Rate of heating

Because the characteristic of tubular reactors approximates plug-flow, they are used if careful control of residence time is important, as in the case where there are multiple reactions in series. High surface area to volume ratios are possible, which is an advantage if high rates of heat transfer are required. It is sometimes possible to approach isothermal conditions or a predetermined temperature profile by careful design of the heat transfer arrangements. 

However, if high rates of heat transfer are required or the catalyst requires frequent regeneration, then fixed beds are not suitable, and under these circumstances, a fluidized bed is preferred, as we shall discuss later. 

LOW RATE OF HEAT TRANSFER AND/OR HIGH HEAT OF REACTION... 

Figure 13.1a shows two possible thermal profiles for exothermic plug-fiow reactors. If the rate of heat removal is low and/or the heat of reaction is high, then the temperature of the reacting stream will increase along the length of the reactor. If the rate of heat removal is high and/or the heat of reaction is low, then the temperature will fall. Under conditions between the two profiles shown in Fig. 13.1a, a maximum can occur in the temperature at an intermediate point between the reactor inlet and exit. 

Fixing the rate of heat transfer in a batch reactor is often not the best way to control the reaction. The heating or cooling characteristics can be varied with time to suit the characteristics of the reaction. Because of the complexity of hatch operation and the fact that operation is usually small scale, it is rare for any attempt to be made... 

All calorimeters consist of the calorimeter proper and its surround. This surround, which may be a jacket or a batii, is used to control tlie temperature of the calorimeter and the rate of heat leak to the environment. For temperatures not too far removed from room temperature, the jacket or bath usually contains a stirred liquid at a controlled temperature. For measurements at extreme temperatures, the jacket usually consists of a metal block containing a heater to control the temperature. With non-isothemial calorimeters (calorimeters where the temperature either increases or decreases as the reaction proceeds), if the jacket is kept at a constant temperature there will be some heat leak to the jacket when the temperature of the calorimeter changes. 

Reflux Distillation Unit. The apparatus shown in Fig. 38 is a specially designed distillation-unit that can be used for boiling liquids under reflux, followed by distillation. The unit consists of a vertical water-condenser A, the top of which is fused to the side-arm condenser B. The flask C is attached by a cork to A. This apparatus is particularly suitable for the hydrolysis of esters (p. 99) and anilides (p. 109), on a small scale. For example an ester is heated under reflux with sodium hydroxide solution while water is passed through the vertical condenser water is then run out of the vertical condenser and passed through the inclined condenser. The rate of heating is increased and any volatile product will then distil over. 

Alternatively the semi micro apparatus shown in Fig. 38 (p. 63) may be used. Heat the anilide and sulphuric acid under reflux for 15 minutes in such a manner that the vapour does not rise higher than half-way up the vertical condenser through which water is passed. Then dilute the solution in the flask with 5 ml. of water. Empty the vertical condenser and run cold water through the inclined condenser. Now increase the rate of heating and distil off 1-2 ml. of aqueous acetic acid. 

The m.ps. of the-ir acids v,iry with the rate of heating, and the values given are those obtained on rapid heating in sealed tubes, t Anhydrous. 

Several forms of apparatus employing electrical heati iig wi 11 be described. A simple form may be readily constructed from a domestic electric iron of 400-500 watts rating. The handle is removed, and two holes of 8 mm. diameter are drilled through the base (ca. 11 mm. thick) so that they meet in the centre of the block. One hole is for a 360° thermometer (small bulb) the other hole is spare and can be used for comparison with a standard thermometer. The heater is mounted on a sheet of thick asbestos board which is fixed to an appropriate wooden base. The wires from the heating unit are connected to two insulated terminals fitted on the board (Fig. 11, 11, 1). The rate of heating is controlled by either of the following methods ... 

With a little experience, the correct setting for any desired rate of heating (from rapid heating to about 1° per minute) may be obtained. 

The melting points of the derivatives of a number of amino acids are collected in Table 111,132. Most a-amino acids decompose on heating so that the melting points would be more accurately described as decomposition points the latter vary somewhat with the rate of heating and the figures given are those obtained upon rapid heating. 

These melting points are probably better described as decomposition points their values will depend somewhat upon the rate of heating. 

I) The melting point of pure maleic acid depends to a marked degree upon the rate of heating, and values between 133° and 143-144° may be observed. Slow heating (about 20 minutes) gives a value of 133-134° with more rapid heating... 

If condensation requires gas stream cooling of more than 40—50°C, the rate of heat transfer may appreciably exceed the rate of mass transfer and a condensate fog may form. Fog seldom occurs in direct-contact condensers because of the close proximity of the bulk of the gas to the cold-Hquid droplets. When fog formation is unavoidable, it may be removed with a high efficiency mist collector designed for 0.5—5-p.m droplets. Collectors using Brownian diffusion are usually quite economical. If atmospheric condensation and a visible plume are to be avoided, the condenser must cool the gas sufftciendy to preclude further condensation in the atmosphere. 

Although bulk polymerization of acrylonitrile seems adaptable, it is rarely used commercially because the autocatalytic nature of the reaction makes it difficult to control. This, combined with the fact that the rate of heat generated per unit volume is very high, makes large-scale commercial operations difficult to engineer. Lastiy, the viscosity of the medium becomes very high at conversion levels above 40 to 50%. Therefore commercial operation at low conversion requires an extensive monomer recovery operation. 

---