Devolatilizer

A schematic of a continuous bulk SAN polymerization process is shown in Figure 4 (90). The monomers are continuously fed into a screw reactor where copolymerization is carried out at 150°C to 73% conversion in 55 min. Heat of polymerization is removed through cooling of both the screw and the barrel walls. The polymeric melt is removed and fed to the devolatilizer to remove unreacted monomers under reduced pressure (4 kPa or 30 mm Hg) and high temperature (220°C). The final product is claimed to contain less than 0.7% volatiles. Two devolatilizers in series are found to yield a better quaUty product as well as better operational control (91,92). 

A twin-screw extmder is used to reduce residual monomers from ca 50 to 0.6%, at 170°C and 3 kPa with a residence time of 2 min (94). In another design, a heated casing encloses the vented devolatilization chamber, which encloses a rotating shaft with specially designed blades (99,100). These continuously regenerate a large surface area to faciUtate the efficient vaporization of monomers. The devolatilization equipment used for the production of polystyrene and ABS is generally suitable for SAN production. 

If a linear mbber is used as a feedstock for the mass process (85), the mbber becomes insoluble in the mixture of monomers and SAN polymer which is formed in the reactors, and discrete mbber particles are formed. This is referred to as phase inversion since the continuous phase shifts from mbber to SAN. Grafting of some of the SAN onto the mbber particles occurs as in the emulsion process. Typically, the mass-produced mbber particles are larger (0.5 to 5 llm) than those of emulsion-based ABS (0.1 to 1 llm) and contain much larger internal occlusions of SAN polymer. The reaction recipe can include polymerization initiators, chain-transfer agents, and other additives. Diluents are sometimes used to reduce the viscosity of the monomer and polymer mixture to faciUtate processing at high conversion. The product from the reactor system is devolatilized to remove the unreacted monomers and is then pelletized. Equipment used for devolatilization includes single- and twin-screw extmders, and flash and thin film evaporators. Unreacted monomers are recovered for recycle to the reactors to improve the process yield. 

Low Temperature Carbonization. Low temperature carbonization, when the process does not exceed 700°C, was mainly developed as a process to supply town gas for lighting purposes as well as to provide a smokeless (devolatilized) soHd fuel for domestic consumption (30). However, the process by-products (tars) were also found to be valuable insofar as they served as feedstocks (qv) for an emerging chemical industry and were also converted to gasolines, heating oils, and lubricants (see Gasoline and OTHER motor fuels Lubrication and lubricants) (31). 

High Temperature Carbonization. When heated at temperatures in excess of 700°C (1290°F), low temperature chars lose their reactivity through devolatilization and also suffer a decrease in porosity. High temperature carbonization, at temperatures >900° C, is, therefore, employed for the production of coke (27). As for the low temperature processes, the tars produced in high temperature ovens are also sources of chemicals and chemical intemiediates (32). 

Step 4 of the thermal treatment process (see Fig. 2) involves desorption, pyrolysis, and char formation. Much Hterature exists on the pyrolysis of coal (qv) and on different pyrolysis models for coal. These models are useful starting points for describing pyrolysis in kilns. For example, the devolatilization of coal is frequently modeled as competing chemical reactions (24). Another approach for modeling devolatilization uses a set of independent, first-order parallel reactions represented by a Gaussian distribution of activation energies (25). 

Commercial polystyrenes are normally rather pure polymers. The amount of styrene, ethylbenzene, styrene dimers and trimers, and other hydrocarbons is minimized by effective devolatilization or by the use of chemical initiators (33). Polystyrenes with low overall volatiles content have relatively high heat-deformation temperatures. The very low content of monomer and other solvents, eg, ethylbenzene, in PS is desirable in the packaging of food. The negligible level of extraction of organic materials from PS is of cmcial importance in this appHcation. 

One of the key benefits of anionic PS is that it contains much lower levels of residual styrene monomer than free-radical PS (167). This is because free-radical polymerization processes only operate at 60—80% styrene conversion, whereas anionic processes operate at >99% styrene conversion. Removal of unreacted styrene monomer from free-radical PS is accompHshed using continuous devolatilization at high temperature (220—260°C) and vacuum. This process leaves about 200—800 ppm of styrene monomer in the product. Taking the styrene to a lower level requires special devolatilization procedures such as steam stripping (168). 

The devolatilized coal particles are transported to a direct-fired multihearth furnace where they are activated by holding the temperature of the furnace at about 1000°C. Product quaUty is maintained by controlling coal feed rate and bed temperature. As before, dust particles in the furnace off-gas are combusted in an afterburner before discharge of the gas to the atmosphere. Finally, the granular product is screened to provide the desired particle size. A typical yield of activated carbon is about 30—35% by weight based on the raw coal. 

The process for the thermal activation of other carbonaceous materials is modified according to the precursor. For example, the production of activated carbon from coconut shell does not require the stages involving briquetting, oxidation, and devolatilization. To obtain a high activity product, however, it is important that the coconut shell is charred slowly prior to activation of the char. In some processes, the precursor or product is acid-washed to obtain a final product with a low ash content (23,25). 

The stmcture of residual char particles after devolatilization depends on the nature of the coal and the pyrolysis conditions such as heating rate, peak temperature, soak time at the peak temperature, gaseous environment, and the pressure of the system (72). The oxidation rate of the chat is primarily influenced by the physical and chemical nature of the chat, the rate of diffusion and the nature of the reactant and product gases, and the temperature and pressure of the operating system. The physical and chemical characteristics that influence the rate of oxidation ate chemical stmctural variations, such as the... 

The main stages of coal combustion have different characteristic times in fluidized beds than in pulverized coal combustion. Approximate times are a few seconds for coal devolatilization, a few minutes for char burnout, several minutes for the calcination of limestone, and a few hours for the reaction of the calcined limestone with SO2. Hence, the carbon content of the bed is very low (up to 1% by weight) and the bed is 90% CaO in various stages of reaction to CaSO. About 10% of the bed s weight is made up of coal ash (91). This distribution of 90/10 limestone/coal ash is not a fixed ratio and is dependent on the ash content of the coal and its sulfur content. 

Devolatilization and combustion occur close to the coal inlet tubes. However, because of rapid mixing in the bed the composition of the soflds in the bed may be assumed to be uniform. 

The importance of these concepts can be illustrated by the extent to which the pyrolysis reactions contribute to gas produdion. In a moving-bed gasifier (e.g., producer-gas gasifier), the particle is heated through several distinct thermal zones. At the initial heat-up zone, coal carbonization or devolatilization dominates. In the successively hotter zones, char devolatihzation, char gasification, and fixed carbon... 

A1 soap in which about 50% of the org adds are derived from coconut oil, 25% from naphthenic acids and 25% from oleic acid. When stirred into gasoline at a temp range from 16—29°, M1 swells until the entire vol of gasoline becomes a more or less homogeneous gel M2 Thickener. A standard (for US Air Force) incendiary oil thickener. It is an intimate mixt of 95%Ml Thickener and 5% devolatilized silica... 

Various reactor combinations are used. For example, the product from a relatively low solids batch-mass reactor may be transferred to a suspension reactor (for HIPS), press (for PS), or unagitated batch tower (for PS) for finishing. In a similar fashion, the effluent from a continuous stirred tank reactor (CSTR) may be transferred to a tubular reactor or an unagitated or agitated tower for further polymerization before devolatilization. 

The advantage of suspension processes over mass processes is the excellent temperature control that can be obtained through the suspending medium, water. This allows for rapid heat removal and shorter polymerization times. It reduces or eliminates hot spots or heat-kicks characteristic of mass reactors. It also allows the polymerization to be driven very close to completion so that no devolatilization step is normally required. 

It is likely that some devolatilization occurred during the extrusion step, possibly aided by the acetic acid, since it is doubtful that there could be sufficient residence time in the final 180°C tower section to drive the conversion to 99.5%. 

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