Temperature rise reactor

Adiabatic operation. If adiabatic operation leads to an acceptable temperature rise for exothermic reactors or an acceptable fall for endothermic reactors, then this is the option normally chosen. If this is the case, then the feed stream to the reactor requires heating and the efiluent stream requires cooling. The heat integration characteristics are thus a cold stream (the reactor feed) and a hot stream (the reactor efiluent). The heat of reaction appears as elevated temperature of the efiluent stream in the case of exothermic reaction or reduced temperature in the case of endothermic reaction. 

Figure 13.16 shows two possible thermal profiles for endothermic plug-fiow reactors. This time the temperature falls for low rates of heat addition and/or high heat of reaction. The temperature rises for the reverse conditions. Under conditions between the profiles shown in Fig. 13.16, a minimum can occur in the temperature profile at an intermediate point between the inlet and exit. 

In a typical adiabatic polymerization, approximately 20 wt % aqueous acrylamide is charged into a stainless steel reactor equipped with agitation, condenser, and cooling jacket or coils. To initiate the polymerization, an aqueous solution of sodium bisulfite [7631-90-5] is added, followed by the addition of a solution of ammonium persulfate [7727-54-0] N2HgS20g. As the polymerization proceeds, the temperature rises to about 90°C, and then begins to fall at the end of the polymerization. The molecular weight obtained depends primarily on the initiator concentration employed. 

Catalytic methanation processes include (/) fixed or fluidized catalyst-bed reactors where temperature rise is controlled by heat exchange or by direct cooling using product gas recycle (2) through wall-cooled reactor where temperature is controlled by heat removal through the walls of catalyst-filled tubes (J) tube-wall reactors where a nickel—aluminum alloy is flame-sprayed and treated to form a Raney-nickel catalyst bonded to the reactor tube heat-exchange surface and (4) slurry or Hquid-phase (oil) methanation. 

Boron Removal. Boron [7440-42-8] is occasionaHy present in water suppHes at an unacceptable level. It cannot be removed with the standard anion-exchange resins unless the water is deionized. Selective removal is possible by using an anion exchanger functionalized with /V-methy1g1ucamine [6284-40-8]. This resin is in limited commercial supply. The borate form of conventional strong base anion exchangers is used in some nuclear reactors to adjust the concentration of boron in water used as a moderator. The resin releases boron as the water temperature rises. 

Liquid Metals. If operating temperatures rise above 250—300°C, where many organic fluids decompose and water exerts high vapor pressure, hquid metals have found some use, eg, mercury for limited appHcation in turbines sodium, especially its low melting eutectic with 23 wt % potassium, as a hydrauhc fluid and coolant in nuclear reactors and potassium, mbidium, cesium, and gallium in some special uses. 

Reaction Conditions. Typical iadustrial practice of this reaction involves mixing vapor-phase propylene and vapor-phase chlorine in a static mixer, foEowed immediately by passing the admixed reactants into a reactor vessel that operates at 69—240 kPa (10—35 psig) and permits virtual complete chlorine conversion, which requires 1—4 s residence time. The overaE reactions are aE highly exothermic and as the reaction proceeds, usuaEy adiabaticaEy, the temperature rises. OptimaEy, the reaction temperature should not exceed 510°C since, above this temperature, pyrolysis of the chlorinated hydrocarbons results in decreased yield and excessive coke formation (27). 

TABLE 23-2 Multibed Reactors, Adiabatic Temperature Rises ... 

Few mechanisms of liquid/liquid reactions have been established, although some related work such as on droplet sizes and power input has been done. Small contents of surface-ac tive and other impurities in reactants of commercial quality can distort a reac tor s predicted performance. Diffusivities in liquids are comparatively low, a factor of 10 less than in gases, so it is probable in most industrial examples that they are diffusion controllech One consequence is that L/L reactions may not be as temperature sensitive as ordinary chemical reactions, although the effec t of temperature rise on viscosity and droplet size can result in substantial rate increases. L/L reac tions will exhibit behavior of homogeneous reactions only when they are very slow, nonionic reactions being the most likely ones. On the whole, in the present state of the art, the design of L/L reactors must depend on scale-up from laboratoiy or pilot plant work. 

Adiabatic plug flow reactors operate under the condition that there is no heat input to the reactor (i.e., Q = 0). The heat released in the reaction is retained in the reaction mixture so that the temperature rise along the reactor parallels the extent of the conversion. Adiabatic operation is important in heterogeneous tubular reactors. 

In a tubular reactor system, the temperature rises along the reactor length for an exothermic reaction unless effective cooling is maintained. For multiple steady states to appear, it is necessary that a... 

Thermal runaway reactions are the results of chemical reactions in batch or semi-batch reactors. A thermal runaway commences when the heat generated by a chemical reaction exceeds the heat that can be removed to the surroundings as shown in Figure 12-5. The surplus heat increases the temperature of the reaction mass, which causes the reaction rate to increase, and subsequently accelerates the rate of heat production. Thermal runaway occurs as follows as the temperature rises, the rate of heat loss to the surroundings increases approximately linearly with temperature. However, the rate of reaction, and thus the... 

A process worker is monitoring the rise in temperature in reactor A. An exothermic reaction occurs producing an alarm requiring the opening of a valve on a circuit which provides cooling water to the reactor. Instead of opening the correct valve, he operates another valve for reactor B, which is the reactor which he monitors on most shifts. Reactor A is destroyed by a runaway reaction. 

The SCB distribution (SCBD) has been extensively studied by fractionation based on compositional difference as well as molecular size. The analysis by cross fractionation, which involves stepwise separation of the molecules on the basis of composition and molecular size, has provided information of inter- and intramolecular SCBD in much detail. The temperature-rising elution fractionation (TREE) method, which separates polymer molecules according to their composition, has been used for HP LDPE it has been found that SCB composition is more or less uniform [24,25]. It can be observed from the appearance of only one melt endotherm peak in the analysis by differential scanning calorimetry (DSC) (Fig. 1) [26]. Wild et al. [27] reported that HP LDPE prepared by tubular reactor exhibits broader SCBD than that prepared by an autoclave reactor. The SCBD can also be varied by changing the polymerization conditions. From the cross fractionation of commercial HP LDPE samples, it has been found that low-MW species generally have more SCBs [13,24]. 

The chapter by Haynes et al. describes the pilot work using Raney nickel catalysts with gas recycle for reactor temperature control. Gas recycle provides dilution of the carbon oxides in the feed gas to the methanator, hence simulating methanation of dilute CO-containing gases which under adiabatic conditions gives a permissible temperature rise. This and the next two papers basically treat this approach, the hallmark of first-generation methanation processes. 

The chapter by White et al. proposes a different approach to metha-nator temperature control. Here the temperature rise is controlled by limiting the amount of reaction in each stage, and that is done by introducing steam (a product of the reaction). High initial temperatures are followed by successively lower temperatures entering each reactor in series. This is a second-generation methanation approach which may follow closely on the first-generation approaches typified by the previous three papers. 

Kinetically Limited Process. Basically, this system limits the temperature rise of each adiabatically operated reactor to safe levels by using high enough space velocities to ensure only partial approach to equilibrium. The exit gases from each reactor are cooled in external waste heat boilers, then passed forward to the next reactor, and so forth. This resembles the equilibrium-limited reactor system as shown in Figure 8, except, of course, that the catalyst beds are much smaller. 

The possible advantages of this system over the equilibrium-limited reactor system are smaller catalyst beds, lower gas recycle requirements, and lower capital requirements. The possible disadvantages of this system are (a) practically no turn-down since any turn-down would be equivalent to decreased space velocities, closer approach to equilibrium, and higher temperature rises (b) maldistribution of gases across the bed would give rise to excessive temperature rises in zones of low flow and (c) considerably shortened catalyst life because of possible high local or zonal temperature and, concurrently, greater chances for carbon laydown. 

The scheme of commercial methane synthesis includes a multistage reaction system and recycle of product gas. Adiabatic reactors connected with waste heat boilers are used to remove the heat in the form of high pressure steam. In designing the pilot plants, major emphasis was placed on the design of the catalytic reactor system. Thermodynamic parameters (composition of feed gas, temperature, temperature rise, pressure, etc.) as well as hydrodynamic parameters (bed depth, linear velocity, catalyst pellet size, etc.) are identical to those in a commercial methana-tion plant. This permits direct upscaling of test results to commercial size reactors because radial gradients are not present in an adiabatic shift reactor. 

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