toulic acid is soluble in water and is easy to remove as
compared to 4-CBA. The Product slurry is then crystallized at a lower temperature of 25oC and
atmospheric pressure in order to crystallize a pure product. Almost all the P-toulic acid remains
in water and the Purified TPA is then centrifuged and dried in order to obtain a 99.99% pure
TPA product[14].
53
PRODUCTION OF PURIFIED TPA CHAPTER 02
54
PRODUCTION OF PURIFIED TPA CHAPTER 02
Name P-xy Acetic CMB Feed Feed Feed Air Air Reactor
pump acid catalyst mixer Mixture Pre- compressor cooler (CSTR)
pump pump pump heater
Item P-201 T-201 P-202 H-201 CS-201 H-202 R-201 V-201 CR-201
#
Name Water Re- Slurry Slurry Hydrogen Hydrogen Reactor Throttle Crystallizer
Pump Slurry Pump Pre- compressor cooler (Fixed valve
Tank heater bed)
For example, in the annual reports of Lotte chemicals Pakistan ltd. they mentioned that the
local polyester industry demand of TPA has increased 10% from 2017 to 2018. The chart shows
the comparison of TPA demand, production of Pakistan and operating rates of the Lotte
Chemicals Pakistan ltd[15].
55
PRODUCTION OF PURIFIED TPA CHAPTER 02
The total demand of TPA of Pakistan is 780,000 MT per year as of 2018. The Lotte Chemicals
have a plant of a capacity of 500,000 MT TPA per year. They are the sole bulk producers of
TPA in Pakistan. Moreover, Pakistan is still importing the deficit amount TPA from
neighboring countries like China.
From the above discussion and data, we selected the capacity of 265 MT per day. We will be
complete about 12% demand of TPA in Pakistan[15].
56
CHAPTER 3
Material
&
Energy Balance
PRODUCTION OF PURIFIED TPA CHAPTER 03
58
PRODUCTION OF PURIFIED TPA CHAPTER 03
3-2-1 Assumptions
Steady State
3-2-2 General Material Balance Equation
P-xylene TPA
C8H10+2.5O2 8H6O3+2H20
4-CBA
Conversion = 98%
59
PRODUCTION OF PURIFIED TPA CHAPTER 03
60
PRODUCTION OF PURIFIED TPA CHAPTER 03
*Key note
Internal jacketed crystallizer
Partial condenser of efficiency 70%
61
PRODUCTION OF PURIFIED TPA CHAPTER 03
62
PRODUCTION OF PURIFIED TPA CHAPTER 03
Acetic 534.650
acid(v)
Acetic 1247.517
acid(l)
Total input 54611.481 Total output 54611.481
*Key note
F11 streams goes to the recovery section
Efficiency of centrifuge 70%
63
PRODUCTION OF PURIFIED TPA CHAPTER 03
64
PRODUCTION OF PURIFIED TPA CHAPTER 03
*Key Note
Fixed bed catalytic reactor
Conversion = 99%
C8H6O3 + 2H2 8H8O2 + H20
4-CBA P-toulic acid
65
PRODUCTION OF PURIFIED TPA CHAPTER 03
66
PRODUCTION OF PURIFIED TPA CHAPTER 03
67
PRODUCTION OF PURIFIED TPA CHAPTER 03
68
PRODUCTION OF PURIFIED TPA CHAPTER 03
ENERGY BALANCE
69
PRODUCTION OF PURIFIED TPA CHAPTER 03
70
PRODUCTION OF PURIFIED TPA CHAPTER 03
71
PRODUCTION OF PURIFIED TPA CHAPTER 03
Cp = 9.16E+04 J/kmoleK
Q = -571.1930961 kW
F8
F9
CR-101
F10
72
PRODUCTION OF PURIFIED TPA CHAPTER 03
73
PRODUCTION OF PURIFIED TPA CHAPTER 03
F8 F8'
C-102
T1 T2
-100.56 -74.6
Duty of condenser(J/hr) -4.57E+09
In kwatt -1270.618176
F12
F13' F13
DR-101
F14'
74
PRODUCTION OF PURIFIED TPA CHAPTER 03
T = 313K
75
PRODUCTION OF PURIFIED TPA CHAPTER 03
F16' F16
CS-201
Figure 3- 20 Compressor 2 heat balance
76
PRODUCTION OF PURIFIED TPA CHAPTER 03
At = 190K
Table 3- 36 Reactor 2 heat balance
TPA 7.36E+09 TPA 7.36E+09
CBA 1.50E+09 CBA 3.42E+06
Water 5.71E+13 Water 5.72E+13
Hydrogen 8.25E+07 P-toluic acid 9.59E+05
Total 5.71E+13 Hydrogen 2.43E+06
Total 5.72E+13
- /hr) of product 4.39E+09 (J/hr)
1220.491
77
PRODUCTION OF PURIFIED TPA CHAPTER 03
F19
F18
F19''
CR-201
F20
78
PRODUCTION OF PURIFIED TPA CHAPTER 03
F19' F19
F22
F23 F23'
DR-201
F24
79
PRODUCTION OF PURIFIED TPA CHAPTER 03
80
CHAPTER 4
Equipment Design
PRODUCTION OF PURIFIED TPA CHAPTER 04
4 EQUIPMENT DESIGN
82
PRODUCTION OF PURIFIED TPA CHAPTER 04
Economical
Difficult cleaning
Cleaning easily
83
PRODUCTION OF PURIFIED TPA CHAPTER 04
Where;
Cp = heat capacity
Q = 1680 kW
m = 31756 kg/hr
LMTD = 116 oC
84
PRODUCTION OF PURIFIED TPA CHAPTER 04
4-1-4-5 Assumption:
U = 568 W/m2K
A = 25.42 m2
BWG = 16
Length = 3.66 m
Passes = 2
Db =
k1 = 0.249
n1 =2.207
Db = 0.3058
85
PRODUCTION OF PURIFIED TPA CHAPTER 04
Mass velocity = G = mt / at
G =313367 kg/m2hr
86
PRODUCTION OF PURIFIED TPA CHAPTER 04
hi =
hi = 990.925
ho[18] =
ho = 3719.497
1/U = 0.001278
Ud = 782 W/m2 oC
Equivalent diameter = De =
De = 0.0135m
Flow area = As =
Shell side
87
PRODUCTION OF PURIFIED TPA CHAPTER 04
Ps =
= 6.12 psi
Tube side
Np = number of passes = 2
1.57 psi
88
PRODUCTION OF PURIFIED TPA CHAPTER 04
Temperature =
89
PRODUCTION OF PURIFIED TPA CHAPTER 04
Classification
of Reactors
Mode of Phases in
operation contact
For the production of Purified Terephthalic Acid (PTA) basically our reaction is liquid gas
reaction.
90
PRODUCTION OF PURIFIED TPA CHAPTER 04
The contacting pattern between gas and liquid can be one of the following:
Wetted-wall column
91
PRODUCTION OF PURIFIED TPA CHAPTER 04
Well mixed
92
PRODUCTION OF PURIFIED TPA CHAPTER 04
Calculating the volume of continuous stirred tank reactor using performance equation
as follows
= V / Vo
Volume of cylinder = r 2l
A= 2 rl
93
PRODUCTION OF PURIFIED TPA CHAPTER 04
Figure 4- 3 Lumped kinetic scheme for the oxidation of p-xylene to terephthalic acid[6]
k = 0.0345 min-1
CA = 0.066 kmol/m3
-ra = k CAn
By putting values,
94
PRODUCTION OF PURIFIED TPA CHAPTER 04
V = 189.732 m3
Approximately,
V = 190 m3
V = 190×0.10 +190
V = 209 m3
L=3D D=
A= 2 rl
A = 2×3.14×2.161×12.963
A = 175.88 m2
H = 14.65 MW
95
PRODUCTION OF PURIFIED TPA CHAPTER 04
DOWTHERM (eutectic mixture of two very stable organic compounds, biphenyl and
diphenyl oxide).
.
Q = mCp T m = Q/Cp T
By putting values;
.
m = 159.42 kg/sec
Calculating T LMTD
T LMTD = 146
Q = UA TLMTD
U = Q/A TLMTD
By putting values,
U = 572 W/ m2K
Where Vi = µ / µw
96
PRODUCTION OF PURIFIED TPA CHAPTER 04
[18]
Re = 735798.9 Pr = 23.850
ho = 7781 W/ m2K
U = 571 W/m2K
A = 176 m2
Viscosity of liquid
Degree of Mixing
Power Requirement
RPM
97
PRODUCTION OF PURIFIED TPA CHAPTER 04
Viscosity For low to For moderate For low to high viscous fluids
moderate viscous liquids
Viscous liquids
Flow For Axial flow For radial and For radial and Tangential flow,
pattern Tangential Flow sometimes Axial flow also
Types Square pitched Flat paddle, Flat, Curved and Pitched Blade
Blades 3-blade, 4-blade, 2 and 4 bladed 2-8 Blades, But six blades is used
Toothed paddles as standard
1150-1750
98
PRODUCTION OF PURIFIED TPA CHAPTER 04
Flow Arrangement
For gas liquid, radial flow pattern for gas dispersion as well as Axial for
Heat transfer enhancement and promotion of chemical reaction is required.
99
PRODUCTION OF PURIFIED TPA CHAPTER 04
Design Procedure
Calculating impeller diameter (Da), distance of turbine blades from the tank bottom
(E), width of blades (W) and length of blades (L).
NRe = Da2 Nr /
Calculating number of revolutions per minute by using tip velocity relation given by:
V = Da Nr Nr = V/ Da
100
PRODUCTION OF PURIFIED TPA CHAPTER 04
Nr = 1.133 RPS
NRe = Da2 Nr /
NRe = 9218354
As the Value of Reynolds no. is greater than 10,000 so power number Npo = KT
By putting values;
P = 16 hp
Power Consumption 16 hp
101
PRODUCTION OF PURIFIED TPA CHAPTER 04
It includes
Choice of Head
Stainless Steel
Martensitic Austenitic
Ferritic
I have selected Austenitic type Stainless Steel -304 whose maximum allowable
temperature is 900.
102
PRODUCTION OF PURIFIED TPA CHAPTER 04
Choice of Heads
Heads of various shapes close the ends of a cylindrical vessel. The principal types used are[17]:
Hemispherical heads
Ellipsoidal heads
Tori-spherical heads
Decision-making
Standard tori-spherical heads (dished ends) are the most commonly used end closure
for vessels up to operating pressures of 15 bar.
They can be use for higher pressures, but above 10 bar their cost should be compared
with that of an equivalent ellipsoidal head.
Above 15 bar an ellipsoidal head will usually prove to be the most economical closure
to use.
Hemispherical heads are use for high pressures but are not economical. Therefore, I
choose ellipsoidal head for my reactor, as my operating pressure is 16 bar.
Design pressure
A vessel must be designed to withstand the maximum pressure to which it is likely to
be subjected in operation.
For vessels under internal pressure, the design pressure is normally 5 to 10 per cent
above the normal working pressure[17].
Design temperature
The strength of metals decreases with increasing temperature so the maximum allowable
design stress will depend on the material temperature[17].
103
PRODUCTION OF PURIFIED TPA CHAPTER 04
The equation used for calculating the wall thickness of cylindrical shell is as follows[18]:
By putting values,
t = 0.0460 m
The equation used for calculating the wall thickness of Ellipsoidal heads is as follows[18]:
By putting Values,
t = 0.047 m
104
PRODUCTION OF PURIFIED TPA CHAPTER 04
105
PRODUCTION OF PURIFIED TPA CHAPTER 04
Brief Introduction
Classification of dryers
Selection of dryer
Design considerations
In general, drying a solid means the removal of relatively small amounts of water or other
liquid from the solid material to reduce the content of residual liquid to an acceptably low
Drying is usually the final step in a series of operations, and the product from a dryer is often
ready for final packaging. In a dryer, Water or other liquids are removed from solids thermally
by vaporization.
The method in which solid is directly exposed to the hot gases (usually air).
The method in which heat is transferred to the solid from an external medium such as
condensing steam, usually through a metal surface with which the solid is in contact.
Dryers that expose the solids to the hot gases are called adiabatic or direct dryers while
those in which heat is transfer from the external medium are known as non-adiabatic or
indirect dryers[23].
106
PRODUCTION OF PURIFIED TPA CHAPTER 04
For throughputs greater than 50,000 Kg/day, continuous dryers are used. So
indirect Heat Continuous Dryers are selected.
It consists of a cylinder, rotated upon suitable bearings and usually slightly inclined to
the horizontal.
Wet feed enters one end of the cylinder progress through it by virtue of rotation and
slope of the cylinder and discharge as finished product at the other end.
In this dryer solids are directly exposed to hot gas usually air[23].
107
PRODUCTION OF PURIFIED TPA CHAPTER 04
A-dryer shell, B-shell supporting rolls, C-drive gear, D-Air discharge hood, E- discharge fan, F- feed chute,
G-lifting flights, H-Product discharge, J-Air heater
Drum Slope
Rotational Speed
Lifting Flights
Residence Time
Outlet Humidity
Moisture Contents
108
PRODUCTION OF PURIFIED TPA CHAPTER 04
Xa = 0.0478= 4.78 %
Xb = 0 %
Temperature of air
We are using steam heated air for drying and for this air inlet temperature varies (given in
M from 120 to 175 Co
The higher the temperature of inlet gas stream, the higher the efficiency of the dryer in general.
Inlet humidity of air is found with the help of dry bulb temperature (room temp) of air and wet
bulb temperature of entering air from Humidity chart.
s handbook
Now this air is heated by steam from 32 Co to 148 Co (dry bulb temp. of heated air) and the wet
bulb temperature of heated air is found with the help of dry bulb & humidity of heated air
entering the dryer from humidity chart.
109
PRODUCTION OF PURIFIED TPA CHAPTER 04
It is estimated from
Where
Ta = 421K
T Wb = 318.53K
Temperature of Feed
110
PRODUCTION OF PURIFIED TPA CHAPTER 04
As it is clear from figure that feed inlet temp. Should be less than gas outlet temp. and it
should also less than wet bulb temp. of air, so our selected feed inlet temperature is correct.
From the above figure it is clear that outlet temp. of solid is slightly greater than gas outlet
temp. So our selected solid outlet temperature is correct.
4-3-11 Temperatures
111
PRODUCTION OF PURIFIED TPA CHAPTER 04
Heat the feed (solid & liquid) to the vaporization (wet bulb) temperature.
Vaporize the liquid.
Heat the solids to their final temperature.
Heat the vapor to its final temperature.
In general, rate of heat transfer per unit mass can be calculated as follows
Where;
ms = 97.216 kmol/hr
Tsa = 298.15 K
Tsb = 408.15 K
Ta = 421K
Tb = 341.3941
T Wb = 318.53
Xa = 0.0478= 4.78%
Xb = 0
112
PRODUCTION OF PURIFIED TPA CHAPTER 04
qt = 461989 kJ/hr
Where
H1 = Inlet humidity
mg = 5458 kg/hr
The allowable mass velocity of air in direct contact rotary dryer ranges from 400 to 5000 lb/Ft2
hr.
It can be found as
A= 0.797 m2
113
PRODUCTION OF PURIFIED TPA CHAPTER 04
D =1.007 m
Drying diameter ranges from 1 to 3m (McCabe, Herriot, & smith), thus the computed diameter
is accepted.
The following empirical equation is used to calculate the overall heat transfer coefficient from
perry, mccabe handbook with the index n=0.67(McCormick, 1962). The k value fall in the range
3.75 to 5.25 as suggested by AICHE for SI unit.
Assuming k = 5.25
Ua =1935.715 kg/m3hrK
V= Qt / Ua Tlm
V = 4.463 m3
4-3-21 Calculation for log mean of drying gas wet bulb depression at inlet
& exit end of dryer ( Tm)
Log mean depression of Wet bulb ( Tlm) is found from given formula
114
PRODUCTION OF PURIFIED TPA CHAPTER 04
Tlm = 53.46 K
L = 5.603 m
L/D = 5.6025/1.007
L/D = 5.56
L/D ratio is more efficient between 4 and 10 for industrial dryers, therefore above length and
diameter can be accepted.
Speed value ranges 0.1 to 0.5 m/s, assuming the peripheral speed of rotation to be 0.1m/s.
RPM = 6
The revolution of the dryer varies between 2-5 rpm. Therefore, the above value can be accepted.
No. of Flights
No. of Flights = 3D
The flight heights in direct rotary dryer will range from 1/12 to 1/8 the of dryer diameter.
115
PRODUCTION OF PURIFIED TPA CHAPTER 04
FD = D/8
FD = 0.125 m
The shape of the flights depends upon the handling characteristics of the solids. For free flowing
materials, a radial flight with a 900 lip is employed.
Use the following empirical equation for the residence time (in minutes) in dryers are
rec
B = 5dp-0.5
B = (130)-0.5 = 0.439
= 3min
Residence time for the rotary dryer typically ranges at 5-90 min (copper, Penney, Perry, wales,
2005).
Where
H2 = Outlet Humidity
H1 = Inlet Humidity
116
PRODUCTION OF PURIFIED TPA CHAPTER 04
ms =11652.996 kmol/hr
mg =5457.342 kg/hr
Xa = 0.047
Xb = 0
117
PRODUCTION OF PURIFIED TPA CHAPTER 04
Operation Continuous
Design Data
Utilities Steam
118
PRODUCTION OF PURIFIED TPA CHAPTER 04
Temperatures
Temperature (K)
119
PRODUCTION OF PURIFIED TPA CHAPTER 04
1) Tank Crystallizer
2) Scraped-Surface Cooled Crystallizer
3) Circulating Magma or Forced Circulation Crystallizer
4) Circulating Liquor Crystallizer
This typed is similar in principle to the tank type, but the cooling surfaces are continuously
scraped or agitated to prevent fouling by deposited crystals and to promote heat transfer. They
are suitable for processing high viscosity liquor. Scraped surface crystallizers can be operated
batch-wise, with recirculation of the mother liquor, or continuously. A disadvantage of this
type is that they tend to produce very small crystals. A typical unit is Swenson-Walker
crystallizer.
In this type, both the liquor and growing crystals are circulated through the zone in this zone
in which super-saturation occurs. Circulating magma are probably the most important type of
large scale crystallizers used in the chemical process industry. Designs are available in which
super-saturation is achieved by direct cooling, evaporation or evaporative cooling under
vacuum.
120
PRODUCTION OF PURIFIED TPA CHAPTER 04
In this type only the liquor is circulated through the heating or cooling equipment, the crystals
are retained in suspension in the crystallizing zone by the up flow of liquor. Circulating liquor
crystallizer produce crystals of regular size. The basic design consists of three components; a
vessel in which the crystals are suspended and grow and are removed, a means of producing
super-saturation and mea
design for this type of crystallizing equipment. Circulating liquor crystallizers are used for the
large scale production of a wide range of crystal products.
4-4-6 Pre-Requisites
According to our operation some of the pre-requisites or requirements are as listed below
Continuous operation
Super-saturation must be obtained by cooling
Processing of organic material
Prevention of foul prevention
121
PRODUCTION OF PURIFIED TPA CHAPTER 04
4-4-7-1 Advantages
4-4-7-2 Disadvantage
122
PRODUCTION OF PURIFIED TPA CHAPTER 04
4-4-8-2 Properties
Listed below are the tables that shows the properties of the magma stream.
4-4-8-3 Solubility:
Solubility(kg/kg of solvent)
10
Solubility (Kg/Kg of solvent)
9
8
7
6
5
4
3
2
1
0
0 50 100 150 200 250 300
Temperature (oC)
Figure 4- 6 Solubility trend of TPA in Water
123
PRODUCTION OF PURIFIED TPA CHAPTER 04
4-4-8-4 Assumptions
The value of residence time and crystal size are taken from literature which are as follows;
Sizing
Vessel Sizing
Where,
V = Volume of Crystallizer
D = 2.986 m
124
PRODUCTION OF PURIFIED TPA CHAPTER 04
Cone Volume
Vc = 6.0381 m3
Angle of Repose
Angle of Repose for Terephthalic acid is 40o. Hence the angle of Cone should be around 35o
i.e less than angle of repose.
Height of Cone
H = Tan
Hc = 0.94 m
V = 44.219 m3
H = 5.42 m[24]
125
PRODUCTION OF PURIFIED TPA CHAPTER 04
mw = 130811.987 kg/hr
Initial T1 = 100 t1 = 25
Final T2 = 25 t2 = 90
Temperature Differences T1 = T1 - t1 T2 = t2 - T2
75 65
lm = 69.88 oC
Also, average overall heat transfer coefficient for this specific problem is taken from Plant
Design and Economics by Peter and Timmershaus.
Uc = 1200 W/ m2 oC
Heat of Crystallization is
Qc = 0.121 kJ/kg
2.807 kg/sec
Hence,
Qc = 339.663 kJ/hr
Or,
126
PRODUCTION OF PURIFIED TPA CHAPTER 04
A = 51 m2
Tube Side
At = 0.326 m2
Number of Tubes = Nt =
Nt = 157
NRe = 4069.306
hi = 2267.41 W/m2 oC
Shell Side
127
PRODUCTION OF PURIFIED TPA CHAPTER 04
K1 = 0.319, n1 = 2.142
Db = 0.308 m
Dia of Shell = Ds = Db
Ds = 0.400 m
Equivalent Dia = De =
De = 0.0123
As = 0.00479 m2
NRe = 41833.22
jH = 100
ho[18] =
ho = 7588.28 W/m2 oC
128
PRODUCTION OF PURIFIED TPA CHAPTER 04
Hence,
Ud = 481 W/m2 oC
Where;
q = Heat of crystallization
129
PRODUCTION OF PURIFIED TPA CHAPTER 04
Evaporation rate is
46089.450 kg/hr
Hence
E = 6483.869 kg/hr
Where ever there is considerable evaporation of liquid, the maximum vapor velocity is an
important parameter to calculate as it can affect the design of such vessel. It is given by souders-
brown equation[17] and it is written as follows
Where;
= density of vapors
= density of liquid
u = 0.940 m/sec
130
PRODUCTION OF PURIFIED TPA CHAPTER 04
So, Yield is
Y = 11120.537 Kg of crystals
131
PRODUCTION OF PURIFIED TPA CHAPTER 04
132
CHAPTER 5
Cost Estimation
PRODUCTION OF PURIFIED TPA CHAPTER 05
5 Cost Estimation
Purchased cost = Bare cost from figure time base (2004) material factor pressure factor
Diameter = 4.321 m
For
Material factor = 2
Pressure factor = 1
Purchased cost = Bare cost from figure time base (2004) material factor pressure factor
Diameter = 2.986 m
For
Pressure factor = 1
134
PRODUCTION OF PURIFIED TPA CHAPTER 05
Purchased cost = Bare cost from figure time base (2004) material factor pressure factor
Area = 32 m2
Material factor = 1
Pressure factor = 1
135
PRODUCTION OF PURIFIED TPA CHAPTER 05
The cost of single stage centrifugal pump can be estimated from the following graph:
Purchased cost in (2004) = Bare cost from graph material factor pressure factor
Purchased cost = Bare cost from figure time base (2004) material factor pressure factor
Diameter = 0.64 m
Length = 6 m
For
Material factor = 2
Pressure factor = 1
136
PRODUCTION OF PURIFIED TPA CHAPTER 05
Hence
137
PRODUCTION OF PURIFIED TPA CHAPTER 05
Direct cost
Indirect cost
TCI = $4014705.4
Assume that FCI depreciate by straight line method for 15 years assuming 5% of salvage
value at the end of plant life
138
PRODUCTION OF PURIFIED TPA CHAPTER 05
Depreciation = D = (v-vs)/N
V = FCI = $3704290.0
N = No. of years = 15
D = $234605.0
Total manufacturing cost = Fixed charges + direct production cost + plant overhead
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Taxes =$819991226.5
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CHAPTER 6
Process Simulation
PRODUCTION OF PURIFIED TPA CHAPTER 06
6 Process Simulation
Process Simulation is a key activity in Process Engineering covering the whole life cycle of a
process, from Research & Development to Conceptual Design and Plant Operation.
HYSYS is a powerful simulation tool that has been designed to solve complex engineering
problems along with the steady state and dynamic modeling capabilities and represent a
significant progression in the engineering software industry.
The numerous components of Aspen HYSYS provide a powerful approach to steady state
modeling, mass and energy balances, equipment design, optimization and cost estimation etc.
First open the Aspen HYSYS and opened the new window.
Then added the components in the components section.
1. Acetic Acid
2. P- Xylene
3. Cobalt Acetate (As Hypothetical Solid)
4. Manganese Acetate (As Hypothetical Solid)
5. Hydrogen Bromide Acid
Then added the fluid package in the fluid package section
o NRTL (Non-Reacting Two Liquid Model)
Then added the reaction in the reaction type section and add reaction kinetics.
Then added the Shell and Tube Pre-Heater H-101 and named the steams which are
added and removed from it.
Then added the parameters and conditions H-101 and calculated the results from it.
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Figure 6- 3 Worksheet
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CHAPTER 7
Instrumentation &
Control
PRODUCTION OF PURIFIED TPA CHAPTER 07
Here is given a short outline of these control schemes, so that to justify out selection of a control
loop for specified equipment.
7-2-1 Process
Any operation or series of operations that produce a desired final result in a process.
As all parts of control system, measuring element is perhaps the most important. If
measurements are not made properly the remainder of the system cannot operate satisfactorily,
also the measured variable is chosen to represent the desired conditions in the process.
7-2-3 Controller
The controller is the mechanism that responds to any error detecting mechanism. The output
of the controller is predetermined function of the error.
The final control element receives the signal from the controller and by some predetermined
relationship change energy input to the process.
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This is used to control the temperature of outlet and inlet streams in heat exchanger, condenser,
heater and column, most temperature measurement in the industrial processes is made by
means of thermocouples to facilitate bringing measurements to a controlised location.
Usually where high measurement accuracy is required resistance thermometer are used. For
the control of temperature, pneumatic feedback control is used. Outlet temperature of the
system is measured, with the help of thermocouple. This temperature is fed to a comparator.
The difference between the set point and the input signal is called error, is fed to the controller,
which controls diaphragm valve to adjust the flow of hot or cooling medium[26].
The control objective is to keep the exit temperature at 200 oC for our shell and tube pre heater.
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CHAPTER 8
HAZOP Study
&
Enviromental Impact
Assessment
PRODUCTION OF PURIFIED TPA CHAPTER 08
A HAZOP survey is one of the most common and widely accepted methods of systematic
qualitative hazard analysis. It is used for both new or existing facilities and can be applied to a
whole plant, a production unit, or a piece of equipment It uses as its database the usual sort of
plant and process information and relies on the judgment of engineering and safety experts in
the areas with which they are most familiar. The end result is, therefore reliable in terms of
engineering and operational expectations, but it is not quantitative and may not consider the
consequences of complex sequences of human errors. The objectives of a HAZOP study can
be summarized as follows:
To identify (areas of the design that may possess a significant hazard potential.
To identify and study features of the design that influence the probability of a
hazardous incident occurring.
To ensure that a systematic study is made of the areas of significant hazard potential.
To provide a mechanism for feedback to the client of the study team detailed
comments.
Specify the purpose, objective, and scope of the study. The purpose may be the analysis
of a yet to be built plant or a review of the risk of unexisting unit. Given the purpose
and the circumstances of the study, the objectives listed above can he made more
specific. The scope of the study is the boundaries of the physical unit, and also the range
of events and variables considered. For example, at one time HAZOP's were mainly
focused on fire and explosion endpoints, while now the scope usually includes toxic
release, offensive odor, and environmental end-points.
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The initial establishment of purpose, objectives, and scope is very important and should
be precisely set down so that it will be clear, now and in the future, what was and was
not included in the study. These decisions need to be made by an appropriate level of
responsible management.
Select the HAZOP study team. The team leader should be skilled in HAZOP and in
interpersonal techniques to facilitate successful group interaction. As many other
experts should be included in the team to cover all aspects of design, operation, process
chemistry, and safety. The team leader should instruct the team in the HAZOP
procedure and should emphasize that the end objective of a HAZOP survey is hazard
identification; solutions to problems are a separate effort.
8-3 Study:
1) Collect data. Theodore16 has listed the following materials that are usually needed.
Process description.
Data on the chemical, physical and toxicological properties of all raw materials,
intermediates, and products.
Layout drawings.
Operating procedures.
Maintenance procedures.
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Conduct the study. Using the information collected, the unit is divided into study "nodes" and
the sequence diagrammed in Figure, is followed for each node. Nodes are points in the process
where process parameters (pressure, temperature change between nodes as a result of the
operation of various pieces of equipment' such as distillation columns, heat exchanges, or
pumps. Various forms and work sheets have been developed to help organize the node process
parameters and control logic information.
When the nodes are identified and the parameters are identified, each node is studied by
applying the specialized guide words to each parameter. These guide words and their meanings
are key elements of the HAZOP procedure. They are listed in Table (9.1).
Hazop Study
Repeated cycling through this process, which considers how and why each parameter might
vary from the intended and the consequence, is the substance of the HAZOP study.
2) Write the report. As much detail about events and their consequence as is uncovered
by the study should be recorded. Obviously, if the HAZOP identifies a not
improbable sequence of events that would result in a disaster, appropriate follow-
up action is needed. Thus, although risk reduction action is not a part of the HAZOP,
the HAZOP may trigger the need for such action.
The HAZOP studies are time consuming and expensive. Just getting the P & ID's up to date on
an older plant may be a major engineering effort.
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Still, for processes with significant risk, they are cost effective when balanced against the
potential loss of life, property, business, and even the future of the enterprise that may result
from a major release.
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8-4 Definition
Provides for a plan which will reduce or offset the negative impacts of a project
The proposed project is for the production of 265 tons/day production of Terephthalic acid
located at Gwadar, Baluchistan. The raw materials used for this production are para-xylene,
acetic acid, catalyst that is the combination cobalt acetate, manganese acetate salts and
hydrogen bromide as promoter. Hydrogen is used in purification section.
8-5 Exposure
The Toxicity of the product is not very high. Terephthalic acid has low order of toxicity.
The normal precautions used in handling industrial chemicals should be observed. If
ventilation is inadequate a toxic dust respirator should be used to avoid prolonged
exposure. However, the industry has other chemicals as waste (Acetic Acid, Para
Xylene etc.).
Degradation of terephthalic acid by soil bacteria was shown by multiple studies to
happen rapidly (near complete removal via several different studies within a few days)
via both aerobic and anaerobic bacterial degradation.
The half-life of terephthalic acid in aquatic media is estimated to be 1.1 years with
respect to chemical destruction via hydroxyl radicals. However, the net aquatic half-
life should be much shorter due to biodegradation[27].
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8-6 Flammability
The flammability limits for Terephthalic acid are given below.
Ignition Index 3
Concentration
By spark ignition 80
Concentration
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8-8 Treatment
Considering all these factors the waste water from the plant should be treated properly before
letting into the water channel. Since the waste water contains organic compounds like acetic
acid and p-Xylene it is necessary to recover these organic contents and then proceed with the
treatment of the water. Water treatment procedure contains three stages. The primary method
comprises of the removal of large floatation and suspended impurities.
The equipment used are Sedimentation Tanks, etc. The secondary treatment is a step where the
process of biodegradation takes place. Here the oxygen supplied to the bacteria is consumed
under controlled condition. The idea behind it is to consume all the oxygen in the plant rather
than in the water course. The process is also known as activated sludge process. Trickling filters
are commonly used for this purpose[27].
8-8-1 Concentration:
This step involves the removal of water so that the volume is reduced as much as possible to
facilitate the efficient handling of the sludge.
8-8-2 Digestion:
This is the stage where the sludge is stabilized by digesting it under aerobic or anaerobic
conditions.
8-8-3 Conditioning:
The stabilized sludge is added with some chemicals like iron salt, alum, lime and
polyelectrolyte to improve its dewatering characteristics.
8-8-4 Dewatering:
The sludge is further processed for removal of water by mechanical means. This product from
this stage is a solid waste material.
8-8-5 Oxidation:
The sludge is oxidized to remove any un-oxidized organic matter and stabilized further.
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Terephthalic acid is used primarily to make polyethylene terephthalate (PET) resins and fibers.
The majority of end uses for PET are consumer applications. PET containers are used for a
wide variety of food and beverage packaging. Terephthalic acid is non-volatile, so the potential
for residual Terephthalic acid off-gassing is limited. Possible consumer exposures to
Terephthalic acid may occur through dermal contact with PET products, as a result of
consumption of food products stored in PET containers, or through the inadvertent ingestion
of PET particles or films. Although there is little information in the public domain concerning
residual Terephthalic acid in PET, the residual level is believed to be very low. This is because
the nature of the equilibrium condensation polymerization that is used to make PET requires
that residual monomer levels be very low in order to produce a high molecular weight polymer
such as those used in typical fiber and packaging applications. Theoretical calculations for a
typical PET polymer predict that the residual Terephthalic acid should be less than 10 ppm [1].
Migration of Terephthalic acid into food simulants has been found to be less than 0.2 mg/kg
food simulant even under severe test conditions (3% acetic acid, 2 hours at 100oC and HB307
synthetic triglyceride oil, 2hours at 100oC. Migration under more typical, less severe conditions
of use is expected to be significantly less. Based on this information, there is very little potential
for exposure to Terephthalic acid from consumption of food stored in PET containers or
through dermal contact[27].
A small number of large producers using continuous enclosed processes, with limited
occupational exposure, manufactures Terephthalic acid as a solid or a melt. Based on data,
workers in Terephthalic acid loading and chemical operations are estimated to have potential
inhalation dose rates ranging from <0.07 to 180 mg/day. In one U.S manufacturing site, the air
concentrations of Terephthalic acid for worker exposures were an average of 1.18 mg/m3
(range 0.006 to 13.59 mg/m3).These exposures do not take into account the use of respiratory
protection.
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PRODUCTION OF PURIFIED TPA CHAPTER 08
If respirators are used, and appropriately selected, used and maintained in accordance with an
acceptable respiratory protection program, dose rates would be less than 30 mg/day[27].
Environmental Precautions:
Prevent further leakage or spillage if safe to do so. Do not contaminate water. Avoid discharge
into drains, water courses or onto the ground. In case of large spill, dike if needed.
Remove all sources of ignition. Stop the flow of material, if this is without risk. Prevent entry
into waterways, sewer, basements or confined areas. Dike the spilled material, where this is
possible.
Use spark-proof tools and explosion-proof equipment. All equipment used when handling the
product must be grounded. Absorb spill with an inert material (e.g. vermiculite, dry sand, earth,
cloth, and fleece) and place in a suitable non-combustible container for reclamation or disposal.
Do not use combustible materials, such as sawdust. Clean contaminated surface thoroughly.
Neutralize spill area and washings with soda ash or lime. Never return spills in original
containers for re-use. Clean up in accordance with all applicable regulations[31].
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265 MTPD Production of Purified Terephthalic Acid by Amoco Process
Appendix
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265 MTPD Production of Purified Terephthalic Acid by Amoco Process
9 APPENDIX
Tables
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265 MTPD Production of Purified Terephthalic Acid by Amoco Process
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Charts
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265 MTPD Production of Purified Terephthalic Acid by Amoco Process
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265 MTPD Production of Purified Terephthalic Acid by Amoco Process
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