Maximum temperature of the synthesis

The scenario presented here was developed by R. Gygax [1, 2]. Let us assume that while the reactor is at the reaction temperature (TP), a cooling failure occurs (point 4 in Figure 3.2). The scenario consists of the description of the temperature evolution after the cooling failure. If, at the instant of failure, unconverted material is still present in the reactor, the temperature increases due to the completion of the reaction. This temperature increase depends on the amount of non-reacted material, thus on the process conditions. It reaches a level called the Maximum Temperature of the Synthesis Reaction (MTSR). At this temperature, a secondary decomposition reaction may be initiated. The heat produced by this reaction may... 

The cooling failure scenario presented above uses the temperature scale for the assessment of severity and the time-scale for the probability assessment. Starting from the process temperature (TP), in the case of a failure, the temperature first increases to the maximum temperature of the synthesis reaction (MTSR). At this point, a check must be made to see if a further increase due to secondary reactions could occur. For this purpose, the concept of TMRad is very useful. Since TMRad is a function of temperature (see Section 2.5.5) it may also be represented on the temperature scale. For this, we can consider the variation of TMRad with temperature and look for the temperature at which TMRad reaches a certain value (Figure 3.4), for example, 24 hours or 8 hours, which are the levels in the assessment criteria presented in Sections 3.3.2 and 3.3.3. 

If the feed is suddenly stopped, it behaves as an adiabatic batch reactor with an accumulation corresponding to the non-converted fraction, thus the maximum temperature of the synthesis reaction is... 

Feed by portions this method, presented in Section 7.8.1, is obviously only applicable to discontinuous processes as semi-batch. It reduces the amount of reactant present in the reactor, that is, the accumulation and therefore the energy that may be released by the reaction in case of loss of control. The amount allowed in one portion can be determined in such a way that the maximum temperature of the synthesis reaction (MTSR) does not reach a critical level as the maximum temperature for technical reasons (MTT) or the temperature at which secondary reactions become critical (TD24). The difficulty is to ensure that an added portion has reacted away, before adding the next portion. Generally, the feed control is performed by the operator, but can also be automated. 

The major drawbacks to standard sol-gel synthesis include slow growth rate and the typically amorphous product, rather than defined crystals, which requires crystallization and post annealing steps. Growth rate and crystallization of the fabricated hybrid can be improved via solvothermal, reflux [224], sonication, and microwave [225] treatment. However, the air oxidation of CNTs (600 °C) and graphene (450 °C) may still be lower than MO crystallization temperature. Moreover, it has been shown that the MO coatings on CNTs can drastically affect their thermal oxidation, particularly with easily reducible metal oxides (e.g. TiOz = 520 °C, Bi203 = 330 °C) [180]. It appears that metal oxides can catalyze the oxidation of CNTs via a Mars van Krevelen mechanism, limiting the maximum temperature of their synthesis as well as applications (i.e. catalysis, fuel cells). 

The second important reason lies in the limited information yield of such screening tests. This statement shall be explained with the help of Figure 2-4, which describes a scenario for an exothermic discontinuous batch process [10]. It shows the performance of a desired process, which suffers from a loss of cooling at the time 1. Depending on the accumulated amount of unreacted material at the time of malfunction a certain temperature increase will be observed up to the level called maximum accessible temperature of the synthesis reaction MTSR. 

Figure 2 shows the cumulative pore volume vs. pore radius for AC-ref SC-100 and SC-155 obtained by mercury intrusion technique. The curve corresponding to AC-ref shows a wide pore radius distribution instead, the curves assigned to SC-100 and SC-155 showed sharpened zones with maximum slope in 459A and 524A respectively, denoting a small increase of these values with the increase of the synthesis temperature. This phenomenon is probably produced by the growing of the big pores of the silica network at the expense of the... 

Therefore, it is proposed that the species identified by MCR is an o=5 or an o=6 structure, which presents an MS concentration profile similar to that obtained by ATR FTIR, or a mixture of more silsesquioxane structures. The hypothesis of an o=6 structure is supported by the fact that the ATR FTIR concentration profile for the silsesquioxane species as a function of time is rather similar to the MS concentration profile obtained for the o=6 silsesquioxane (cf. Figs 9.9 and 9.13). The slightly different position of the maximum in the two plots is considered to be due to the longer time required in the ATR FTIR experiment to reach the reflux temperature. (This explanation was confirmed by repeating part of the MS study of the synthesis of silsesquioxane 7h3 at 50°C (instead of reflux tem-... 

Figure 3.2 Cooling Failure Scenario After a cooling failure, the temperature rises from process temperature to the maximum temperature of synthesis reaction. At this temperature, a secondary decomposition reaction may be triggered. The left-hand part of the scheme is devoted to the desired...

Maximum temperature of synthesis reaction (MTSR) this temperature depends essentially on the degree of accumulation of unconverted reactants and so is strongly dependant on process design. 

Moreover, reactor safety also requires fulfilling a more ambitious objective, that is, to design a reactor that will remain stable in case of mal-operation. The result will be a robust process towards deviations from normal operating conditions. This goal can be reached if the accumulation of non-converted reactants is controlled and maintained at a safe level during the course of reaction. The concept of maximum temperature of synthesis reaction (MTSR) was introduced for this purpose. This point will be described in the second section. In the... 

The maximum temperature of synthesis reaction was calculated for the substitution reaction example as a function of the process temperature and with different feed rates corresponding to a feed time of 2, 4, 6, and 8 hours. The straight line (diagonal in Figure 7.11) represents the value for no accumulation, that is, for a fast reaction. This clearly shows that the reactor has to be operated at a sufficiently high temperature to avoid the accumulation of reactant B. But a too high temperature will also result in a runaway due to the high initial level, even if the accumulation is low. In this example, the characteristics of the decomposition reaction... 

Figure 7.11 Maximum temperature of synthesis reaction occurring at stoichiometric point as a function of the process temperature TP, with different feed rates, = 2, 4, 6, 8 hours.

The reaction conditions are constrained. In other words, there is usually a strict upper and lower limit for each reaction parameter. In the case of the synthesis described above, for example, the lower temperature is set by the need to provide sufficient thermal energy to initiate the reaction and the upper temperature by the need to remain below the decomposition temperature of the glue (see Section 2). The lower and upper limits on the total flow rate meanwhile are determined, respectively, by the maximum length of time one is prepared to allow for a single reaction and the minimum reaction time needed to produce crystals of nanometer dimensions. In this work, we select minimum and maximum total flow rates of 2 and 40 il min 1 which, for the typical chip volumes we use ( 16.6 il), correspond to average residence times of about 500 and 25 s, respectively. 

Gas phase ceramic synthesis is the subject of several review papers. The treatment here is analogous to that in Magan [1], Friedlander [2], and Pratsinis and Kodas [3] but instead of using the traditional aerosol nomenclature, this chapter uses the nomenclature developed in Chapter 3 on population balances for educational continuity. Each of the gas phase powder synthesis methods is summarized in Table 7.1. The maximum temperatures are also listed. The adiabatic flame temperature is the maximum possible temperature achieved in flame synthesis and will depend on the concentration of reactants in the feed. Powder synthesis in a furnace uses conduction, convection, and radiation, giving a maximum temperature of 2300 K. A plasma is an ionized gas. High velocity electrons remove other electrons from the neutral gas molecules present in the plasma, thereby producing ions and electrons that sustain the plasma. 

The main characteristics of the green mixture used to control the CS process include mean reactant particle sizes, size distribution of the reactant particles reactant stoichiometry, j, initial density, po size of the sample, D initial temperature, Tq dilution, b, that is, fraction of the inert diluent in the initial mixture and reactant or inert gas pressure, p. In general, the combustion front propagation velocity, U, and the temperature-time profile of the synthesis process, T(t), depend on all of these parameters. The most commonly used characteristic of the temperature history is the maximum combustion temperature, T -In the case of negligible heat losses and complete conversion of reactants, this temperature equals the thermodynamically determined adiabatic temperature (see also Section V,A). However, heat losses can be significant and the reaction may be incomplete. In these cases, the maximum combustion temperature also depends on the experimental parameters noted earlier. 

The most important part of an ammonia synthesis plant is the pressure reactor, which is filled with catalyst and in which ammonia formation takes place at temperatures between 400 and 500°C. A maximum temperature of 530°C must not be exceeded, otherwise catalyst damage will ensue. 

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