Adiabatic temperature, maximum

Two standard estimation methods for heat of reaction and CART are Chetah 7.2 and NASA CET 89. Chetah Version 7.2 is a computer program capable of predicting both thermochemical properties and certain reactive chemical hazards of pure chemicals, mixtures or reactions. Available from ASTM, Chetah 7.2 uses Benson s method of group additivity to estimate ideal gas heat of formation and heat of decomposition. NASA CET 89 is a computer program that calculates the adiabatic decomposition temperature (maximum attainable temperature in a chemical system) and the equilibrium decomposition products formed at that temperature. It is capable of calculating CART values for any combination of materials, including reactants, products, solvents, etc. Melhem and Shanley (1997) describe the use of CART values in thermal hazard analysis. 

Adiabatic temperature rise Maximum increase in temperature that can be achieved. This increase occurs when the substance or reaction mixture decomposes or reacts completely under adiabatic conditions. The adiabatic temperature rise follows from ... 

In order to show how specific guidelines for the reactor layout can be derived, the maximum allowable micro-channel radius giving a temperature rise of less than 10 K was computed for different values of the adiabatic temperature rise and different reaction times. For this purpose, properties of nitrogen at 300 °C and 1 atm and a Nusselt number of 3.66 were assumed. The Nusselt number is a dimensionless heat transfer coefficient, defined as... 

Many kinetic data can be collected from ARC experiments the exothermic onset temperature, the rate of temperature rise, the rate of pressure rise, and the apparent activation energy. The basic data obtained are, however, thermodynamic properties the adiabatic temperature rise, the maximum pressure potential, the quantity of gaseous products generated, and the heat of reaction can be obtained in one run. The heat of reaction is estimated from ... 

Freeder, B. G. et al., J. Loss Prev. Process Ind., 1988, 1, 164-168 Accidental contamination of a 90 kg cylinder of ethylene oxide with a little sodium hydroxide solution led to explosive failure of the cylinder over 8 hours later [1], Based on later studies of the kinetics and heat release of the poly condensation reaction, it was estimated that after 8 hours and 1 min, some 12.7% of the oxide had condensed with an increase in temperature from 20 to 100°C. At this point the heat release rate was calculated to be 2.1 MJ/min, and 100 s later the temperature and heat release rate would be 160° and 1.67 MJ/s respectively, with 28% condensation. Complete reaction would have been attained some 16 s later at a temperature of 700°C [2], Precautions designed to prevent explosive polymerisation of ethylene oxide are discussed, including rigid exclusion of acids covalent halides, such as aluminium chloride, iron(III) chloride, tin(IV) chloride basic materials like alkali hydroxides, ammonia, amines, metallic potassium and catalytically active solids such as aluminium oxide, iron oxide, or rust [1] A comparative study of the runaway exothermic polymerisation of ethylene oxide and of propylene oxide by 10 wt% of solutions of sodium hydroxide of various concentrations has been done using ARC. Results below show onset temperatures/corrected adiabatic exotherm/maximum pressure attained and heat of polymerisation for the least (0.125 M) and most (1 M) concentrated alkali solutions used as catalysts. 

Interestingly, this compound was known for some years [38, 39] before MCE research came back into vogue. Here, the maximum — ASM for a decoupled system is 42 J kg-1 K-1 and is almost met for AH = 0 - 7 T and 1.8 K. So, we have a reasonably high metal content, with a small, though ferromagnetic, interaction, with the appropriate high spin metals. Heat capacity data allow the adiabatic temperature change to be calculated here, this was found to be 12.7 K below 2 K, one of the best by this measure until recently. 

D. R. Stull11 developed a rating system to establish the relative potential hazards of specific chemicals the rating is called the reaction hazard index (RHI). The RHI is related to the maximum adiabatic temperature reached by the products of a decomposition reaction. It is defined as... 

The adiabatic flame temperature is defined as the maximum possible temperature achieved by the reaction in a constant pressure process. It is usually based on the reactants initially at the standard state of 25 °C and 1 atm. From Equation (2.20), the adiabatic temperature (7 i[Pg.30]

For most homogeneous hydrogenations, heat transfer is generally not an issue. With heat of reactions in the range 100 to 150 kj mol 1 (see above), and considering that dilute (0.5 to 2 kmol m ) solutions of the substrate are most often used, the maximum adiabatic temperature rise can be estimated (Eq. (39)) ... 

It is obvious that reducing cr (i.e., increasing the dilution), results in a reduction in the adiabatic temperature rise and, thus, can help to keep the reaction temperature within acceptable constraints. The global heat balance over the system, with all heat generation terms included, is required to obtain the actual adiabatic temperature rise. From the safety perspective, the adiabatic temperature rise is a useful design parameter, although it must be emphasized that it shows only a maximum effect and not a rate. 

Reaction calorimetry provides information on the maximum heat generation at process temperatures and on the adiabatic temperature rise. This ATad provides insight into the worst-case temperature consequences. 

For small vessels and slow reactions, corrections must be made because of the heat content of the reaction vessel itself. For large-scale reaction vessels and for rapid reactions, the system will be close to adiabatic operations. This aspect must be taken into account in scale-up. In effect, the extrapolation of data obtained in small-scale equipment has limitations as discussed in [193]. In case of a runaway, the maximum temperature in the reaction system is obtained from the adiabatic temperature rise, that is, Tmax = (Tr + ATad). In reality, the adiabatic temperature rise is significantly underestimated if other exothermic reaction mechanisms occur between Tr and (Tr + ATad). Therefore, a determination must be made to see if other exothermic events, which may introduce additional hazards during a runaway, occur in the higher temperature range. This can determine if a "safe operating envelope" exists. 

De Haven [127] gives an overview of the results of accelerating rate calorimeter (ARC) experiments. The ARC was described in Section 2.3.2.3. As mentioned in the previous description, care must be taken in scale-up of results from experiments with relatively high phi-factors. For direct simulation of plant operating conditions, a phi-factor of 1.0 to 1.05 is required. As stated in [127], a decrease in the phi-factor from 2.0 to 1.0 increases the adiabatic temperature rise by a factor of 2, but the maximum self-heat rate increases by a factor of 20. Later in Chapter 3 (Section 3.3.4.6), an example of scale-up of ARC results is given. 

Maximum pressure after decomposition the maximum pressure obtainable in a closed vessel this pressure is a function of the adiabatic temperature rise and the specific gas production. 

Calculate the maximum adiabatic temperature for the reaction mixture. 

Heat of mixing may be a concern in some circumstances. The maximum adiabatic temperature rise is XX C (see XYZ Encyclopedia of Chemical Technology). 

If DSC data have been obtained for a pure material or a reaction mixture, several thermal stability indicators (ASTM E 1231-96) may be estimated from the data. These are adiabatic temperature rise, explosion potential, instantaneous power density, time to maximum rate, and NFPA instability index (Leggett 2002). 

The special process feature for case 3 is a relatively high reaction enthalpy in combination with a low maximum permissible temperature Texo- An alternative safety solution would be to control both these two parameters. For example by adding a pump to the reactor and with solvent makeup the process can be made continuous (CSTR). This allows the adoption of a higher maximum permissible temperature Texo, because of the short residence time and the dilution effect, and a reduction of the adiabatic temperature increase ATadiab because of the dilution effect. Such a (drastic) process and facility change will always require an iterative safety-technical reaction PHA furthermore additional may become necessary. 

The adiabatic surface temperature (for stagnation flow) and the adiabatic PSR temperature are shown in Fig. 26.4a as a function of the inlet fuel composition. The residence time in the PSR is simply taken as the inverse of the hydrodynamic strain rate. In both cases, the adiabatic temperature exhibits a maximum near the stoichiometric composition. The limits of the adiabatic operation are 8% and 70% inlet H2 in air for the stagnation reactor. For a PSR, the corresponding limits are 12% and 77% inlet H2 in air. Beyond these compositions, the heat generated from the chemical reactions is not sufficient to sustain combustion. 

One interesting characteristic of this type of reactor is that the maximum temperature of the products can be above the adiabatic temperature predicted for reactant temperatures before heat exchange. Heat is retained in the reactor by preheating the feed, and temperatures in some situations can be many hundreds of degrees above adiabatic. This can be useful in combustors for pollution abatement where dilute hydrocarbons need to be heated to high temperatures to cause ignition and attain high conversion with short residence times. 

A tubular reactor in which the feed is heated by product in a countercurrent adiabatic configuration can attain a maximum temperature much hotter than the adiabatic temperature (and in fact it can be infinite). Sketch T(z) to show why this is so. 

In a similar way, the maximum temperature rise possible in the system (the adiabatic temperature rise ATad) has a dimensionless measure 0ad given by... 

The left-hand side of this equation is the extent of reaction the quotient 0ss/0ad on the right-hand side is the fractional temperature rise compared with the maximum possible (adiabatic temperature rise). 

The adiabatic flame temperature is the maximum theoretical temperature that can be reached by the products of combustion of a specific fuel and air (or oxygen) combination assuming no loss of heat to the surroundings until combustion is complete. This theoretical temperature also assumes no dissociation, a phenomenon discussed later under this heading. The heal of combustion of Ihe fuel is the major factor in the flame temperature, but increasing the temperature of the air or of the fuel will also have the effect of raising the flame temperature. As would be expected, this adiabatic temperature is a maximum with zero excess air (only enough air chemically required lo combine with the fuel), since any excess is not... 

---