Commercial Units

Separation Processes for PX. There are essentially two methods that are currendy used commercially to separate and produce high purity PX (/) crystallization and (2) adsorption. A third method, a hybrid crystallization /adsorption process, has been successfiiUy field-demonstrated and the first commercial unit is expected in the near future. 

Mobil s Low Pressure Isomerization Process (MLPI) was developed in the late 1970s (123,124). Two unique features of this process are that it is Operated at low pressures and no hydrogen is used. In this process, EB is converted to benzene and diethylbenzene via disproportionation. The patent beheved to be the basis for the MLPI process (123) discusses the use of H-ZSM-5 zeoHte with an alumina binder. The reaction conditions described are start-of-mn temperatures of 290—380°C, a pressure of 273 kPa and WHSV of 5—8.5/h. The EB conversion is about 25—40% depending on reaction conditions, with xylene losses of 2.5—4%. The PX approach to equiHbrium is about 99 ndash 101%. The first commercial unit was Hcensed in 1978. A total of four commercial plants have been built. 

In the 1980s cost and availabiUty of acetylene have made it an unattractive raw material for acrylate manufacture as compared to propylene, which has been readily available at attractive cost (see Acetylene-DERIVED chemicals). As a consequence, essentially all commercial units based on acetylene, with the exception of BASF s plant at Ludwigshafen, have been shut down. AH new capacity recendy brought on stream or announced for constmction uses the propylene route. Rohm and Haas Co. has developed an alternative method based on aLkoxycarbonylation of ethylene, but has not commercialized it because of the more favorable economics of the propylene route. 

The behavior of drops in the centrifugal field has been studied (211) and the residence times and mass-transfer rates have been measured (212). PodbieHiiak extractors have been widely used in the pharmaceutical industry, eg, for the extraction of penicillin, and are increasingly used in other fields as weU. Commercial units having throughputs of up to 98 m /h (26,000 gal/h) have been reported. 

Propeller Fa.ns, Propeller fans may have from 2 to 6 blades mounted on a central shaft and revolving within a narrow mounting ting, either driven by belt drive or directiy coimected. The form of the blade ia commercial units varies from a basic airfoil to simple flat or curved plates of many shapes. The wheel hub is small ia diameter compared to the wheel. The blades may even be mounted to a spider frame or tube without any hub. The housiag surrounding the blades can range from a simple plate or flat ring to a streamlined or curved beU—mouth orifice. 

Development of New Processes. There has been significant research activity to develop new processes for producing formaldehyde. Even though this work has been extensive, no commercial units are known to exist based on the technologies discussed ia the following. 

In general, the proven technology to upgrade methane is via steam reforming to produce synthesis gas, CO + Such a gas mixture is clean and when converted to Hquids produces fuels substantially free of heteroatoms such as sulfur and nitrogen. Two commercial units utilizing the synthesis gas from natural gas technology in combination with novel downstream conversion processes have been commercialized. 

Commercially, the burner chamber and the absorber cooler sections are combined as a single unit for small-scale production. However, in large capacity plants, these units are separated. A typical commercial unit is schematically described in Figure 5 (32). 

In a commercial unit, a spray nitrator (39) is operated adiabaticaHy. The Hquid HNO feed is sprayed direcdy into the hot and preheated propane feed. The heat of nitration provides the heat to vaporize the HNO and to preheat it to the desired temperature for nitration. At one time, several spray nitrators were operated in series, with additional HNO being sprayed into each nitrator (32). In such an arrangement, the optimum propane HN02 ratios did not occur, and considerable amounts of nitroparaffins degraded. 

Exploiting the relative basicity of the xylene isomers, commercial units employ superacids, typically HE—BF, as the acid complexing agent for the separation of / -xylene (feedstock for isophthalic acid) (15). Amoco produces high purity / -xylene at its Texas City facility using the HE—BF process (see Btx processing). Similar processes can be used for the separation of high purity mesitylene and isodurene from their and C q isomers, respectively. 

Commercial samplers are available that combine a traversing-type sampler and an unacceptable table sampler. An alternative design is the radial cutter or Vezin sampler. These samplers vary in size from a 15-cm laboratory unit to a 152-cm commercial unit. 

The water-vapor transmission rate (WVTR) is another descriptor of barrier polymers. Strictly, it is not a permeabihty coefficient. The dimensions are quantity times thickness in the numerator and area times a time interval in the denominator. These dimensions do not have a pressure dimension in the denominator as does the permeabihty. Common commercial units for WVTR are (gmil)/(100 in. d). Table 2 contains conversion factors for several common units for WVTR. This text uses the preferred nmol/(m-s). The WVTR describes the rate that water molecules move through a film when one side has a humid environment and the other side is dry. The WVTR is a strong function of temperature because both the water content of the air and the permeabihty are direcdy related to temperature. Eor the WVTR to be useful, the water-vapor pressure difference for the value must be reported. Both these facts are recognized by specifying the relative humidity and temperature for the WVTR value. This enables the user to calculate the water-vapor pressure difference. Eor example, the common conditions are 90% relative humidity (rh) at 37.8°C, which means the pressure difference is 5.89 kPa (44 mm Hg). 

The traditional definition of a barrier polymer requited an oxygen permeabihty less than 2 nmol /(m-s-GPa) (originally, less than (1 comil)/(100 in. datm)) at room temperature. This definition was based pardy on function and partiy on conforming to the old commercial unit of permeabihty. The old commercial unit of permeabihty was created so that the oxygen permeabihty of Saran Wrap brand plastic film, a trademark of The Dow Chemical Company, would have a numerical value of 1. 

Disproportionation of Olefins. Disproportionation or the metathesis reaction offers an opportunity to convert surplus olefins to other desirable olefins. Phillips Petroleum and Institut Fransais du Petrc le have pioneered this technology for the dimerization of light olefins. The original metathesis reaction of Phillips Petroleum was intended to convert propylene to 2-butene and ethylene (58). The reverse reaction that converts 2-butene in the presence of excess ethylene to propylene has also been demonstrated (59). A commercial unit with a capacity of about 136,000 t/yr of propylene from ethylene via 2-butene has been in operation in the Gulf Coast since 1985 (60,61). In this process, ethylene is first dimerized to 2-butene foUowed by metathesis to yield propylene. Since this is a two-stage process, 2-butene can be produced from the first stage, if needed. In the dimerization step, about 95% purity of 2-butene is achieved at 90% ethylene conversion. 

Polymer Gasoline. Refinery trends tend to favor alkylation over polymerisation. Unlike the alkylation process, polymerisation does not require isobutane. The catalyst is usually phosphoric acid impregnated on kieselghur pellets. Polymerisation of butylenes is not an attractive alternative to alkylation unless isobutane is unavailable. The motor octane number of polymer gasoline is also low, and there is considerable shrinkage ia product volume. The only commercial unit to be built ia recent years is at Sasol ia South Africa. The commercial process was developed by UOP ia the 1940s (104). 

Deviations from the ideal frequentiy occur in order to avoid system complexity, but differences between an experimental system and the commercial unit should always be considered carefully to avoid surprises on scale-up. In the event that fundamental kinetic data are desired, it is usually necessary to choose a reactor design in which reactant and product concentration gradients are minimized (36), such as in the recycle (37) or spinning basket reactor designs (38,39). 

Similarly, small (0.2—0.6 mm) air bubbles are introduced into a 2.6-m Deister Flotaire column at an intermediate level allowing rapid flotation of readily floatable material in the upper recovery zone. The bottom air permits longer retention time of the harder-to-float particles in the presence of micrometer-sized bubbles at a reduced downward velocity. The first commercial unit went on stream in 1986. It was used to improve the recovery of <0.6 mm (—28 mesh) coal in the plant s tailings. An average of 5.5% increase in coal recovery resulted from its use (14). The second commercial use processed <0.15 mm (—100 mesh) coal feed. 

In the 1970s commercial fluidized-bed combustors were limited to the atmospheric, bubbling-bed system, called the atmospheric fluidized-bed combustor (AFBC). In the late 1970s the circulating fluidized combustor (CFG) was introduced commercially, and in the 1980s the new commercial unit was the pressurized fluidized-bed combustor (PFBC). 

Extrapolation of KgO data for absorption and stripping to conditions other than those for which the origin measurements were made can be extremely risky, especially in systems involving chemical reactions in the liquid phase. One therefore would be wise to restrict the use of overall volumetric mass-transfer-coefficient data to conditions not too far removed from those employed in the actual tests. The most reh-able data for this purpose would be those obtained from an operating commercial unit of similar design. 

Multiple Phases Reaclions between gas/liquid, liquid/liquid, and fluid/solid phases are often tested in CSTRs. Other laboratoiy types are suggested by the commercial units depicted in appropriate sketches in Sec. 23. Liquids can be reacted with gases of low solubili-... 

Units are fabricated in widths from 0.3 to 1.5 m. Lengths are variable from 3 to 50 m however, most commercial units will not exceed a length of 10 to 16 m per sec tion. Power required for the vibrating drive will be approximately 0.4 kW/m" of deck. 

Thermally efficient calcination of lime dolomite and clay can be carried out in a multicompartmeut fluidized bed (Fig. 17-27). Fuels are burned in a fluidized bed of the product to produce the required heat. Bunker C oil, natural gas, and coal are used in commercial units. Temperature control is accurate enough to permit production of hme of very high availability with close control of slaking characteristics. Also, half calcination or dolomite is an accepted practice. The requirement of large crystal size for the hmestoue limits apphcatiou. SmaU-sized crystals in the hmestoue result in low yields due to high dust losses. 

Often, a pilot plant will operate in the viscous region while the commercial unit will operate in the transition region, or alternatively, the pilot plant may be in the transition region and the commercial unit in the turbulent region. Some experience is required to estimate the difference in performance to be expected upon scale-up. 

In general, it is not necessary to model Z/T ratios between pilot and commercial units. 

In order to make the pilot unit more like a commercial unit in macro-scale characteristics, the pilot unit impeller must be designed... 

Scale-Up on Rate Filtration rates calculated from bench-scale data shouldbe multiplied by a factor of 0.8 for all types of commercial units which do not employ continuous washing of the filter medium and on which there is a possibility of filter-medium bhnding. For those units which employ continuous filter-medium washing, belt-type drum and horizontal units, the scale-up fac tor maybe increased to 0.9. The use of this scale-up fac tor assumes the following ... 

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