Low-pressure process

This section will discuss the evolution of the low-pressure manufacturing process with emphasis on the chronological order in which important technical achievements were reported. For an additional discussion of the status of the low-pressure process as of 2010, the publication by Dennis B. Malpass is recommended [20]. 

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In the low pressure process, a short shot of a resia containing a blowiag ageat is forced iato the mold where the expandable material is aUowed to expand to fiU the mold under pressures of 690—4140 kPa (100—600 psi). This process produces stmctural foam products with a characteristic surface swid pattern produced by the coUapse of ceUs on the surface of molded articles. 

The energy consumption (lower heating value of the feedstock plus fuel) of the low pressure process has successively improved from over 38.3 GJ/1 when it was first introduced to 29.0—30.3 GJ/thy the mid-1990s. Natural gas-based reforming plants have advanced to the point where the scope for stiU further gains in efficiency is small and the gains costiy to obtain. 

Temperature, solvent ratio, and pressure each have an effect upon the spHt point or yield of the oil and asphalt components (Table 3). Contrary to straight reduction which is a high temperature and low pressure process, propane deasphalting is a low temperature and high pressure process. 

The processiag costs associated with separation and corrosion are stiU significant ia the low pressure process for the process to be economical, the efficiency of recovery and recycle of the rhodium must be very high. Consequently, researchers have continued to seek new ways to faciUtate the separation and confine the corrosion. Extensive research was done with rhodium phosphine complexes bonded to soHd supports, but the resulting catalysts were not sufficiently stable, as rhodium was leached iato the product solution (27,28). A mote successful solution to the engineering problem resulted from the apphcation of a two-phase Hquid-Hquid process (29). The catalyst is synthesized with polar -SO Na groups on the phenyl rings of the triphenylphosphine. 

The condensing turbine is selected when steam demand for process drivers is greater than the low-pressure process steam requirements. It is also selected when no high pressure steam is available. 

In the low-pressure systems a shot of material is injected into the mould which, if it did not expand, would give a short shot. However, the expanding gas causes the polymer to fill the mould cavity. One important form of the low-pressure process is the Union Carbide process in which the polymer is fed to and melted in an extruder. It is blended with nitrogen which is fed directly into the extruder. The extruder then feeds the polymer melt into an accumulator which holds it under pressure (14-35 MPa) to prevent premature expansion until a predetermined shot builds up. When this has been obtained a valve opens and the accumulator plunger rams the melt into the mould. At this point the mould is only partially filled but the pressurised gas within the melt allows it to expand. 

The process is attractive for a number of reasons. Firstly, since it is a low pressure process the moulds are generally simple and relatively inexpensive. Also the moulded articles can have a very uniform thickness, can contain reinforcement, are virtually strain free and their surface can be textured if desired. The use of this moulding method is growing steadily because although the cycle times are slow compared with injection or blow moulding, it can produce very large, thick walled articles which could not be produced economically by any other technique. Wall thicknesses of 10 mm are not a problem for rotationally moulded articles. 

Polyethylene can be chlorinated in solution in carbon tetrachloride or in suspension in the piescnce ot a catalyst. Below 55-60% chlorine, it is more stable and more compatible with many polymers, especially polyvinyl chloride, to which it gives increased impact strength. The low pressure process copolymerizes polyethylene with propylene and butylene to increase its resistance to stress cracking. Copolymerization with vinyl acetate at high pressure increases flexibility, resistance to stress cracking, and seal ability of value to the food industry. 

A low-pressure process has been developed by ICl operating at about 50 atm (700 psi) using a new active copper-based catalyst at 240°C. The synthesis reaction occurs over a bed of heterogeneous catalyst arranged in either sequential adiabatic beds or placed within heat transfer tubes. The reaction is limited by equilibrium, and methanol concentration at the converter s exit rarely exceeds 7%. The converter effluent is cooled to 40°C to condense product methanol, and the unreacted gases are recycled. Crude methanol from the separator contains water and low levels of by-products, which are removed using a two-column distillation system. Figure 5-5 shows the ICl methanol synthesis process. 

Figure 5-5. The ICI low-pressure process for producing methanol " (1) desulfurization, (2) saturator (for producing process steam), (3) synthesis loop circulator, (4) reactor, (5) heat exchanger and separator, (6) column for light ends recovery, (7) column for water removal.

High-density polyethylene (HDPE) is produced by a low-pressure process in a fluid-bed reactor. Catalysts used for HDPE are either of the Zieglar-type (a complex of A1(C2H5)3 and a-TiCl4) or silica-alumina impregnated with a metal oxide such as chromium oxide or molybdenum oxide. 

For watertube boilers it is necessary to maintain low O2 levels, and for this purpose a de-aerator in the feed line is required, which will also provide a degree of feed heating. The steam supply can be taken down from the low-pressure process steam main. 

This low pressure process, also known as elastic reservoir molding, consists of making basically a sandwich of plastic-impregnated open-celled flexible polyurethane foam between the face layers of fibrous reinforcements. When this plastic composite is placed in a mold and squeezed, the foam is compressed, forcing the plastic outward and into the reinforcement. The elastic foam exerts sufficient pressure to force the plastic-impregnated reinforcement into contact with the heated mold surface. Other plastics are used. 

The fall-off effects in unimolecular and recombination reactions are important in modern low-pressure processes such as chemical vapor deposition (CVD) and plasmaetching of semiconductor chips, and also for reactions in the upper atmosphere. 

Main characteristics of the linear LDPE low pressure processes are presented. The heat transfer and kinetic aspects are discussed in a more detailed manner in the case of the fluidised bed technology. 3 refs. 

Solution polymerizafion. Highly exothermic reactions can be handled by this process. The reaction is carried out in an excess of solvent that absorbs and disperses the heat of reaction. The excess solvent also prevents the formation of slush or sludge, which sometimes happens in the bulk process when the polymer volume overtakes the monomer. The solution process is particularly useful when the polymer is to be used in the solvent, say like a coating. Some of the snags with this process its difficult to remove residual traces of solvent, if that s necessary the same is true of catalyst if any is used. This process is used in one version of a low-pressure process for high-density polyethylene and for polypropylene. 

PP-structural foam mouldings were produced on an injection moulding machine in a pre-pressurised mould cavity by the classical low-pressure process and an alternative low-pressure process. Melt temperature, injection direction and sprae diameter were varied. Cross-sections cut from the middle of the small cylinder in longitudenal orientation were investigated by site-resolved X-ray scattering. Morphological properties were investigated. 4 refs. 

Aqueous-based EVA polymer emulsions suited for the use in heat seal applications are produced at a comparatively low pressures process, less than 14 M Pa (2). 

Acetic Acid. Carbonylation of methanol is the most important reaction in the production of acetic acid.189-192 BASF developed a process applying C0I2 in the liquid phase under extreme reaction conditions (250°C, 650 atm).122 193 The Monsanto low-pressure process, in contrast, uses a more active catalyst combining a rhodium compound, a phosphine, and an iodine compound (in the form of HI, Mel, or T2).122 194—196 Methanol diluted with water to suppress the formation of methyl acetate is reacted under mild conditions (150-200°C, 33-65 atm) to produce acetic acid with 99% selectivity at 100% conversion. 

The basic equations needed are essentially the same used in the case of low pressure processes but the difference is given by some peculiar behaviour of fluids when the pressure is relatively high and close to the critical one of some components in the mixture. 

About the production of polyethylene it is shown that the total costs of the low-pressure process are similar to those of the high pressure one. 

In many cases, the linear low-density polyethylene (LLDPE) produced in low-pressure processes competes for the same market as LDPE. For this reason, in Figure 8.2-7 capital- and operation costs of the high-pressure polymerization are compared with those of a low-pressure solution process having the same capacity. Also, the production costs of the low-pressure process are dominated by the costs of the monomer, but some differences can be noted which are typical for the economics of low- and high-pressure processes. 

Figure 8.2-7. Comparison of costs of high- and low-pressure processes. Capacity 100,000 t/a, on 1997 prices, production of pellets.

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