Catalysts hot spots

Catalyst hot spot because of flow maldistribution or instabilities... 

Generally speaking, temperature control in fixed beds is difficult because heat loads vary through the bed. Also, in exothermic reactors, the temperature in the catalyst can become locally excessive. Such hot spots can cause the onset of undesired reactions or catalyst degradation. In tubular devices such as shown in Fig. 2.6a and b, the smaller the diameter of tube, the better is the temperature control. Temperature-control problems also can be overcome by using a mixture of catalyst and inert solid to effectively dilute the catalyst. Varying this mixture allows the rate of reaction in different parts of the bed to be controlled more easily. 

Heterogeneous catalysts are more common. However, they degrade and need replacement. If contaminants in the feed material or recycle shorten catalyst life, then extra separation to remove these contaminants before the feed enters the reactor might be justified. If the cataylst is sensitive to extreme conditions, such as high temperature, then some measures can help to avoid local hot spots and extend catalyst life ... 

Vanadium phosphoms oxide-based catalysts ate unstable in that they tend to lose phosphoms over time at reaction temperatures. Hot spots in fixed-bed reactors tend to accelerate this loss of phosphoms. This loss of phosphoms also produces a decrease in selectivity (70,136). Many steps have been taken, however, to aHeviate these problems and create an environment where the catalyst can operate at lower temperatures. For example, volatile organophosphoms compounds are fed to the reactor to mitigate the problem of phosphoms loss by the catalyst (137). The phosphoms feed also has the effect of controlling catalyst activity and thus improving catalyst selectivity in the reactor. The catalyst pack in the reactor may be stratified with an inert material (138,139). Stratification has the effect of reducing the extent of reaction pet unit volume and thus reducing the observed catalyst temperature (hot... 

Catalyst Effectiveness. Even at steady-state, isothermal conditions, consideration must be given to the possible loss in catalyst activity resulting from gradients. The loss is usually calculated based on the effectiveness factor, which is the diffusion-limited reaction rate within catalyst pores divided by the reaction rate at catalyst surface conditions (50). The effectiveness factor E, in turn, is related to the Thiele modulus,

first-order rate constant, a the internal surface area, and the effective diffusivity. It is desirable for E to be as close as possible to its maximum value of unity. Various formulas have been developed for E, which are particularly usehil for analyzing reactors that are potentially subject to thermal instabilities, such as hot spots and temperature mnaways (1,48,51). 

Catalysts such as iron oxides cause isomeriza tion of the ethylene oxide to acetaldehyde with the evolution of heat. The acetaldehyde has a much lower autoignition temperature in air than does ethylene oxide, and the two effects may lead to hot-spot ignition (190,191). 

During filling, the catalyst is distributed uniformly to avoid the possibility of channeling that coiild lead to poor heat transfer, poor conversion, and harm to the catalyst because of hot spots. During startup, sudden surges of flow may disturb the bed and are to be avoided. For instance, in a study of a hydrodesulfuiizer by Murphree et al. (Ind. Eng. Chem. Proc. Des. size unit varied between 47 and 80 percent with different modes of loading and startup. 

A salient feature of the fluidized bed reactor is that it operates at nearly constant temperature and is, therefore, easy to control. Also, there is no opportunity for hot spots (a condition where a small increase in the wall temperature causes the temperature in a certain region of the reactor to increase rapidly, resulting in uncontrollable reactions) to develop as in the case of the fixed bed reactor. However, the fluidized bed is not as flexible as the fixed bed in adding or removing heat. The loss of catalyst due to carryover with the gas stream from the reactor and regenerator may cause problems. In this case, particle attrition reduces their size to such an extent where they are no longer fluidized, but instead flow with the gas stream. If this occurs, cyclone separators placed in the effluent lines from the reactor and the regenerator can recover the fine particles. These cyclones remove the majority of the entrained equilibrium size catalyst particles and smaller fines. The catalyst fines are attrition products caused by... 

Hot spot formation witliin tlie reactor can result in catalyst breakdown or physical deterioration of tlie reactor vessel." If tlie endothermic cyanide reaction has ceased (e.g., because of poor catalyst performance), the reactor is likely to overheat. Iron is a decomposition catalyst for hydrogen cyanide and ammonia under the conditions present in the cyanide reactor, and e. posed iron surfaces in the reactor or reactor feed system can result in uncontrolled decomposition, which could in turn lead to an accidaital release by overheating and overpressure. 

Catalyst° Time on Stream, hrs Inlet S/G Inlet Hot Spot Outlet... 

N02 at concentrations up to 8 ppm(v) in the inlet gas did not poison the C150-1-03 catalyst. The location of the hot spot fluctuated between the 31 and 44% levels. The hot spot did not drop sharply down into the catalyst bed as it had during the poisoning studies with H2S and HC1. 

Operability. All four series of experiments prove that HGR metha-nation is a usable and operable system. With a total gas recycle ratio of about 10 1 and with CO concentrations in the mixed feed entering the catalyst bed as high as 4.3% (wet basis), temperature control was excellent and no hot spots developed. It appears likely that lower recycle... 

The phosphotriesterase from Pseudomonas diminuta was shown to catalyze the enantioselective hydrolysis of several racemic phosphates (21), the Sp isomer reacting faster than the Rp compound [65,66]. Further improvements using directed evolution were achieved by first carrying out a restricted alanine-scan [67] (i.e. at predetermined amino acid positions alanine was introduced). Whenever an effect on activity/ enantioselectivity was observed, the position was defined as a hot spot. Subsequently, randomization at several hot spots was performed, which led to the identification of several highly (S)- or (R)-selective mutants [66]. A similar procedure was applied to the generation of mutant phosphotriesterases as catalysts in the kinetic resolution of racemic phosphonates [68]. 

An interesting way to retard catalyst deactivation is to expose the reaction mixture to ultrasound. Ultrasound treatment of the mixture creates local hot spots, which lead to the formation of cavitation bubbles. These cavitation bubbles bombard the solid, dirty surface leading to the removal of carbonaceous deposits [38]. The ultrasound source can be inside the reactor vessel (ultrasound stick) or ultrasound generators can be placed in contact with the wall of the reactor. Both designs work in practice, and the catalyst lifetime can be essentially prolonged, leading to process intensification. The effects of ultrasound are discussed in detail in a review article [39]. 

The application of microchannel technology is a natural fit for the production of synthetic fuels via the FT process. The primary limitations of conventional FT technology include the removal of process heat that can produce hot spots and severely shorten catalyst life, and effective management of two-phase flow as synthesis gas transforms into hquid hydrocarbons. Both these issues can be addressed with microchaimel technology, which greatly improves heat transfer and precisely controls flow through thousands of parallel chaimels. 

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