Back mixing

In this condenser, part of the stripper off-gases are condensed (the heat of condensation is used to generate low pressure steam). The carbamate formed and noncondensed NH and CO2 are put into the reactor bottom and conversion of the carbamate into urea takes place. The reactor is sized to allow enough residence time for the reaction to approach equiUbrium. The heat required for the urea reaction and for heating the solution is suppHed by additional condensation of NH and CO2. The reactor which is lined with 316 L stainless steel, contains sieve trays to provide good contact between the gas and Hquid phases and to prevent back-mixing. The stripper tubes are 25-22-2 stainless steel. Some strippers are still in service after almost 30 years of operation. 

In addition to production of simple monofunctional products in hydrocarbon oxidation there are many complex, multifimctional products that are produced by less weU-understood mechanisms. There are also important influences of reactor and reaction types (plug-flow or batch, back-mixed, vapor-phase, Hquid-phase, catalysts, etc). 

Efficiency of Intermediate Formation. The variation of the efficiency of a primary intermediate with conversion of the feed hydrocarbon can be calculated (22). Ratios of the propagation rate constants ( 2 / i) reactor type (batch or plug-flow vs back-mixed) are important parameters. 

Eigure 2 shows that even materials which are rather resistant to oxidation ( 2/ 1 0.1) are consumed to a noticeable degree at high conversions. Also the use of plug-flow or batch reactors can offer a measurable improvement in efficiencies in comparison with back-mixed reactors. Intermediates that cooxidize about as readily as the feed hydrocarbon (eg, ketones with similar stmcture) can be produced in perhaps reasonable efficiencies but, except at very low conversions, are subject to considerable loss through oxidation. They may be suitable coproducts if they are also precursors to more oxidation-resistant desirable materials. Intermediates which oxidize relatively rapidly (/ 2 / i — 3-50 eg, alcohols and aldehydes) are difficult to produce in appreciable amounts, even in batch or plug-flow reactors. Indeed, for = 50, to isolate 90% or more of the intermediate made, the conversion must... 

Eig. 2. Efficiency to a primary intermediate as % of maximum (zero conversion) efficiency x axis is feed conversion. Parameters are oxidation rate-constant ratios ( 2 / i) for primary intermediate vs feed and reactor type A, plug-flow or batch B, back-mixed. 

Wet Oxidation Reactor Design. Several types of reactor designs have been employed for wet oxidation processes. Zimpro, the largest manufacturer of wet oxidation systems, typically uses a tower reactor system. The reactor is a bubble tower where air is introduced at the bottom to achieve plug flow with controlled back-mixing. Residence time is typically under one hour. A horizontal, stirred tank reactor system, known as the Wetox process, was initially developed by Barber-Cohnan, and is also offered by Zimpro. 

Macromixing is estabflshed by the mean convective flow pattern. The flow is divided into different circulation loops or zones created by the mean flow field. The material is exchanged between zones, increasing homogeneity. Micromixing, on the other hand, occurs by turbulent diffusion. Each circulation zone is further divided into a series of back-mixed or plug flow cells between which complete intermingling of molecules takes place. 

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. 

The smaller reactor approaches plug-flow behavior and exhibits a large temperature gradient. In this case, external recycle provides the same degree of back-mixing as is provided by internal circulation in the larger diameter reactor. 

Heat Release and Reactor Stability. Highly exothermic reactions, such as with phthaHc anhydride manufacture or Fischer-Tropsch synthesis, compounded with the low thermal conductivity of catalyst peUets, make fixed-bed reactors vulnerable to temperature excursions and mnaways. The larger fixed-bed reactors are more difficult to control and thus may limit the reactions to jacketed bundles of tubes with diameters under - 5 cm. The concerns may even be sufficiently large to favor the more complex but back-mixed slurry reactors. 

Bubble columns in series have been used to establish the same effective mix of plug-flow and back-mixing behavior required for Hquid-phase oxidation of cyclohexane, as obtained with staged reactors in series. WeU-mixed behavior has been established with both Hquid and air recycle. The choice of one bubble column reactor was motivated by the need to minimize sticky by-products that accumulated on the walls (93). Here, high air rate also increased conversion by eliminating reaction water from the reactor, thus illustrating that the choice of a reactor system need not always be based on compromise, and solutions to production and maintenance problems are complementary. Unlike the Hquid in most bubble columns, Hquid in this reactor was intentionally weU mixed. 

More recent process research aimed at anionic PS is that of BASF AG. Unlike the Dow Process, the BASF process utilizes continuous linear-flow reactors (LFR) with no back-mixing to make narrow polydispersity resins. This process consists of a series alternating reactors and heat exchangers (Fig. 22). Inside the reactors, the polymerization exotherm carries the temperature from 30°C at the inlet to 90°C at the outlet. The heat exchangers then take the temperature back down to 30°C. This process, which requires no solvent, results in the formation of narrow polydispersity PS. 

Styrene—maleic anhydride (SMA) copolymers are used where improved resistance to heat is required. Processes similar to those used for SAN copolymers are used. Because of the tendency of maleic anhydride to form alternating copolymers with styrene, composition drift is extremely severe unless the polymerization is carried out in CSTR reactors having high degrees of back-mixing. 

There are essentially three types of coal gasifiers moving-bed or countercurrent reactors fluidized-bed or back-mixed reactors and entrained-flow or plug-flow reactors. The three types are shown schematically in Eigure 2. 

Fig. 21. Iadirect-heat, two-stage, back mixed, and plug flow fluid-bed dryer.

Epichlorohydrin Elastomers without AGE. Polymerization on a commercial scale is done as either a solution or slurry process at 40—130°C in an aromatic, ahphatic, or ether solvent. Typical solvents are toluene, benzene, heptane, and diethyl ether. Trialkylaluniinum-water and triaLkylaluminum—water—acetylacetone catalysts are employed. A cationic, coordination mechanism is proposed for chain propagation. The product is isolated by steam coagulation. Polymerization is done as a continuous process in which the solvent, catalyst, and monomer are fed to a back-mixed reactor. Pinal product composition of ECH—EO is determined by careful control of the unreacted, or background, monomer in the reactor. In the manufacture of copolymers, the relative reactivity ratios must be considered. The reactivity ratio of EO to ECH has been estimated to be approximately 7 (35—37). 

Sieve plates have less back mixing than bubble-cap plates because of less obstruction to flow. 

Increased gas rate increases turbulence and the degree of back mixing of liquid. 

In design of separating chambers, static vessels or continuous-flow tanks may be used. Care must be taken to protect the flow from turbulence, which coiild cause back mixing of partially separated fluids or which could cany unseparated hquids rapidly to the separated-hquid outlet. Vertical baffles to protect rising biibbles from flow currents are sometimes employed. Unseparated fluids should be distributed to the separating region as uniformly and with as little velocity as possible. When the bubble rise velocity is quite low, shallow tanks or flow channels should be used to minimize the residence time required. 

Spray Towers These are simple gravity extractors, consisting of empty towers with provisions for introducing and removing liquids at the ends (see Fig. 15-32). The interface can be run above the top distributor, below the bottom distributor, or in the middle, depending on where the best performance is achieved. Because of severe axial back mixing, it is difficult to achieve the equivalent of more than one or two theoretical stages or transfer units on one side of the interface. For this reason they have only rarely been applied in extraction applications. 

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