Catalytic external heat transfer

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."... 

The hydrogen producing reactions are limited by thermodynamic equilibrium. The reactions must take place under carefully controlled external firing, with heat transfer taking place from the combustion gas in the firebox to the process gas in the catalyst-filled tubes. Carbon monoxide in the product gas is converted almost completely to hydrogen in the downstream catalytic reactor. 

The effects of non-uniform distribution of the catalytic material within the support in the performance of catalyst pellets started receiving attention in the late 60 s (cf 1-4). These, as well as later studies, both theoretical and experimental, demonstrated that non-uniformly distributed catalysts can offer superior conversion, selectivity, durability, and thermal sensitivity characteristics over those wherein the activity is uniform. Work in this area has been reviewed by Gavriilidis et al. (5). Recently, Wu et al. (6) showed that for any catalyst performance index (i.e. conversion, selectivity or yield) and for the most general case of an arbitrary number of reactions, following arbitrary kinetics, occurring in a non-isothermal pellet, with finite external mass and heat transfer resistances, the optimal catalyst distribution remains a Dirac-delta function. 

In general, large industrial fixed beds operate under near-adiabatic conditions, whereas small laboratory-scale fixed beds may approach isothermal operation (Ruthven, 1984). Especially, for most environmental applications, for catalytic, adsorption, and ion-exchange operations, the species to be removed are in such low concentrations that the operarion is nearly isothermal. Thus, the heat transfer to the external fixed-bed wall is often of minimal importance. 

Q = rate of heat transfer per unit mass of catalyst hf = heat transfer coefficient per unit of external surface area Tb = temperature at the bulk of the fluid Ts = temperature at catalytic surface. 

When external gradients correspond to substantial differences in concentration or temperature between the bulk of the fluid and the external surface of the catalyst particle, the rate of reaction at the surface is significantly different from that which would prevail if the concentration or temperature at the surface were equal to that in the bulk of the fluid. The catalytic reaction is then said to be influenced by external mass or heat transfer, respectively, and, when this influence is the dominant one, the rate corresponds to a regime of external mass or heat transfer. 

Non-Isothermal Mass and Heat Balance Model of the Catalytic Pellet BVP with Finite External Mass and Heat Transfer Resistance... 

In this section we have presented and solved the BVPs associated with the diffusion and reaction that take place in the pores of a porous catalyst pellet. The results were expressed graphically in terms of the effectiveness factor rj versus the Thiele modulus d> for two cases One with negligible external mass and heat transfer resistances, i.e., when Sh and Nu —> oo, and another with finite Sh and Nu values. This problem is very important in the design of fixed-bed catalytic reactors. The sample results presented here have shown that for exothermal reactions multiple steady states may occur over a range of Thiele moduli d>. Efficient numerical techniques have been presented as MATLAB programs that solve singular two-point boundary value problems. 

In catalytic cracking, a large amount of heat needs to be supplied at the reactor inlet to vapourize the feed and provide the heat of reaction. In commercial units, this heat is provided by the hot catalyst recirculated from the regenerator. High heat transfer rates are achieved when the fluidized catalyst is mixed with the feed. In some experimental units, feed and catalyst are injected at reactor temperature. The heat of reaction must then be supplied by an external heating element, at much slower rates of heat transfer. The product selectivity from such laboratory units cannot be expected to simulate that of commercial units... 

In order to avoid the unfavorable process conditions, different flue-gas treatment processes for combustion plants based on catalytic filters were developed, which combine fly-ash removal with SCR of ISKh with NH3 [4—8], The advantages of these processes are space and treatment-cost savings, reduced internal and external mass transfer resistances compared to honeycomb SCR catalysts, heat recovery from offgases with good efficiency, and low corrosion problems due to the removal of both dust and NOx at high temperatures. 

The mass transfer effects cause, in general, a decrease of the measured reaction rate. The heat transfer effects may lead in the case of endothermic reactions also to a decrease of the equilibrium value and the resulting negative effect may be more pronounced. With exothermic reactions, an insufficient heat removal causes an increase of the reaction rate. In such a case, if both the heat and mass transfer effects are operating, they can either compensate each other or one of them prevails. In the case of internal transfer, mass transport effects are usually more important than heat transport, but in the case of external transfer the opposite prevails. Heat transport effects frequently play a more important role, especially in catalytic reactions of gases. The influence of heat and mass transfer effects should be evaluated before the determination of kinetics. These effects should preferably be completely eliminated. 

The simplest heterogeneous model is one with plug-flow in the fluid phase, mass and heat transfer between the fluid and solid phases, and surface catalytic reaction on the solid — if the catalyst is indeed deposited near the pellet external surface. 

An advantage offered by catalytic combustion that may be important for heat generation is the potentially improved heat transfer, since heat is generated on a solid surface. Heat generation systems operating at catalyst temperatures up to 800-1000 C may thus be controlled more efficiently through external cooling of the catalyst. 

Endothermic reactions, such as steam reforming, are usually carried out in long narrow tubes filled with catalysts and externally heated by flames. The heat could be provided more uniformly and more accurately at the necessary level by a combustion catalyst coated on the outside of the tubes, and heat transfer rates could be further improved by coating the endothermic reaction catalyst on the inner wall of the tube. In this way, the heat of combustion is transferred to the heat sink (the endothermic reaction) through the solid wall, avoiding solid-gas heat transfer resistances. However, the tubular geometry is not most efficient for this application because of the difficulty to coat the inside of the tubes and the need to include static mixers to facilitate mass transfer to the catalytic surfaces. 

Theoretically, catalytic distillation can overcome limitations in a typical two-step process consisting of reaction followed by distillation or separation. Often, a two-step process is limited by chemical equilibrium, heat transfer, mass transfer, or some combination of these. Catalytic distillation can overcome many of these constraints by simultaneously separating products from reactants, maintaining nearly isothermal operation and lowering the external ratio of reaction diluents. 

In many catalytic systems multiple reactions occur, so that selectivity becomes important. In Sec. 2-10 point and overall selectivities were evaluated for homogeneous well-mixed systems of parallel and consecutive reactions. In Sec. 10-5 we saw that external diffusion and heat-transfer resistances affect the selectivity. Here we shall examiineHEieHnfiuence of intrapellet res ahces on selectivity. Systems with first-order kinetics at isothermal conditions are analyzed analytically in Sec. 11-12 for parallel and consecutive reactions. Results for other kinetics, or for nonisothermal conditions, can be developed in a similar way but require numerical solution. ... 

Gas-solid (catalytic) reactions. Mass transfer is likely to be more important within the pellet than in the external film, and heat transfer more important in the film than within the pellet. In other words, intraphase mass transfer and interphase heat transfer would normally be the dominant transport processes. Thus the pellet can reasonably be assumed to be isothermal. 

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