A SURVEY REPORT ON
Reactors used in Polymer Industry
BY
SACHIN SHINDE MALI
(Gr. No. 11910317)
SANJAY SURWASE
(Gr. No. 11910398)
CHINMAY THETE
(Gr. No. 11911132)
FARAAZ USMANI
(Gr. No. 11910439)
MEHER YEDE
(Gr. No. 11910743)
Department of Chemical Engineering
BRACT’S Vishwakarma Institute of Technology,
666, Upper Indiranagar, Bibwewadi, Pune – 411 037
Reactors used in Polymer Industry
ABSTRACT
Converting monomer to long chain polymer is the final step in the polymer
manufacturing sequence. Polymerization is usually highly favorable in
thermodynamic terms, mainly on energetic grounds because ordering molecules
into linked chains is a process where the entropy is decreased. Heat is always given
out during polymerization owing to the very favorable energetics of reaction. In
this project we focused on the reactor system design and also the heat removal
aspect of the reactor and at last we focused on reviewing the future scope of use of
polymer industry reactors.
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ACKNOWLEDGMENTS
This document is prepared by the inspiration received from Prof.Dr.Gayatri Gawande,
Department of Chemical Engineering and Professor Manik Deosarkar, Head of Department of
Chemical Engineering, BRACT’s Vishwakarma Institute of Technology. Many colleagues at the
Chemical Engineering Department have carefully read and improved the document; their
contributions are gratefully acknowledged.
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Bansilal Ramnath Agarwal Charitable Trust’s
VISHWAKARMA INSTITUTE OF TECHNOLOGY
(An Autonomous Institute Affiliated to University of Pune)
666, Upper Indiranagar, Bibwewadi, Pune – 411 037
CERTIFICATE
It is certified that the project work entitled
“Reactors used in Polymer Industry”
Submitted by
Sachin Shinde Mali Gr. No. 11910317 Roll No. 57
Sanjay Surwase Gr. No. 11910398 Roll No. 64
Chinmay Thete Gr. No. 11911132 Roll No. 67
Faraaz Usmani Gr. No. 11910439 Roll No. 69
Meher Yede Gr. No. 11910743 Roll No. 76
is the original work carried out by them under the supervision of Prof.Gayatri Gawande.
(Prof. Gayatri Gawande) (Prof. Manik Deosarkar)
Guide, Head,
Department of Chemical Department of Chemical
Engineering Engineering
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INDEX
Sr.No Content Page No.
1 Introduction 6
2 Reactor System Design 9
3 Heat Removal 12
4 Future Scope of Polymer Science 15
5 Conclusion 17
6 References 18
INTRODUCTION
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Important considerations in polymerization reactor design include heat removal,
kinetics, and process dynamics, as well as polymer properties and product quality.
Polymer reaction engineering is an interesting field, with many rich and rewarding
problems to be solved. To be successful in this field, a chemical engineer needs to
understand a few principles beyond the basics of reaction engineering. This project
explores some of the most important of those principles related to selecting, sizing,
and troubleshooting polymerization reactors.
Polymers tend to be viscous, which often imposes lower limits on their
concentrations in diluents and on reaction temperatures. At very low temperatures,
or in the absence of a solvent, the viscosity of a reacting mixture might be so high
that it severely limits heat transfer. Worse yet, the polymer might crystallize and
coat the catalyst- and monomer-injection systems.
One common approach is to carry out the reaction in a low-viscosity continuous
phase that includes monomer and other important components, with the
polymerization occurring in a discrete phase made up of viscous, and sometimes
even solid, polymer particles (Figure 1). Such heterogeneous polymerization
systems are often used in free-radical polymerization.
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▲ Figure 1. Polymerization of a viscous discrete phase (orange circles) in a less-viscous continuous
phase (gray background).
An interesting example of a heterogeneous system is olefin polymerization in
fluidized-bed reactors. A supported catalyst in the form of very small particles, with
diameters of only a few microns, is injected into the reactor. Monomer in the
continuous gas phase forms chains at the catalyst active sites. As the cycle of chain
birth, growth, and death repeats, catalyst particles fragment and create more surface
area for the monomer to attach to; the polymer links the fragmented catalyst pieces
together, forming polymer particles whose final diameters are easily ten times those of
the original particles (Figure 2). The viscosity problem is avoided, but the high
reaction rates can cause a different problem: Particles that are unable to transfer
energy to the gas phase at the same rate they are generating it are at risk of
overheating, melting, and sticking to each other or to solid surfaces .
▲ Figure 2. In a fluidized-bed reactor, catalyst particles fragment, and polymer links the fragments. The
polymer particle expands and can be an order of magnitude larger than the original catalyst particle.
Viscosity, like melt strength, is an end-use property — the kind of property that
producers and their customers use to measure product performance. Underlying these
properties sits another layer of properties that relate to molecular architecture and
include molecular weight, polydispersity index, and degree of branching.
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The molecular architecture of a polymer can be influenced by chemistry, reactor
configuration, and process conditions, all of which must be well understood for
reactor selection and design. Without that understanding, an attempt to improve
throughput, for example, by raising reactor temperature, might lead to unexpected
results in the customer’s application .
Olefin polymerization normally employs catalysts that are extremely sensitive to
poisoning.. The polymerization process can be complicated by side reactions that
form macromers (i.e., chains containing a terminal double bond) and their subsequent
reincorporation as branches along the chain backbone .
Although it is important to control the temperature and the level of chain-transfer
agent, doing this is not as straightforward as it may seem, because in many reactors
there is not just one temperature and one level of chain-transfer agent. As these
conditions change in space or in time, the polymer that exits the reactor is usually a
composite of polymer populations with different molecular architectures.
REACTOR SYSTEM DESIGN
System design extends beyond the design of the vessel itself; other components
require close attention as well. This section discusses some of the challenges
involved in polymer manufacturing (Figure 3) and their impact on process
equipment; some are explained in more detail in later sections.
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▲ Figure 3. Reaction system design must take into account a wide range of considerations.
Product sequence. Polymerization reactors are rarely built to make only one
product over the entire life of the equipment. Normally, a reactor switches
among a handful of products. In addition, markets change, so manufacturers
prefer a flexible design — one that is good today, and, with little or no
modification, 30 years from now.
Reactor configuration. Reactor configuration is determined by the reaction
scheme for making the product of choice with the desired molecular
architecture. Living polymers, for example, maintain their narrow distributions
as long as all chains have the same residence time, which can be achieved in a
well-mixed batch reactor or a plug-flow reactor.
Reactor conditions. Polymer properties, like catalyst activity, also vary with
temperature and with the level of chain-transfer agent. Reactor conditions
depend on the reactor configuration. Some reactors are vulnerable to temporal
or spatial variations, the products of which are really composites of chain
populations produced at various times or various locations in the reactor.
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Heat removal. The heat released by many polymerization reactions of commercial
interest is usually more than a simple heat-removal mechanism, such as a jacket
or a coil, can handle. As a result, engineers need to be creative in developing
mechanisms that do not significantly increase capital cost — for example, an
external heat exchanger with a recirculation pump. The high viscosities of most
polymerization systems, and the corresponding low heat-transfer coefficients,
make this task particularly challenging.
Fluid mechanics. Polymers and their mixtures do not always behave like
Newtonian fluids. This issue is particularly critical in a monomer-injection
system, where fluids with very different properties and temperatures must mix
rapidly to avoid creating polymer populations with the wrong properties.
Mass-transfer limitations. Mass-transfer limitations are common in heterogeneous
systems, because the monomer and other components must diffuse through a
continuous phase in order to reach the discrete phase where polymerization
takes place. Systems that appear to be simpler can have these limitations as
well. For example, if the monomer is volatile and a headspace exists in the
reactor, the monomer may accumulate in the headspace, lowering its rate of
consumption in the liquid phase.
Thermodynamic constraints. Even if only one phase is expected to exist in the
reactor, process operators and engineers should stay vigilant to ensure that a
second phase does not form. Running the reactor at a very low pressure risks
the formation of a vapor phase. Running at a very low temperature risks coating
the reactor internals with polymer. Neither of these is a welcome sight,
especially the latter.
Process dynamics. In continuous processes, the more complex the product
sequence, the more important it is to manage a quick transition between
polymer grades. Some grades might be completely incompatible because of the
markets to which they are destined, so the need to avoid cross-contamination
puts an additional stress on the manufacturer, and highlights the need for
efficient product-grade-transition schemes.
Reactor stability. The thought of releasing increasing amounts of energy from a
reactor brings to mind the possibility of multiple steady states, sustained
oscillations, chaotic behavior, and the danger of a reactor runaway. Some
people believe these problems are only concerns of academia, but they can
easily lead to trouble. A good reaction system design avoids operating a reactor
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too close to a limit point, for example, where a small disturbance causes a rapid
deviation from the desired steady state.
HEAT REMOVAL
Polymers share a common problem with small molecules. Polymerization reactions,
which are strongly exothermic, can release significant amounts of energy (6). (For
example, olefin polymerization releases 96 kJ/mol; in the case of propylene, that
translates to 2,300 kJ/kg.) The removal of that energy is thus a key aspect of reactor
design.
Consider a 100,000-ton/yr plant for polypropylene production. The plant would
release energy at an average rate of 7,300 kJ/sec. Some of that energy can go into
heating the feed stream, but the majority of it must be removed by some other means.
Imagine that 90% conversion is expected from a continuous stirred-tank reactor
(CSTR) with a 30-min residence time and a feed stream containing 40% propylene.
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Such conditions would require a reactor volume of approximately 25 m 3. A jacketed
reactor of this volume has a heat-transfer area in the neighborhood of 30 m 2. With an
assumed heat-transfer coefficient of 1 kJ/m 2-sec-°C, the required temperature gradient
between process fluid and coolant is an excessive 243 °C.
A jacket as the main method of heat removal imposes a serious limitation on the
polypropylene plant. This limitation is often avoided by adding an external heat
exchanger (Figure 4). Such a configuration is probably the most common arrangement
used in polymer manufacturing today.
▲ Figure 4. Many continuous stirred-tank reactors (CSTRs) employ an external heat exchanger
to remove the large amount of heat produced during polymerization.
It is easy to see why the external heat exchanger is an attractive configuration. A
shell-and-tube heat exchanger has an area per unit volume of 4/d (where d is the
diameter of each tube). A shell-and-tube exchanger with 2-in.-dia. tubes and a volume
that is 25% of the combined volume of the tank, heat exchanger, and the pipes
connecting them has an available heat-transfer area of 500 m 2; a temperature gradient
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of 15°C is sufficient to handle the energy released by the propylene polymerization
system.
If necessary, the process could be designed with an exchanger that has a larger area
for heat transfer. Larger heat exchangers account for a larger portion of the total
process volume. In the extreme, instead of a separate reactor and heat exchanger, the
process would consist of a tubular loop reactor in which reaction and heat exchange
both occur (7).
A simple energy balance for the tank in Figure 4 (ignoring the effect of reaction
outside the tank) states that the energy generated by the reaction is removed in the
heat exchanger or used to raise the temperature of the feed stream to reaction
temperature:
where wMf and wM are the weight fractions of monomer in the feed
stream and the reactor, respectively; –∆Hp is the heat of
polymerization; R is the recycle ratio; Cp is the average heat capacity of any of the
streams; and T, Tr, and Tf are the temperatures of the reactor, the recycle stream
leaving the heat exchanger (entering the reactor), and the feed stream, respectively.
Figure 5 plots the temperature difference across the heat exchanger in the 100,000-
ton/yr polypropylene plant (Figure 4) as a function of recycle ratio, with a feed
temperature
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▲ Figure 5. The temperature drop across a heat exchanger is a function of recycle ratio. This
plot is for the exchanger in Figure 4 when T – Tf = 50°C.
that is 50°C below the reactor temperature (Tf = T – 50). Low recycle ratios, say R ≤
10, require very large temperature differences. Recycle
ratios of R > 10 may not be feasible, though — depending, for example, on the
size of the recycle pump that you can afford.
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FUTURE SCOPE OF POLYMER SCIENCE
The main concerns for humans in the future will be energy & resources, food,
health, mobility & infrastructure and communication. There is no doubt that
polymers will play a key role in finding successful ways in handling these
challenges. Polymers will be the material of the new millennium and the
production of polymeric parts i.e. green, sustainable, energy-efficient, high quality,
low-priced, etc. will assure the accessibility of the finest solutions round the globe.
Synthetic polymers have since a long time played a relatively important role in
present-day medicinal practice. Many devices in medicine and even some artificial
organs are constructed with success from synthetic polymers. It is possible that
synthetic polymers may play an important role in future pharmacy, too. Polymer
science can be applied to save energy and improve renewable energy technologies.
Biopolymers could especially increment as more solid adaptations are produced,
and the cost to fabricate these bio-plastics keeps ongoing fall. Bio-plastics can
supplant routine plastics in the field of their applications likewise and can be
utilized as a part of various areas, for example, sustenance bundling, plastic plates,
mugs, cutlery, plastic stockpiling packs and in this way can help in making the
environment economical.
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In areas of applications of plastics materials, a well-known long standing example
is electrical industries have led to increasing acceptance of plastics for plugs,
sockets, wire and cable insulations and for housing electrical and electronic
equipment. The major polymer targeting industries of the present day life includes
Ceramic industries, in stem cell biology and Regenerative Medicine, packaging
industries, in retorting methods used for food processing industries in automotive
industries, in aerospace industries and in electrical and electronic industries.
● Polymers in Stem Cell Biology
● Self-Healing and Reprocess-able Polymer Systems
● Smart Polymers
● Green Synthesis of Functional Materials
● In Gene Delivery Systems
● Ceramic Industry
● Biopolymers in Drug Delivery
● Market growth of Polymers
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CONCLUSION
Polymers are long chain molecules with properties dominated by their chain
behavior and the nature of their chemical make-up or constitution. The distinction
between thermoplastics and thermosets has become rather blurred with the
development of new materials for more demanding environments than previously.
They include high performance polymers which are more resistant to high
temperatures, possess greater moduli or strengths, and can be combined with
additives to enhance their intrinsic properties yet further. An understanding of the
atomic and molecular construction of polymers provides an insight into how
improved materials can be developed, in the subject of molecular engineering. It
includes an understanding of both molecular configuration and
conformation.Today, polymer production involves three main types of
reactors:Batch Reactor, Plug Flow Reactor, Fluidized Bed Reactor, Batch Plug
Flow, and Fluidized BedWithin these reactors two main reaction processes occur:
High Pressure and Low Pressure Polymerization.
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REFERENCES
1. Pradeep Jain, Shrikant Dhodapkar, Carlos Villa., february 2016.Designing
Polymerization Reaction Systems
2. Wang, Z.L., F. Pia and J.P. Corriou (1995). Nonlinear adaptive control of
batch styrene polymerization.
3. Blog by Conference Series,November 07-08, 2022 London, UK.Future
Scope of Polymer Science
4. Philipp A. Mueller,John R. Richards, John P. Congalidis.,August 2011.
Polymerization Reactor Modeling in Industry
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