Accelerating-Rate Calorimeter ARC

FIGURE 2.24. Accelerating Rate Calorimeter (ARC). (Note Not to scale.) 

According to the literature [77], a process is considered to be low hazard from the thermal standpoint if the normal operating temperature or temperature due to upset is 50°C or more lower than the ARC onset temperature, and the maximum process temperature is held for only a short period of time. However, other factors must be considered in evaluating the thermal hazard of a process such as total enthalpy of reaction or decomposition, potential for reactant accumulation, the boiling point of the reaction mass, and the rate of reaction. The testing must involve all appropriate materials including reactants, intermediates, and products. In some cases, though, the 50°C differential 

FIGURE 2.25. The Heat-Wait-Search Operation Mode of the ARC. 

Further, the time to maximum rate (TMR) is measured in the ARC, which can indicate the time available for taking defensive or mitigation measures in process upset situations. 

From an ARC experiment, the enthalpy of decomposition, AHd, or the enthalpy of reaction, AHi, can be calculated by Equation (2-19)  

For experiments conducted at slower heating rates under adiabatic conditions, the accelerating-rate calorimeter (ARC) is the instrument of choice [13]. The ARC allows precise control of temperature and exposes the cell to more uniform conditions over longer periods. A typical experiment requires a few days rather than a few hours, as in the case of the heating block. Because of the adiabatic environment, the onset of self-heating due to chemical reactions in the interior of the cell can be detected with greater sensitivity. 

The ARC increases the temperature in discrete steps, waits for the thermal transients to decay, then monitors the temperature of the cell for a fixed time. If the cell temperature is not increasing above a threshold value, typically 0.02 °C/min, the temperature is increased by another step and the process repeated. If the cell temperature is increasing at a rate equal to or above the threshold value, the ARC switches to exothermic mode, during which the ARC temperature closely matches cell temperature, thus maintaining the adiabatic state. The ARC matches the rate of temperature rise of the ceU even at quite high heating rates. 

Isothermal age mode The sample is directly heated to the desired initial temperature. At this temperature, the instrument seeks for an exothermal effect as above. 

By this technique, the temperature directly tracks the exothermal process under pseudo-adiabatic conditions. Pseudo, because a part of the heat released in the sample serves to heat the cell itself. Nevertheless, essentially in the USA, it became a very popular method as a screening technique. Concerning its sensitivity, for a well-tuned instrument, able to detect a self heating rate of 0.01 Kmin 1, with a sample mass of 2g, the sensitivity is as low as 0.5 W kg 1. 

There are other types of adiabatic calorimeters available on the market [14, 15], such as the VSP (Vent Sizing Package) [16], PHITEC [6], and RSST (Reactive System Screening Tool). These instruments are essentially designed for vent sizing requirements [17-20] and present a lower thermal inertia than the ARC. 

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Figure Bl.27.12. Schematic diagram of an accelerating rate calorimeter (ARC).

In a testing context, it refers to the first detection of exothermic-activity on the thermogram. The differential scanning calorimeter (DSC) has a scan rate of I0°C/min, whereas the accelerating rate calorimeter (ARC) has a sensitivity of 0.02°C/min. Consequently, the temperature at which thermal activity is detected by the DSC can be as much as 50°C different from ARC data. 

Accelerating Rate Calorimeter (ARC) The ARC can provide extremely useful and valuable data. This equipment determines the self-heating rate of a chemical under near-adiabatic conditions. It usu-aUy gives a conservative estimate of the conditions for and consequences of a runaway reaction. Pressure and rate data from the ARC may sometimes be used for pressure vessel emergency relief design. Activation energy, heat of reaction, and approximate reaction order can usually be determined. For multiphase reactions, agitation can be provided. 

Accelerating rate calorimeters (ARC) are customarily used to determine the overall reactivity of compounds. One limitation of these instruments is that pressure data at pre-exotherm temperatures are not recorded. However, such information may be important for the analysis of reactive systems in which pressure events are observed prior to the exotherm. An ARC has been modified so that pressure data can be acquired and stored for kinetic analysis by interfacing with a personal computer. Results are presented using this technique for the study of the decomposition chemistry of 4,4 -diisocyanatodiphenylmethane (MDI). 

Several commercial calorimeters are available to characterize runaway reactions. These include the accelerating rate calorimeter (ARC), the reactive system screening tool (RSST), the automatic pressure-tracking adiabatic calorimeter (APTAC), and the vent sizing package (VSP). Each calorimeter has a different sample size, container design, data acquisition hardware, and data sensitivity. 

These tests can also be used to evaluate the induction time for the start of an exothermic decomposition, and the compatibility with metals, additives, and contaminants. The initial part of the runaway behavior can also be investigated by Dewar tests and adiabatic storage tests. To record the complete runaway behavior and often the adibatic temperature rise, that is, the consequences of a runaway, the accelerating rate calorimeter (ARC) can be used, although it is a smaller scale test. 

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. 

The Accelerating Rate Calorimeter (ARC ) is another adiabatic test instrument that can be used to test small samples. The ARC with the clamshell containment design can handle explosive compounds. It is a sensitive instrument that can indicate the onset of exothermicity where the reaction mixture can be accurately simulated (HSE 2000). ARC testing results can be used in determining a time to maximum rate of decomposition, as well as in calculating a temperature of no return for a container or vessel with specific heat removal characteristics. Further information and references related to the ARC are given in CCPS (1995a) and Urben (1999). 

A number of sophisticated tools can be of assistance in these areas. Two of the more common tools are the Differential Scanning Calorimeter (DSC) and the Accelerating Rate Calorimeter (ARC). 

In this context, the term adiabatic refers to calorimetry conducted under conditions that minimize heat losses to the surrounding environment to better simulate conditions in the plant, where bulk quantities of stored or processed material tend to minimize cooling effects. This class of calorimetry includes the accelerating rate calorimeter (ARC), from Arthur D. Little, Inc., and PHI-TEC from Hazard Evaluation Laboratory Ltd. 

Information gained from simulations can reveal key insights that explain gaps or contradictions in information. The time line is a useful tool in this development. For incidents of unexpected chemical reactions, it is common to attempt a lab scale simulation of the conditions involved in the exotherm or explosion. Many chemical processes can be modeled and duplicated dynamically by computer algorithms. Accelerated rate calorimeters (ARC) have proven to he highly useful tools for studying exothermic or overpressure runaway reactions. 

Non-adiabatic screening tests such as Carius tube111 and the Accelerating Rate Calorimeter (ARC ), corrected for sample heat losses due to thermal inertia, can also be used for screening. If it is known that the reaction is a vapour pressure system, DSC may be used. 

Adiabatic conditions may be achieved either by a thermal insulation or by an active compensation of heat losses. Examples are the Dewar calorimeter, achieving a thermal insulation [2-4] or the Accelerating Rate Calorimeter (ARC) [5] or the Phitec [6], using a compensation heater avoiding the heat flow from the sample to the surroundings. These calorimeters are especially useful for the characterization of runaway reactions. 

Accelerating Rate Calorimeter (ARC). The ARC is sturdily constructed for the main purpose of simulating runaway reaction conditions on a small scale, typically using a 2 to 5 g sample. The sample is heated to a predetermined starting temperature in a spherical metal bomb. The sample is allowed to incubate at this temperature while the instrument control system scans for initiation of an exotherm. If no exothermic activity is found, the sample temperature is raised, and the wait-exotherm search routine is... 

An accelerating rate calorimeter (ARC) can be used to provide design values for emergency pressure-relief flow requirements of runaway systems. The ARC is a device used to obtain runaway history of chemical reactions in a closed system (DeHaven, 1983 Huff, 1982,1984a Townsend and Tou, 1980). The experimental technique is fairly straightforward, but considerable engineering expertise is required to do the calculations needed to design a relief system from the ARC data. 

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