Continuously Pilot Synthesis

Keywords Lij[Nii/3Coi/3Mni/302, continuously pilot synthesis, microwave-heating, electrochemical performances... 

In 1930, DuPont launched the synthetic fiber industry with the discovery of nylon-6,6.2 In 1938, a pilot plant for nylon-6,6 production was put into operation, and in 1939, production was commenced at a large-scale plant in Seaford, Delaware. The classical method for the synthesis of nylon-6,6 involves a two-step process. In the first step, hexamethylene diamine (HMDA) is reacted with adipic acid (AA) to form a nylon salt. Polymerization of the aqueous salt solution is carried out at temperatures in the range of about 210-275°C at a steam pressure of about 1.7 MPa. When 275°C is reached, the pressure is reduced to atmospheric pressure and heating is continued to drive the reaction to completion. 

Crameri et al. (1997) have reported an asymmetric hydrogenation constituting an important step in the production of a new calcium antagonist, Mibefradil (POSICOR) (of Hoffmann-LaRoche). Pilot-scale synthesis of (S)-2-(4-flurophenyl)-3-methylbutanoic acid by the asymmetric hydrogenation of 2-(4-fluorophenyl)-3-methyl but-2-enoic acid with a [Ru (/ )-MeOBIPHEP)(OAc)2]-catalyst has been described. The hydrogenation was performed in a continuous mode in a cascade stirred-tank reactor system at a pressure of 270 bar. A large reduction in total reactor volume compared to the batch mode was realized. 

The pilot-scale SBCR unit with cross-flow filtration module is schematically represented in Figure 15.5. The SBCR has a 5.08 cm diameter and 2 m height with an effective reactor volume of 3.7 L. The synthesis gas passes continuously through the reactor and is distributed by a sparger near the bottom of the reactor vessel. The product gas and slurry exit at the top of the reactor and pass through an overhead gas/liquid separator, where the slurry is disengaged from the gas phase. Vapor products and unreacted syngas exit the gas/liquid separator and enter a warm trap (373 K) followed by a cold trap (273 K). A dry flow meter downstream of the cold trap measures the exit gas flow rate. 

Kinetic Study of the Phenolysis Reaction. With the demonstration that all of the already outlined deficiencies of ammonium lignin sulfonates as a phenol replacement can be reduced by phenolysis, attention was turned to consideration of the construction of a pilot plant scale continuous tube reactor. This is needed in order to prepare the large amounts of phenolyzed lignin sulfonates required for resin synthesis and testing under plywood production conditions. 

The deactivation of methanol-synthesis catalyst was studied in laboratory and pilot-plant slurry reactors using a concentrated, poison-free, CO-rich feedstream. The extent of catalyst deactivation correlated with the loss of BET surface area. A model of catalyst deactivation as a function of temperature and time was developed from experimental data. The model suggested that continuous catalyst addition and withdrawal, rather than temperature programming, was the best way to maintain a constant rate of methanol production as the catalyst ages. Catalyst addition and withdrawal was demonstrated in the pilot plant. 

Experimental studies have demonstrated that conventional methanol-synthesis catalysts deactivate slowly in a slurry reactor, even with a concentrated, CO rich feedstream. The catalyst activity correlates with the BET surface area and the rate of deactivation increases rapidly with temperature. This limits the utility of temperature programming as a means for maintaining a constant methanol production rate as the catalyst ages. Continuous catalyst addition and withdrawal is the preferred means to maintain constant methanol production. The key mechanical and process features of this technique were demonstrated In the pilot plant. 

At the start of the project, and continuing throughout the project and for troubleshooting, we need a range of input data about the chemicals and reactions and about species used and produced in the process. Information may be supplied from chemists who have imraveled the mysteries of a synthesis or from a pilot plant or small-scale operations that provide key design data (as illustrated in step 4a in Table 16.1). 

In the history of PU, some continuous processes for polyether polyol synthesis by anionic polymerisation were developed, but only at small scale (i.e., pilot plant). Tubular reactors with static mixing systems or a column with plate reactor types were used, but these technologies were not extended to industrial scale levels. The first continuous process for high MW polyether synthesis was developed by Bayer (IMPACT Technology) and is based on the very rapid coordinative polymerisation of alkylene oxides, especially PO, with dimetallic catalysts (DMC catalysts - see Chapter 5). A principle technological scheme of a polyether polyol fabrication plant is presented in Figure 4.30. 

Pilot-plant operation is conducted usually at 300-325 C., 20-atmos-pheres pressure, with recycle of 3-4 volumes end gas/volume fresh feed. The latter is 1.8 to 2.0 H2 to 1 CO, prepared by oxidationof natural gas with oxygen-steam mixtures at 300—400 p.s.i. and 1200 C. The synthesis operation is in fixed fluidized bed that is, the bed of catalyst is suspended in the flowing gas with no carry-over of powdered catalyst outside the converter. Carry-over is completely avoided by the use of Aloxite filters in the expanded section of the top of the converter. Catalyst density in the fluidized bed is 60-80 pounds/cubic foot at the start. This density decreases during the first 2-14 days of operation to 10-20 pounds/cubic foot because of spalling of the catalyst induced by carbon formation. With a hydrogen-rich total feed gas, 1600 hours of continuous operation was achieved, and with a carbon dioxide-rich feed gas, only about 400 hours. Operation is limited to 1.5-2.5 linear feet/second gas velocity at this velocity conversions of 90-95% are obtained per pass so that multistage opera-... 

Since its discovery some 55 years ago, the synthesis of caprolactam has been the subject of intense research and development. Interest in alternative routes continues today and current activities receiving a lot of attention are carbon monoxide-based routes under development by DSM, EniChem and DuPont [32]. Numerous routes using a variety of feedstocks have been patented and many have been piloted, however, only seven have actually been commercialized. The first was the process developed by I. G. Farben based on Schlack s chemistry known today as the Rashig or conventional route. Other commercial routes are the CAPROPOL process, the BASF process, the DSM-HPO process, the Allied process, the Toray PNC process, and the SNIA Viscosa process. 

MK-421. Large-scale synthesis of AlaPro in a continuous flow system. Process design and results obtained at the large pilot scale (20). 

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