Soran University

Faculty of Engineering
Chemical Department

Reactor & control process

Supervisor:_ Dr .Arkan Jasim Hadi

Prepared by:_ Arazoo Shakir hado
Dynamic Simulation of Industrial Poly(vinyl chloride) Batch Suspension
Polymerization Reactors

Introduction

Poly (vinyl chloride) (PVC) is one of the oldest polymers and the second largest in volume
thermoplastic manufactured in the world (Smallwood, 1990). The actual demand in Western
Europe for PVC in 1992 was 5.2 million tons, and the forecast for 1999 is estimated at 6 million
tons (Bevis, 1996). The enormous expansion of the PVC industry is due to the high versatility of
PVC as a plastic raw material together with its low price. . Approximately 75% of the world’s
PVC is produced by the suspension polymerization process. According to this technique,
droplets of liquid vinyl chloride monomer (VCM) containing oil-soluble initiator(s) are dispersed
in the continuous aqueous phase by a combination of strong stirring and the use of suspending
agents (stabilizers). The reaction takes place in the suspension droplets. For modeling purposes,
each droplet can be treated as a small batch bulk polymerization reactor. VCM, which boils at
-13.4 °C, is normally polymerized in a batch reactor by dispersing the liquid monomer, under
pressure, in water, in a well stirred jacketed reactor. The reactor’s contents are heated to the
required temperature where the initiator(s) start(s) to decompose and polymerization begins. The
heat of polymerization is transferred from the monomer droplets to the aqueous phase and then
to the reactor wall, which is cooled by chilled water flowing through the reactor’s jacket. When
all the free liquid monomer has been used up, the pressure in the reactor starts to fall as a result
of the monomer mass transfer from the vapor phase to the polymer phase due to sub saturation
conditions. In industrial PVC production. The reaction is usually stopped when a certain pressure
drop has been recorded. Since PVC is effectively insoluble in its own monomer, once the
polymer chains are first generated, they precipitate immediately to form two separate phases in
the polymerizing droplet. From a kinetic point of view the polymerization of VCM is considered
to take place in three stages.

Stage 1. During the first stage, primary radicals formed by the thermal fragmentation of initiator
rapidly react with monomer molecules to produce PVC macromolecules which are insoluble in
the monomer phase. The reaction mixture consists mainly of pure monomer, since the polymer
concentration is less than its solubility limit (conversion e0.1%).

Stage 2. This stage extends from the time of appearance of the separate polymer phase to a
fractional conversion, Xf, at which the separate monomer phase disappears. The reaction mixture
consists of four phases, namely, the monomer-rich phase, the polymerrich phase, the aqueous
phase, and the gaseous phase. The reaction takes place in the monomer and polymer phases at
different rates and is accompanied by transfer of monomer from the monomer phase to the
polymer phase so that the latter is kept saturated with monomer.The disappearance of the
monomer phase is associated with a pressure drop in the reactor.

Stage 3. Finally, at higher conversions (Xf < X < 1.0) only the polymer-rich phase swollen with
monomer exists. The monomer mass fraction in the polymer phase decreases as the total
monomer conversion approaches a final limiting value. The operational objective in an industrial
PVC suspension polymerization process is to produce resins with desired molecular and
morphological properties in a safe and efficient way, that can be handled and processed easily.
This means that the polymer must consistently meet the required product specifications.
Therefore, there is a strong incentive to develop comprehensive mathematical models capable of
predicting the reactor behavior as well as the development of molecular properties during the
course of polymerization.

PVC is produced by polymerization of vinyl chloride monomer (VCM). The main

polymerization methods include suspension, emulsion, and bulk (mass) methods. About 80% of
production involves suspension polymerization. First, the raw material VCM is pressurized and
liquefied, and then fed into the polymerization reactor, which contains water and suspending
agents in advance. Next, the initiator is fed into the reactor, and PVC is produced under a few
bars at 40 – 60°C.
The role of water is to remove and control the heat given off in the polymerization process. PVC
forms as tiny particles which grow and when they reach a desired size the reaction is stopped and
any unreacted vinyl chloride is distilled off and re-used. The PVC is separated off and dried to
form a white powder also known as PVC resin (see flow diagram). Polymerization finer resin
grades having much smaller particles, which are required by certain application.
Batch reactor

When using batch reactors, reactants are first placed inside the reactor and then allowed to react
over time. Batch reactors are closed systems that operate under unsteady-state conditions.

Batch reactors contain ports for injecting reactants and removing products, and can be outfitted
with a heat exchanger or a stirring system. While batch reactors are generally of constant
volume, some are designed to maintain a constant pressure by varying the reactor volume. Batch
reactors are used in a wide variety of applications. Typically, they are used for liquid phase
reactions that require a fairly long reaction time. The reactors below are used for beverage
processes.

Derivation of Batch Reactor Design Equations

For constant _volume batch reactor; v=v0

dNA 1 dNA d ( N A V 0) dCA

=r A V =rA → =rA → =rA
dt V dt dt dt

For constant pressure batch reactor

d (N A ) 1 d (C¿¿ A) d c A C A dT d C A C A d (lnV )
N A =C AV→ 1 = = + =rA → r A= + ¿
v dt v dt dt dt dt dt dt
Control process for batch reactors

Pressure Control

An autoclave can also be made into a batch reactor so that the reactions can run at higher
pressures. These are mainly used for reactions that need pressures above 5,000 psi. Instead of
having a mechanical agitator the reaction is stirred by a magnetic stirrer. Sensors and valves are
also necessary to ensure the safety of the system since it is being ran at such high pressures.

Temperature control

Quick response to heating and cooling loads and proper wall temperature control are critical for
the successful operation of a batch reactor .A typical batch reactor body, like the one in the
figure below, is surrounded by an outer jacket which circulates heat transfer fluid. Larger vessels
have multiple injection points to better distribute the heat transfer fluid within the jacket.

The picture below shows two common designs of batch reactor jackets. The one on the left is the
one-piece jacket, which forms an outer chamber around the vessel. Heat transfer fluid is injected
tangentially into the jacket at high speed to support mixing and dispersion of heat transfer fluid
within the jacket. The one on the right is the "half coil" jacket. This one consists of a series of
pipes cut along their longitude and welded outside the vessel. Heat transfer fluid travels in a plug
flow manner through the channels.
The picture below shows a batch reactor with a constant heat flux control system. This system is
a good solution to many temperature control problems in batch reactors.

This constant flux jacket is composed of multiple small heat-transfer channels. Each one of these
channels is a pipe clamped or welded around the external surface of the vessel and connected to
a multi-port piston valve. Heat transfer area is effectively controlled by varying the number of
coils in service. Therefore, the system can change heating or cooling power at constant jacket
heat flux. Constant flux jackets have essentially constant jacket temperatures.
Feedback control system for polyvinyl chloride production: Cascade control technique can be
effectively deployed to control reactor temperature within a very narrow specification limit
within ± 0.25℃. Cascade control is mainly used in this process control to obtain a fast rejection
of disturbance in the jacket dynamics, before it propagates to the other parts of the batch reactor.
It is one of the most successful methods for enhancing single-loop control performance
particularly when the disturbances are associated with the manipulated variable or when the final
control element exhibits a nonlinear be heavier. Figure 1 is the block diagram of cascade control
scheme for a batch reactor temperature T and Jacket temperature Tj have been taken as two
measurements. Coolant temperature Tj in is the only manipulated variable. The complete system
is a feedback and cascaded control system, where the controller in the outer loop is the primary
controller that regulates the primary controlled variable, reactor temperature T by setting the set
point for the inner loop. Controller in the inner loop is the secondary controller that regulates
the secondary controlled variable, jacket temperature Tj by manipulating the coolant temperature
T j in. For a cascade control system to function properly, the inner loop should respond much
faster than the outer loop, this improves the fast rejection of disturbances before it propagates to
the Primary process. The control objective is to improve the efficiency of PVC resin production
process with minimum overshoot, constant reactor temperature of 48.5 ℃ and with fast settling
time with in allowable tolerance levels of ±0.25℃.

Figure 1. Block diagram of closed loop cascade control scheme for PVC resin process
Reference

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