REACTOR OPERATIONS

If polymers are, in fact, products by process , then the mode of operation, as well as the choice of reactor type, will have a direct impact on polymer quality. In this section the various types of dynamic behavior which are possible with polymerization reactors will be explored, and the impact of these types of behavior on safe and efficient operation will be discussed. 

By the dynamic behavior of a polymerization reactor is meant the time evolution of the states of the reactor. The states are those fundamental dependent quantities which describe the natural state of the system. A set of equations which describes how the natural state of the system varies with time is called the set of state equations. Temperature, pressure, monomer conversion and copolymer composition could be considered states of a polymerization reactor. Independent variables such as coolant temperature in a jacketed reactor or initiator addition rate are not states but (controlled or uncontrolled) inputs. For various reactor types, different modes of dynamic behavior are observed. These can range from stable operation at a single steady state to instability, multiple steady states or sustained oscillations. 

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Selectivity for series reactions of the types given in Eqs. (2.7) to (2.9) is increased by low concentrations of reactants involved in the secondary reactions. In the preceding example, this means reactor operation with a low concentration of PRODUCT—in other words, with low conversion. For series reactions, a significant reduction in selectivity is likely as the conversion increases. 

The thermal catalytic route proposed involves heating the fresh reactant feed plus recycle up to 790°C and feeding this material into a M0S2 catalyst fixed-bed reactor operating at 0.1 MPa (1 atm). The route yields a production of H2 almost 50% higher than the decomposition of H2S route. 

Lightwater reactors, the primary type of nuclear power reactor operated throughout the world, are fueled with uranium dioxide [1344-57-6] UO2 miched from the naturally occurring concentration of 0.71% uranium-235 [15117-96-17, to approximately 3% (1). As of this writing all civiUan nuclear... 

The second important component is the cooling agent or reactor coolant which extracts the heat of fission for some usefiil purpose and prevents melting of the reactor materials. The most common coolant is ordinary water at high temperature and high pressure to limit the extent of boiling. Other coolants that have been used are Hquid sodium, sodium—potassium alloy, helium, air, and carbon dioxide (qv). Surface cooling by air is limited to unreflected test reactors or experimental reactors operated at very low power. 

A number of pool, also called swimming pool, reactors have been built at educational institutions and research laboratories. The core in these reactors is located at the bottom of a large pool of water, 6 m deep, suspended from a bridge. The water serves as moderator, coolant, and shield. An example is the Lord nuclear reactor at the University of Michigan, started in 1957. The core is composed of fuel elements, each having 18 aluminum-clad plates of 20% enriched uranium. It operates at 2 MW, giving a thermal flux of 3 x 10 (cm -s). The reactor operates almost continuously, using a variety of beam tubes, for research purposes. 

Several modes of waste management are available. The simplest is to dilute and disperse. This practice is adequate for the release of small amounts of radioactive material to the atmosphere or to a large body of water. Noble gases and slightly contaminated water from reactor operation are eligible for such treatment. A second technique is to hold the material for decay. This is appHcable to radionucHdes of short half-life such as the medical isotope technetium-9 9m = 6 h), the concentration of which becomes negligible in a week s holding period. The third and most common approach to waste... 

Molecular Weight Distribution. In industry, the MWD of PE resins is often represented by the value of the melt flow ratio (MER) as defined in Table 2. The MER value of PE is primarilly a function of catalyst type. Phillips catalysts produce PE resins with a broad MWD and their MER usually exceeds 100 Ziegler catalysts provide resins with a MWD of a medium width (MFR = 25-50) and metallocene catalysts produce PE resins with a narrow MWD (MFR = 15-25). IfPE resins with especially broad molecular weight distributions are needed, they can be produced either by using special mixed catalysts or in a series of coimected polymerization reactors operating under different reaction conditions. 

The Amoco reactor operates at 70—80°C and 2 MPa (300 psi) reactor pressure. The existence of several partially isolated compartments allows a semi-iadependent control of temperature as well as comonomer and hydrogen concentrations within each section, which ia turn offers a substantial control of the molecular weight and MWD of resias. Amoco technology also accommodates a large variety of polymerization catalysts, including Phillips and Ziegler catalysts. 

Shell Higher Olefins Process (SHOP). In the Shell ethylene oligomerization process (7), a nickel ligand catalyst is dissolved in a solvent such as 1,4-butanediol (Eig. 4). Ethylene is oligomerized on the catalyst to form a-olefins. Because a-olefins have low solubiUty in the solvent, they form a second Hquid phase. Once formed, olefins can have Htfle further reaction because most of them are no longer in contact with the catalyst. Three continuously stirred reactors operate at ca 120°C and ca 14 MPa (140 atm). Reactor conditions and catalyst addition rates allow Shell to vary the carbon distribution. 

Some reactors are designed specifically to withstand an explosion (14). The multitube fixed-bed reactors typically have ca 2.5-cm inside-diameter tubes, and heat from the highly exothermic oxidation reaction is removed by a circulating molten salt. This salt is a eutectic mixture of sodium and potassium nitrate and nitrite. Care must be taken in reactor design and operation because fires can result if the salt comes in contact with organic materials at the reactor operating temperature (15). Reactors containing over 20,000 tubes with a 45,000-ton annual production capacity have been constmcted. 

The principal reactions are reversible and a mixture of products and reactants is found in the cmde sulfate. High propylene pressure, high sulfuric acid concentration, and low temperature shift the reaction toward diisopropyl sulfate. However, the reaction rate slows as products are formed, and practical reactors operate by using excess sulfuric acid. As the water content in the sulfuric acid feed is increased, more of the hydrolysis reaction (Step 2) occurs in the main reactor. At water concentrations near 20%, diisopropyl sulfate is not found in the reaction mixture. However, efforts to separate the isopropyl alcohol from the sulfuric acid suggest that it may be partially present in an ionic form (56,57). 

EBHP is mixed with a catalyst solution and fed to a horizontal compartmentalized reactor where propylene is introduced into each compartment. The reactor operates at 95—130°C and 2500—4000 kPa (360—580 psi) for 1—2 h, and 5—7 mol propylene/1 mol EBHP are used for a 95—99% conversion of EBHP and a 92—96% selectivity to propylene oxide. The homogeneous catalyst is made from molybdenum, tungsten, or titanium and an organic acid, such as acetate, naphthenate, stearate, etc (170,173). Heterogeneous catalysts consist of titanium oxides on a siUca support (174—176). 

In cases where a large reactor operates similarly to a CSTR, fluid dynamics sometimes can be estabflshed in a smaller reactor by external recycle of product. For example, the extent of soflds back-mixing and Hquid recirculation increases with reactor diameter in a gas—Hquid—soflds reactor. Consequently, if gas and Hquid velocities are maintained constant when scaling and the same space velocities are used, then the smaller pilot unit should be of the same overall height. The net result is that the large-diameter reactor is well mixed and no temperature gradients occur even with a highly exothermic reaction. 

Fig. 15. Temperature vs heat generation or removal in estabHshing stationary states. The heavy line (—) shows the effect of reaction temperature on heat-generation rates for an exothermic first-order reaction. Curve A represents a high rate of heat removal resulting in the reactor operating at a low temperature with low conversion, ie, stationary state at a B represents a low rate of heat removal and consequently both a high temperature and high conversion at its stationary state, b and at intermediate heat removal rates, ie, C, multiple stationary states are attainable, c and The stationary state at c ...

Approximately 25—30% of a reactor s fuel is removed and replaced during plaimed refueling outages, which normally occur every 12 to 18 months. Spent fuel is highly radioactive because it contains by-products from nuclear fission created during reactor operation. A characteristic of these radioactive materials is that they gradually decay, losing their radioactive properties at a set rate. Each radioactive component has a different rate of decay known as its half-life, which is the time it takes for a material to lose half of its radioactivity. The radioactive components in spent nuclear fuel include cobalt-60 (5-yr half-Hfe), cesium-137 (30-yr half-Hfe), and plutonium-239 (24,400-yr half-Hfe). 

Process Description. Reactors used in the vapor-phase synthesis of thiophene and aLkylthiophenes are all multitubular, fixed-bed catalytic reactors operating at atmospheric pressure, or up to 10 kPa and with hot-air circulation on the shell, or salt bath heating, maintaining reaction temperatures in the range of 400—500°C. The feedstocks, in the appropriate molar ratio, are vaporized and passed through the catalyst bed. Condensation gives the cmde product mixture noncondensable vapors are vented to the incinerator. 

The Catofin process, which was formerly the property of Air Products (Houdry Division), uses a proprietary chromium catalyst in a fixed-bed reactor operating under vacuum. There are actually multiple reactors operating in cycHc fashion. In sequence, these reactors process feed for about nine minutes and are then regenerated for nine minutes. The chromium catalyst is reduced from Cr to Cr during the regeneration cycle. 

In principle, the catalytic converter is a fixed-bed reactor operating at 500—620°C to which is fed 200—3500 Hters per minute of auto engine exhaust containing relatively low concentrations of hydrocarbons, carbon monoxide, and nitrogen oxides that must be reduced significantly. Because the auto emission catalyst must operate in an environment with profound diffusion or mass-transfer limitations (51), it is apparent that only a small fraction of the catalyst s surface area can be used and that a system with the highest possible surface area is required. 

A typical reactor operates at 600—900°C with no catalyst and a residence time of 10—12 s. It produces a 92—93% yield of carbon tetrachloride and tetrachloroethylene, based on the chlorine input. The principal steps in the process include (/) chlorination of the hydrocarbon (2) quenching of reactor effluents 3) separation of hydrogen chloride and chlorine (4) recycling of chlorine to the reactor and (i) distillation to separate reaction products from the hydrogen chloride by-product. Advantages of this process include the use of cheap raw materials, flexibiUty of the ratios of carbon tetrachloride and tetrachloroethylene produced, and utilization of waste chlorinated residues that are used as a feedstock to the reactor. The hydrogen chloride by-product can be recycled to an oxychlorination unit (30) or sold as anhydrous or aqueous hydrogen chloride. 

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