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1.1.1 History
The next morning, Plunkett was shocked when he discovered that the cylinder
recordedzero pressure despite having the same amount weight as it had on the day
before. Curiously, both Plunkett and his technician cut open the cylinder and discovered
a small amount of slippery white substance alongside the wall of the container. They
soon analyzed the waxy powder and gave name to the new substance as
polytetrafluoroethylene, later trademarked as Teflon by DuPont Company (Ebnesajjad,
2016).
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Figure 1.1: Dr. Roy Plunkett, founder of PTFE (Source: Marcote UK Ltd., n.d.).
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Figure 1.2: Chemical structure of PTFE.
1.1.3 Applications
Since its discovery in 1938, PTFE has been used in a wide scope of field, ranging from
industrial processes to commercial and household appliances. However, PTFE is
famously known as Teflon a trademark product from DuPont Company. The non-
sticking and slippery properties make it an ideal coating to be used by the kitchen utensil
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manufactures for the production of non-stick pans and other utensils.
Besides the two main characteristics, PTFE also has other unique features that have
been exploited in many ways as it has high temperature resistance, high melting point,
low reactivity to most chemicals as well as water-resistance. These properties make
PTFE a useful substance in a number of applications, some of which are as listed below:
PTFE is used widely chosen in the use for gaskets, vessel linings, pump interiors,
washers, rings, seals, spacers, dip tubes and well-drilling components. PTFE is chosen
since it is resistance to corrosion and chemically inert (Mishra and Yagci, 2008)
PTFE is considered one of the best insulators. It has the capability to insulate up to 500
volts per mil (V/mil) and more in terms of dielectric strength. It is commonly used in wire
and cable wrap, and to separate conductive surfaces in capacitors.
Practically, PTFE are made into shapes of thick walled close-tolerance extruded
tubing whereby it can be able to machine or drill long lengths to close tolerances. PTFE
also can be machined into standoff insulators, and many different types of high voltage
encapsulation devices for electrical components (Mishra and Yagci, 2008)
PTFE is inert and its operating temperature range from -350F to 500F. PTFE is the
material of choice for various goods which are commonly used in chip manufacturing
including encapsulation devices for quartz heaters (Mishra and Yagci, 2008)
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iv) Food, Beverage and Pharmaceutical industries
Virgin PTFE can also be use in food, beverages, cosmetics and pharmaceutical
industries. It provides a thin film and sheets that make an inert and non-toxic slide
surface without microscopic depressions which microbes can grow in such environment.
Conveyance components are able to withstand high temperatures inside baking and
drying ovens as well as heated segments of the food, cosmetics or pharmaceuticals
manufacturing processes.
PTFE coatings are important in the pharmaceutical industry since it provides an ease
to clean and purge braid seals as well as to strengthen the system. The pharmaceutical
industry uses a very high standards for all materials within it and PTFE meets the
particular requirement (Mishra and Yagci, 2008)
v) Laboratory applications
PTFE piping, tubing and vessels are used in various laboratory wares. This statement is
true due to PTFEs resistance to chemicals, inertness and the absences of contaminants
on the surface of PTFE products (Mishra and Yagci, 2008)
Various type of fillers can be easily blended with PTFE base resin to enhance properties
of glass or bronze fillers for instance .Fillers can be improve by PTFE to add stiffness
and strength, carbon fillers for conductivity, and moly blends for added lubricity. PTFE
does not melt however it cannot be molded into complex shapes, but must be machined.
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The process with highest score will be selected for the production of PTFE.
The mechanism for the chemical reaction for dispersion polymerization of TFE to
PTFE are explained by Ebnesajjad (2016) as follows:
Chloroform preparation:
CH 4 ( g )+ 3Cl 2 ( g ) CHCl3 ( g ) +3 HCl(g)
Methane ChlorineChloroform Hydrochloric Acid
Chlorodifluoromethane preparation:
CHCl3 ( g ) +2 HF ( g ) CHClF 2 ( g ) +2 HCl( g)
Chloroform Hydrogen Fluoride Chlorodifluoromethane Hydrochloric Acid
TFE synthesis:
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2CHClF 2 ( g ) C2 F 2 + HCl(g)
Polymerization of TFE:
C2 F 4 ( g) H 2 O, initiator ( C 2 F 4 )n ( s)
TFE PTFE
The two forms of PTFE that are most commonly manufactured are granular and fine
powder. Granular PTFE can be produced by suspension polymerization in an aqueous
medium with little or no dispersing agent according toTeng(2012) while under the effect
of vigorous agitation at elevated temperature and pressure as mentioned by Ebnesajjad
(2013). Granular PTFE is widely used for compression molding, isostatic molding and
ram extrusion.
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same arrangement of equipment. The parameters that differentiate between these two
processes are the operating temperature, operating pressure, agitation speed, initiation
concentration, presence of surfactant, mode of operation and batch size.
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certain product weight has been reached. At the end of the polymerization cycle, the
pressure is reduced and agitation stopped. After the reactor is vented and cooled down,
the granular product is recovered.(Ebnesajjad, 2013)
Fig
ure 1.6: Process Flow Diagram of Suspension Polymerization
The photolysis of TFE is carried out at temperature from 21 to 224C. Initiator such
as iodomethane, bromoethane and pentafluorooidoethane are used but it only produces
a small amount oily product and small yield of PTFEas it is mainly produced at a lab-
scale (Cohen and Heicklen, 1965). The chemical reaction mechanism for Photo-Initiated
Polymerization as stated by Cohen &Heicklen (1965) is shown below:-
Hghv Hg
Mercury photolysis Mercury
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HgC 2 F 4 Hg+ 2C F 2
Mercury TFE Mercury Difluoromethane
2C F 2 C2 F 4
Difluoromethane TFE
C F 2+C 2 F 4 CC 3 F 6 + ( C 2 F 4 )n
Difluoromethane TFE Hexaflurobutadiene PTFE
This type of polymerization is generally not practiced because the PTFE precipitation
formed is unable to be further processed. For this process, highly fluorinated
hydrocarbon such as hexafluoropropene and chlorodifluorohydrocarbons are used as the
solvent. The solution polymerization can be initiated by introducing gamma ( rays
and UV irradiation. It is reported that large amount of carboxylic end groups need
complex post-polymerization treatments if copolymerization in aqueous media is used
(Decker C, 1999).
For the process selection, eight criteria have been chosen to be used as a comparison
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between the available processes. A number will be assigned for each criterion to
determine the ranking of each process. The scores are given with the number five (5)
being the best and number one (1) being the worst. The criteria to be evaluated are raw
materials, catalyst/initiator, by-product, type of reactor, operating temperature, operating
pressure, safety, demand and manufacturing practicability.
i) Raw material
For any process, raw material is required in order to produce the desired product.
Therefore, when choosing between several available processes, it is always preferable
to select the process with the least and most common raw material as it is cheaper and
can be easily obtained.
ii) Catalyst/Initiator
iii) By-product
Certain processes produce undesired products which are harmful, toxic and hazardous
to the environment and health. These unwanted components are commonly referred as
by-products and are ideally avoided from being produced in the process.
The reactor is typically referred to as the heart for any chemical manufacturing process.
There are many types of reactor that can be used for the conversion of a raw material to
the desired product. Amongst the commonly used reactors are CSTR, PFR, packed bed
reactor, fluidized bed reactor and many more. Hence, it is crucial to identify the suitable
type of reactor to be used for each process and evaluate based on the maintenance,
price and operating costs.
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v) Operating condition
Operating condition such as temperature and pressure is the key to the success of a
manufacturing process. However, certain processes require conditions which are
different from normal conditions which will be more costly and harder to control.
Therefore, a process which operates at a reasonably normal condition should be
considered first before selecting the others.
vi) Safety
vii) Demand
The main purpose of producing a product is to supply the demand and fulfill the
requirements of the market. Therefore, demand of the final product should be assessed
thoroughly before selecting the process.
Factors in designing chemical plant such as economical, efficient process and most
importantly can produce desired amount of product is crucial. Hence, the process that
satisfies the factors will be chosen to be implemented in the chemical plant.
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1.3.1 Summary of the Available Processes
Safety Ammonium persulfate Ammonium persulfate Gamma rays can cause Mercury is a type of
can give bad impact to can give bad impact to stochastic health. poisoning metal. The
the environment the environment toxic can damage
kidneys and brains.
Demand Fine powder PTFE Granular PTFE Not highly demand due Small amount of PTFE
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emerged as the leading emerged as the leading to no practical value being produced since
product about 50% in product about 33% of since the precipitate of Perfluorocyclopropane
automotive industries total PTFE market. PTFE cannot be further is the main product.
processed.
Manufacturing Practical Practical Lab scale only Lab scale only
Practicability
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Table 1.3: Advantages and disadvantages of each process.
Process/Traits Advantages Disadvantages
Dispersion Fine powder PTFE When the agitation
polymerization fibrillates (a process which speed is at extremely
will form fibres) above its high condition, the
ambient transition particle diameter tend to
temperature. Thus, the increase while
tendency to fibrillate is polymerization rate
controllable. reduces (Kim et al.,
1998)
Semi-batch polymerization is
acceptable to use on a wide At extreme reaction
range of compositions, condition, the
including with a very slow polymerization rate
polymerization rates reduces as the polymer
(Ebnesajjad, 2013) . particles coagulated
during polymerization.
Coagulation leads to a
decrease in the surface
area of the particle,
resulting in a decrease in
the rate of supply of the
monomer and initiating
radicals from the aqueous
phase.
Suspension Granular PTFE can be Without regular
polymerization handled at different ambient surveillance, the
temperatures without much development of hot
difficulty, although it spots on the reactor wall
becomes sticky at certain can result in
temperatures. deflagration; exothermic
and explosive.
The system requires no
surfactants, which are At some point, as the
difficult to remove from the temperature is not in
product. within the range (lower
temperature), the
No ionic end groups present
effectiveness of
which may be unstable
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during processing at high persulfate may
temperatures (Ebnesajjad, diminished due to
2013). insufficient decomposition
rate (Ebnesajjad &
Morgan, 2011).
Polymerization Without any diluents, TFE Amorphous precipitation
in Solution of forms explosive mixture often leads to undefined
Carbon Dioxide with air. Thus, handling TFE morphologies and
with sufficient amount of shows low degrees of
CO2 offers much safer polymerization in
alternative; forming a several cases
pseudoazeotrope. (Desimone, n.d.).
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Effective type of lamp
used, LED, which is the
most energy-saving light
source and able to emit
shorter wavelengths of
light ( < 365 nm) is
not commercially
available yet (Shirai,
2014).
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1.3.2 Scoring Analysis
Raw material 5 4 2 2
Catalyst 4 4 2 3
By-product 3 3 2 2
Reactor used 5 4 3 1
Reaction Temperature 5 4 3 2
Reaction pressure 4 3 2 4
Safety 4 4 2 2
Demand 5 4 2 2
Manufacturing Practicability 5 5 1 1
TOTAL SCORE 40 35 19 19
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Based on the criteria and scoring carried out in the Table 1.3, dispersion
polymerization is chosen as the best method to produce PTFE leading with 40 points
ahead of the other methods.
In terms of demand, the product from dispersion polymerization has higher value
compared to suspension polymerization, photo-initiated polymerization and
polymerization in solution and carbon dioxide. This is because dispersion polymerization
produces finer particles which is approximately 0.05 m compared to suspension
polymerization that is 25 to 500 m. Fine powders PTFE are easier to mold to desired
end products. In addition, photo-initiated polymerization and polymerization in solution
and carbon dioxide produces only small amounts of PTFE as both processes are used
for lab-scale production.
Besides, the reactor cost for suspension polymerization is higher in the long term
compared to dispersion polymerization. This is due to the vigorous agitation involved in
the suspension polymerization whereby high amount of energy is consumed. The
vigorous agitation can also lead to higher amount of maintenance cost as it would
require regular service compared to mild agitation in dispersion polymerization.
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1.4 CONSIDERATIONSFOR PRODUCTION OF PTFE
Among the crucial factors to consider when designing a plant for the production of PTFE is
safety. The monomer TFE is a highly flammable and may explode when exposed to air.
Therefore, for this Design Project, we propose to produce the monomer instead of
purchasing it by using chlorodifluoromethane as the raw material. As opposed to TFE,
chlorodifluoromethane is nonflammable and does not explode easily.
As basis for the production capacity of the plant, 20,000 metric ton per annum is selected.
The value is based on the amount of PTFE produced in China, the leading producer of the
compound globally (MATRADE, 2016). Also, since the plant aims to produce a large amount
of PTFE, it will operate in a continuous mode of operation. The plant is designed to operate
for 10 years with an additional 2 years spent for the plant start up and construction. Hence,
the total years of plant life is 12 years. The plant will continuously operate for 11 months in a
year whereby one month is allocated for shut down process and annual leaves.
Among the limitations faced when designing a plant for the production of PTFE is the supply
of raw material as well as other supporting materials. Based on the market data obtained
from MATRADE, the amount of raw material chlorodifluoromethane and initiator benzoyl
peroxode produced in Malaysia are inadequate to meet the targeted production capacity.
Hence, the materials will have to be imported from China which serves as the primary
supplier.
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1.7 PROCESS FLOW DIAGRAM
Figure 1.8: Process flow diagram for production of PTFE using Aspen HYSYS.
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Figure 1.9: Process flow diagram for production of PTFE.
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1.8 PROCESS DESCRIPTION
The raw material used for the production of PTFE is chlorodifluoromethane (CHClF 2). The
material is stored within a pressurized vessel at 15 bar and 25C to maintain it in liquid phase as
this allows for easier storage and transportation. Upon exiting the tank, the pressure of CHClF 2 is
reduced to 12 bar using a valve to prevent damage to the upcoming equipment due to sudden
inflow of high pressure liquid.
The stream is then heated to 450C as a preparatory step before entering a tubular reactor
(Ebnesajjad, 2013). Within the reactor, gaseous CHClF 2 undergoes pyrolysis reaction and is
converted to TFE (C2F4) alongside hydrochloric acid (HCl) as the side product. When operating
at 810C and 6.55 bar, a conversion of 100% can be achieved as stated by (Ebnesajjad, 2016)
The product stream containing TFE and HCl is then condensed to liquid state before
entering a distillation column for purification and separation. Since HCl has a lower boiling point
than TFE, it will exit through the overhead stream meanwhile TFE exits through the bottom
stream. The separation produces product streams containing 99.9% w/w HCl and 99.5% w/w
TFE, respectively.
The purified HCl is then diluted with water and sold as a second source of revenue.
Meanwhile, the purified TFE is fed to a continuous stirred tank reactor (CSTR) for polymerization
reaction and produce PTFE. Additionally, water and benzoyl peroxide are added to the reaction
which acts as the solvent and organic initiator, respectively (Ebnesajjad, 2013). According to
(Mori, Tsuchiya, & Okahata, 2005), the conversion can achieve as high as 80% and produce
PTFE ranging between 10,000 g/mol to 1,000,000 g/mol.
The product stream is then fed to a mixing tank whereby a surfactant, sodium borate is
added to reduce the interfacial tension and form a stable colloidal dispersion of PTFE.
(Fernandez & Jebbanema, 2007). The sludge-like stream is subsequently transported using an
extruder to a filter press to remove unwanted components (waste stream) from PTFE.
The discharged waste stream containing unreacted TFE, HCl and water is purified using
two distillation columns whereby TFE and HCl are recycled back into the process meanwhile
water is sent to a water treatment facility. The solid PTFE is then transferred onto a conveyer belt
and dried to remove residual moisture and achieve the desired 99% purity.
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REFERENCES
Avataneo, M., De Patto, U., Guarda, P. A., & Marchionni, G. (2011). Perfluoropolyether
tetrafluoroethylene (PFPETFE) Block Copolymers: An Innovative Family of Fluorinated
Materials. Journal of Fluorine Chemistry,132(11), 885-891.
Cooper, A. I. (2000). Polymer synthesis and processing using supercritical carbon dioxide,
207234.
Dyneon GmbH. (2015) Processing of Dyneon PTFE Fine Powder. 3M Advanced Materials
Division: Germany.
Industry, PCI Pants and Coatings. (2007). The Effect of Surfactant Selection on Emulsion
Polymer Properties. Retrieved 1 December, 2016, from
http://www.pcimag.com/articles/87271-the-effect-of-surfactant-selection-on-emulsion-
polymer-properties
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Marcote UK Ltd. (n.d.). Teflon. Retrieved 23 October 2016, from
https://www.marcote.co.uk/teflon/
Mishra, M., & Yagci, Y. (2008). Handbook of Vinyl Polymers: Radical Polymerization,
Process, and Technology (Second Edi). CRC Press.
Nicholson, J. W. (2011). The Chemistry of Polymers (4, Revised ed.). Royal Society of
Chemistry.
Fernandez, A. M., & Jebbanema, L. (2007). The Effect of Surfactant Selection on Emulsion
Polymer Properties. Retrieved 1 December, 2016, from
http://www.pcimag.com/articles/87271-the-effect-of-surfactant-selection-on-emulsion-
polymer-properties
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Mori, T., Tsuchiya, Y., & Okahata, Y. (2005). Polymerizations of Tetrafluoroethylene in
Homogeneous Supercritical Fluoroform and in Detergent-Free Heterogeneous
Emulsion of Supercritical Fluoroform/Water. Macromolecules(39), 604-608.
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