Polymerization reactors contain one or more phases.
There are examples
using solvents in which the reactants and products are in the liquid phase, the reactants are fed as a liquid (gas) but the products are solid, or the reactants are slurry and the products are soluble. Phase transformations can occur, and polymers that form from the liquid phase may remain dissolved in the remaining monomer or solvent, or they may precipitate. Sometimes beads are formed and remain in suspension; sometimes emulsions form. In some processes, solid polymers precipitate from a gas phase into a fluidized bed containing product solids. Polymers are thought of as organic materials; however, inorganic polymers may be also synthesized (e.g., using crystallization and precipitation). Examples of inorganic polymers are zeolites. The structure of the polymer determines its physical properties, e.g., crystallinity, refractive index, tensile strength, glass transition temperature (at which the specific volume changes slope), and processability. The average molecular weight can cover a wide range between 104 to 107. Given the change in molecular weight, the viscosity can change dramatically as conversion increases. For example, in styrene polymerization, the viscosity increases by a factor of 106 as conversion increases from 0 to 60 percent. Initiators of chain polymerization reactions have concentration as low as 108 gmol/L so they are highly sensitive to small concentrations of poisons and impurities. The reaction time can also vary. Reaction times for butadienestyrene rubbers are 8 to 12 h; polyethylene molecules continue to grow for 30 min, whereas ethyl acrylate in 20 percent emulsion reacts in less than 1 min, so monomer must be added gradually to keep the temperature within limits. In some cases, the adiabatic temperature rise may be very high. Since it is impractical to fractionate the products and reformulate them into desirable ranges of molecular weights, immediate attainment of desired properties must be achieved through the correct choice of reactor type and operating conditions, notably of distributions of residence time and temperature. Reactor selection may be made on rational grounds, for historical reasons, or to obtain a proprietary position. Each reactor is designed based on the need for mass transfer, heat transfer, and reaction. Stirred batch (autoclave) and continuous tubular reactors are widely used because of their flexibility. In stirred tanks, ideal mixing is typically not achieved, wide variations in temperatures may result, and stagnant zones and bypassing may exist. Devices that counteract these unfavorable characteristics include inserts that cause radial mixing, scraping impellers, screw feeders, hollow-shaft impellers (with coolant flow through them), recirculation using internal and external draft tubes, and so on. The high viscosity of bulk and melt polymerization
2 Introduction to Polymer Technology | Types of Reactors for Polymer Processing
NONCATALYTIC GAS-PHASE REACTIONS.
Steam cracking of light hydrocarbons in a tubular fired heater. Steam cracking is a petrochemical process in which saturated hydrocarbons are broken down into smaller, often unsaturated, hydrocarbons. It is the principal industrial method to produce the lighter alkenes (commonly named olefins), including ethene (ethylene) and propene (propylene).
Pebble heater for the fixation of nitrogen from air. Nitrogen fixation is a process in which nitrogen (N2) in the atmosphere is converted into ammonium (NH4 + ). A Pebble Heater is a heat exchanger utilizing refractory pellets to store and give off heat.
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Flame reactor for the production of acetylene from hydrocarbon gases or naphthas. These processes use high temperature to convert the raw materials into a wide variety of gases, including hydrogen, carbon monoxide, carbon dioxide, acetylene, and others. Acetylene may be generated by raising the temperature of various hydrocarbons to the point where their atomic bonds break, or crack, in what is known as a thermal cracking process. After the hydrocarbon atoms break apart, they can be made to rebond to form different materials than the original raw materials. This process is widely used to convert oil or natural gas to a variety of chemicals.
Flame reactor for acetylene from light hydrocarbons. Acetylene may also be generated by raising the temperature of various hydrocarbons to the point where their atomic bonds break, or crack, in what is known as a thermal cracking process. After the hydrocarbon atoms break apart, they can be made to rebond to form different materials than the original raw materials. This process is widely used to convert oil or natural gas to a variety of chemicals.
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BATCH AND CONTINUOUS POLYMERIZATIONS.
Polyethylene in a tubular flow reactor. this type of reactors consist of long pipes (1-3 km) with small inner diameters (5-10 cm) and thick reactor walls (2-5 cm) which are divided into several reaction and cooling zones. Each zone is equipped with a jacket cooling system used to remove the large amounts of heat produced by polymerization
Batch process for polystyrene. Batch processes generally have a high conversion efficiency, leaving only small amounts of unreacted styrene to be emitted should the reactor be purged or opened between batches.
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Batch-continuous process for polystyrene. In continuous processes, the chemical reaction does not approach completion as efficiently as in batch processes. As a result, a lower percentage of styrene is converted to polystyrene, and larger amounts of unreacted styrene may be emitted from continuous process sources.
Suspension (bead) process for polyvinylchloride. Suspension polymerization is a heterogeneous radical polymerization process that uses mechanical agitation to mix a monomer or mixture of monomers in a liquid phase, such as water, while the monomers polymerize, forming spheres of polymer. In bead polymerization, the polymer is soluble in its monomer and the result is a smooth, translucent bead.
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Emulsion process for polyvinylchloride. Emulsion polymerisation produces finer resin grades having much smaller particles, which are required by certain applications. This type of resin is sometimes called paste PVC and referred to within the industry using the abbreviation P-PVC to distinguish it from S-PVC.
Reference:
Robert Perry, D. G. (2008). Perry's Chemical Engineers' Handbook.