Shell side reactions

Phosgene synthesis from CO and Cl2 in a multitubular reactor (Fig. 19-225). The activated carbon catalyst is packed inside the tubes with water on the shell side. Reaction by-products include CCl4. The temperature profile in a tube (shown in the figure) is characterized by a hot spot. The position of the hot spot moves toward the exit of the reactor as the catalyst deactivates. 

The dehydrogenation of 2-butanol is conducted in a multitube vapor-phase reactor over a zinc oxide (20—23), copper (24—27), or brass (28) catalyst, at temperatures of 250—400°C, and pressures slightly above atmospheric. The reaction is endothermic and heat is suppHed from a heat-transfer fluid on the shell side of the reactor. A typical process flow sheet is shown in Figure 1 (29). Catalyst life is three to five years operating in three to six month cycles between oxidative reactivations (30). Catalyst life is impaired by exposure to water, butene oligomers, and di-j -butyl ether (27). 

The highly exothermic nature of the butane-to-maleic anhydride reaction and the principal by-product reactions require substantial heat removal from the reactor. Thus the reaction is carried out in what is effectively a large multitubular heat exchanger which circulates a mixture of 53% potassium nitrate [7757-79-1/, KNO 40% sodium nitrite [7632-00-0], NaN02 and 7% sodium nitrate [7631-99-4], NaNO. Reaction tube diameters are kept at a minimum 25—30 mm in outside diameter to faciUtate heat removal. Reactor tube lengths are between 3 and 6 meters. The exothermic heat of reaction is removed from the salt mixture by the production of steam in an external salt cooler. Reactor temperatures are in the range of 390 to 430°C. Despite the rapid circulation of salt on the shell side of the reactor, catalyst temperatures can be 40 to 60°C higher than the salt temperature. The butane to maleic anhydride reaction typically reaches its maximum efficiency (maximum yield) at about 85% butane conversion. Reported molar yields are typically 50 to 60%. 

Tube-Cooled Converter. The tube-cooled converter functions as an interchanger, consisting of a tube-filled vessel with catalyst on the shell side (Fig. 7c). The combined synthesis and recycle gas enters the bottom of the reactor tubes, where it is heated by the reaction taking place in the surrounding catalyst bed. The gas turns at the top of the tubes and passes down through the catalyst bed. The principal advantage of this converter is in... 

Coolant flow is set by the designed temperature increase of the fluid and needed mass velocity or Reynolds number to maintain a high heat transfer coefficient on the shell side. Smaller flows combined with more baffles results in higher temperature increase on the shell side. Reacting fluid flows upwards in the tubes. This is usually the best plan to even out temperature bumps in the tube side and to minimize temperature feedback to avoid thermal runaway of exothermic reactions. 

Safety valves are often required on the shell side of exchangers and sometimes on the tube side. These valves may require sizing based upon process reaction, overpressure, etc., or on external fire. For details, see Chapter 7, Vol. 1 on safety-relieving devices. 

In this case study, an enzymatic hydrolysis reaction, the racemic ibuprofen ester, i.e. (R)-and (S)-ibuprofen esters in equimolar mixture, undergoes a kinetic resolution in a biphasic enzymatic membrane reactor (EMR). In kinetic resolution, the two enantiomers react at different rates lipase originated from Candida rugosa shows a greater stereopreference towards the (S)-enantiomer. The membrane module consisted of multiple bundles of polymeric hydrophilic hollow fibre. The membrane separated the two immiscible phases, i.e. organic in the shell side and aqueous in the lumen. Racemic substrate in the organic phase reacted with immobilised enzyme on the membrane where the hydrolysis reaction took place, and the product (S)-ibuprofen acid was extracted into the aqueous phase. 

Design a shell-and-tube reactor that has a volume of 24 m and evaluate its performance as the reactor element in the process of Example 6.2. Use tubes with an i.d. of 0.0254m and a length of 5m. Assume components A, B, and C all have a specific heat of 1.9 kJ/(kg-K) and a thermal conductivity of 0.15W/(m-K). Assume 7 ,>, = 70°C. Run the reaction on the tube side and assume that the shell-side temperature is constant (e.g., use condensing steam). Do the consecutive, endothermic case. 

The auto-thermal reaction of ethanol occurred in the shell side of a palladium membrane reactor in which a Zn-Cu/AlaOs industrial catalyst (MDC-3) was packed with silica powder. Ethanol-water mixture (nH2o/nEioH=l or 3) and oxygen (noa/nEioH=0.2,0.776 or 1.035) are fed concurrently to the shell side. The reaction temperatures were set at 593-723 K and the pijrasures were 3 10 atm. 

Selectivity may also come from reducing the contribution of a side reaction, e.g. the reaction of a labile moiety on a molecule which itself undergoes a reaction. Here, control over the temperature, i.e. the avoidance of hot spots, is the key to increasing selectivity. In this respect, the oxidative dehydrogenation of an undisclosed methanol derivative to the corresponding aldehyde was investigated in the framework of the development of a large-scale chemical production process. A selectivity of 96% at 55% conversion was found for the micro reactor (390 °C), which exceeds the performance of laboratory pan-like (40% 50% 550 °C) and short shell-and-tube (85% 50% 450 °C) reactors [73,110,112,153,154]. 

The first reaction is exothermic, and the second is endothermic. Overall, the reaction evolves considerable heat. Figure 7.1 shows two alternative reactor designs2. Figure 7.1a shows a shell-and-tube type of device that generates steam on the shell side. The temperature profile shows a peak shortly after the reactor inlet because of a... 

Inorganic membranes employed in reaction/transport studies were either in tubular form (a single membrane tube incorporating an inner tube side and an outer shell side in double pipe configuration or as multichannel monolith) or plate-shaped disks as shown in Figure 7.1 (Shinji et al. 1982, Zaspalis et al. 1990, Cussler 1988). For increased mechanical resistance the thin porous (usually mesoporous) membrane layers are usually supported on top of macroporous supports (pores 1-lS /im), very often via an intermediate porous layer, with pore size 100-1500 nm, (Keizer and Burggraaf 1988). 

Air from the compressor is split into two streams primary air is premixed with the fuel and then fed to the catalyst, which is operated under O2 defect conditions secondary air is used first as a catalyst cooling stream and then mixed with the partially converted stream from the catalyst in a downstream homogeneous section where ignition of gas-phase combustion occurs and complete fuel burnout is readily achieved. The control of the catalyst temperature below 1000 Cis achieved by means of O2 starvation to the catalyst surface, which leads to the release of reaction heat controlled by the mass transfer rate of O2 in the fuel-rich stream and of backside cooling of the catalyst with secondary air. To handle both processes, a catalyst/heat exchanger module has been developed, which consists of a bundle of small tubes externally coated with an active catalyst layer, with cooling air and fuel-rich stream flowing in the tube and in the shell side, respectively [24]. 

Pentane Isomerization. Pentane isomerization, although carried out on a much smaller scale, increased the critical supply of aviation gasolines toward the end of the war. Two pentane processes—one developed by Shell and one by Standard (Indiana) —were commercialized before the end of the war. The principal differences between the butane and pentane processes are the use in pentane isomerization of somewhat milder conditions and the use of an inhibitor to suppress side reactions, principally disproportionation. In general, the problems of the butane processes are inherent also in pentane isomerization, but the quality of the feed stocks is less important. Catalyst life is much... 

Styrene. All commercial processes use the catalytic dehydrogenation of ethylbenzene for the manufacture of styrene.189 A mixture of steam and ethylbenzene is reacted on a catalyst at about 600°C and usually below atmospheric pressure. These operating conditions are chosen to prevent cracking processes. Side reactions are further suppressed by running the reaction at relatively low conversion levels (50-70%) to obtain styrene yields about 90%. The preferred catalyst is iron oxide and chromia promoted with KzO, the so-called Shell 015 catalyst.190... 

The operating conditions for the three processes are very similar— only temperatures are somewhat dissimilar. The Shell Development system, employing a modified Friedel-Crafts system, operates at a lower temperature—150°-210°F vs. 250°-400°F for the other two processes. However, the equilibrium effects of the temperature differences are minimized as shown by the similarity in n-C4 and n-C5 yields shown in Table VI. Unleaded octane numbers for C5/C6 isomerate, obtained from a pure C5/C6 straight-run fraction, could not be found in the literature for the Shell process. However, pilot unit operations charging laboratory blends of n-C5, n-C6, and C6 naphthenes have been reported (26, 45). In the Shell process the use of antimony trichloride and hydrogen has considerably reduced the amount of side reactions for a Friedel-Crafts system so that the yield for this process is quite close to the yield structure for the other two processes. 

Fixed-bed reactors resemble multitube heat exchangers, with the catalyst packed in vertical tubes held in a tubesheet at top and bottom. Reaction heat can be removed by generating steam on the shell side of the reactor or by some other heat-transfer fluid. However, temperature control is more difficult in a fixed-bed than in a fluulized-bed reactor because localized hot spots tend to develop in the tubes. 

Steam Superheater This unit superheats saturated steam from 250°C (and 4000kPa) to 380°C. The product steam is of medium pressure and suitable quality for in-house application and also for export. The superheater cools the reaction gases from the reactor exit temperature of 645°C to 595°C. Design pressure on the shell side is approximately 5000 kPa. The steam superheater is constructed from mild steel. 

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