Reactor, catalytic

Fluidized-bed catalytic reactors. In fluidized-bed reactors, solid material in the form of fine particles is held in suspension by the upward flow of the reacting fluid. The effect of the rapid motion of the particles is good heat transfer and temperature uniformity. This prevents the formation of the hot spots that can occur with fixed-bed reactors. 

Fluidized-bed catalytic reactors tend to generate loss of catalyst through attrition of the solid particles, causing fines to be generated. 

Figure 13.5 shows a flowsheet for the manufacture of phthalic anhydride by the oxidation of o-xylene. Air and o-xylene are heated and mixed in a Venturi, where the o-xylene vaporizes. The reaction mixture enters a tubular catalytic reactor. The heat of reaction is removed from the reactor by recirculation of molten salt. The temperature control in the reactor would be diflficult to maintain by methods other than molten salt. 

Olefin—Paraffin Separation. The catalytic dehydrogenation of / -paraffins offers a route to the commercial production of linear olefins. Because of limitations imposed by equiUbrium and side reactions, conversion is incomplete. Therefore, to obtain a concentrated olefin product, the olefins must be separated from the reactor effluent (81—85), and the unreacted / -paraffins must be recycled to the catalytic reactor for further conversion. 

Properties. Table 4 contains typical gasoline quaUty data from the New Zealand plant (67). MTG gasoline typically contains 60 vol % saturates, ie, paraffins and naphthenes 10 vol % olefins and 30 vol % aromatics. Sulfur and nitrogen levels in the gasoline are virtually lul. The MTG process produces ca 3—7 wt % durene [95-93-2] (1,2,4,5-tetra-methylbenzene) but the level is reduced to ca 2 wt % in the finished gasoline product by hydrodealkylation of the durene in a separate catalytic reactor. 

In open fibers the fiber wall may be a permselective membrane, and uses include dialysis, ultrafiltration, reverse osmosis, Dorman exchange (dialysis), osmotic pumping, pervaporation, gaseous separation, and stream filtration. Alternatively, the fiber wall may act as a catalytic reactor and immobilization of catalyst and enzyme in the wall entity may occur. Loaded fibers are used as sorbents, and in ion exchange and controlled release. Special uses of hoUow fibers include tissue-culture growth, heat exchangers, and others. 

Table 7. Fluidized-Bed Catalytic Reactors for Chemical Synthesis...

A derivative of the Claus process is the Recycle Selectox process, developed by Parsons and Unocal and Hcensed through UOP. Once-Thm Selectox is suitable for very lean acid gas streams (1—5 mol % hydrogen sulfide), which cannot be effectively processed in a Claus unit. As shown in Figure 9, the process is similar to a standard Claus plant, except that the thermal combustor and waste heat boiler have been replaced with a catalytic reactor. The Selectox catalyst promotes the selective oxidation of hydrogen sulfide to sulfur dioxide, ie, hydrocarbons in the feed are not oxidized. These plants typically employ two Claus catalytic stages downstream of the Selectox reactor, to achieve an overall sulfur recovery of 90—95%. 

Process Description. Reactors used in the vapor-phase synthesis of thiophene and aLkylthiophenes are all multitubular, fixed-bed catalytic reactors operating at atmospheric pressure, or up to 10 kPa and with hot-air circulation on the shell, or salt bath heating, maintaining reaction temperatures in the range of 400—500°C. The feedstocks, in the appropriate molar ratio, are vaporized and passed through the catalyst bed. Condensation gives the cmde product mixture noncondensable vapors are vented to the incinerator. 

This is a desirable side reaction in the first catalytic reactor of the Claus sulfur recovery process. 

The hydrocarbon gas feedstock and Hquid sulfur are separately preheated in an externally fired tubular heater. When the gas reaches 480—650°C, it joins the vaporized sulfur. A special venturi nozzle can be used for mixing the two streams (81). The mixed stream flows through a radiantly-heated pipe cod, where some reaction takes place, before entering an adiabatic catalytic reactor. In the adiabatic reactor, the reaction goes to over 90% completion at a temperature of 580—635°C and a pressure of approximately 250—500 kPa (2.5—5.0 atm). Heater tubes are constmcted from high alloy stainless steel and reportedly must be replaced every 2—3 years (79,82—84). Furnaces are generally fired with natural gas or refinery gas, and heat transfer to the tube coil occurs primarily by radiation with no direct contact of the flames on the tubes. Design of the furnace is critical to achieve uniform heat around the tubes to avoid rapid corrosion at "hot spots."... 

A mixture of CO and H2, called synthesis gas, may also be used in other catalytic reactors to make methanol (qv) or hydrocarbons (qv) ... 

This clean and shifted gas is then converted to hydrocarbons and other products ia a series of catalytic reactors. The synthesis reaction is usually carried out usiag two or three reactors ia series because of the highly exothermic nature of the overall reaction. 

A fluidi2ed-bed catalytic reactor system developed by C. E. Lummus (323) offers several advantages over fixed-bed systems ia temperature control, heat and mass transfer, and continuity of operation. Higher catalyst activity levels and higher ethylene yields (99% compared to 94—96% with fixed-bed systems) are accompHshed by continuous circulation of catalyst between reactor and regenerator for carbon bum-off and continuous replacement of catalyst through attrition. 

As an example the use of ceramic membranes for ethane dehydrogenation has been discussed (91). The constmction of a commercial reactor, however, is difficult, and a sweep gas is requited to shift the product composition away from equiUbrium values. The achievable conversion also depends on the permeabihty of the membrane. Figure 7 shows the equiUbrium conversion and the conversion that can be obtained from a membrane reactor by selectively removing 80% of the hydrogen produced. Another way to use membranes is only for separation and not for reaction. In this method, a conventional, multiple, fixed-bed catalytic reactor is used for the dehydrogenation. After each bed, the hydrogen is partially separated using membranes to shift the equihbrium. Since separation is independent of reaction, reaction temperature can be optimized for superior performance. Both concepts have been proven in bench-scale units, but are yet to be demonstrated in commercial reactors. 

The various reaction rate properties of the different solvents influence the design of a catalytic reactor. Eor example, for a specific catalyst bed design, an effluent stream containing a preponderance of monohydric alcohols, aromatic hydrocarbons, or propjiene requires a lower catalyst operating temperature than that required for solvents such as isophorone and short-chain acetates. 

FIG. 12-860 Countercurrent gas-solids flow at the top disengaging section of a moving-bed catalytic reactor. 

FIG. 12-866 Vap or disengaging tray at the top of a gravity-hed catalytic reactor. This design may also he employed for the addition of gas to a bed of solids. 

In most catalytic-reactor systems, no sohds removal is necessary as the catalyst is retained in the system and sohds loss is in the form of fines that are not collected by the dust-recovery system. 

M. O. Tarhan, Catalytic Reactor Design, McGraw-Hill, 1983. 

In a catalytic reactor, concentrations and temperature change along the flow path of the reactants, and in some cases also normal to the flow. The sum of all these changes over the catalyst-filled volume in time will give the production of the reactor. There are several methods to account for all these changes, illustrated on Figure 8.1.1. 

Fluidized bed catalytic reactors seem to have so many advantageous features that they were considered for many processes. One of the advantages is their excellent heat transfer characteristics, due to the large catalyst surface to volume ratio, so very little temperature difference is needed for heat transfer. This would make temperature control problem-free. The second is the uniformity of reaction conditions in the bed. 

Catalytic reactor. The role of the catalyst was described earlier it must burn enough of the incoming fuel to generate an outlet gas temperature high enough to initiate rapid homogeneous combustion just past the catalyst exit. 

Ramachandran, P. A. and Chaudhari, R. V., Three Phase Catalytic Reactors, Gordon and Breach Science Publishers. 

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