PH-Based Control of the Kinetics and Process Safety of the Highly Exothermic Reaction Between Ammonium Chloride and Sodium Nitrite for Flow-Assurance Applications

Abstract

Summary The highly exothermic reaction between ammonium chloride (NH4Cl) and sodium nitrite (NaNO2) has an important application in the area of flow assurance. Because of the high heat generation, this reaction has been used as a heat source for the fluidization of low-melting-point deposits formed during oil and gas production. Because this reaction is strongly pH dependent, the incorrect choice of pH can result in an uncontrollable temperature increase caused by the system’s inability to dissipate the large amount of heat generated in a short time, causing accidents such as structural damage and explosions. Thus, the aim of this work was to study a method that involved adjusting the pH over time to ensure controlled heat generation, with high calorimetric conversion, and avoid the development of a thermal-runaway reaction (pH-based control of the kinetics and process safety). The kinetics and thermodynamics of this reaction were studied using heat-flow reaction calorimetry and attenuated total reflection (ATR)-Fourier-transform infrared (FTIR) (ATR-FTIR) spectroscopy. Following a semiempirical approach, calorimetric and spectroscopic data were fitted to a kinetic equation using nitrite, ammonium (NH4+), and hydronium concentrations. The molar enthalpy calculated was –322.92 kJ/mol, and the Arrhenius parameters were determined as the frequency factor [ln(A)] = 22.21 and the apparent activation energy (Ea) = 63.40 kJ/mol. The kinetic model constructed made it possible to properly evaluate the pH profile that should be maintained to control the kinetics (heat-generation rate) and process safety [time to maximum rate under adiabatic conditions (TMRAD)] of the reaction. The strategy of adjusting the pH over time ensured controlled heat generation and high calorimetric conversion, which cannot be achieved by simply adding catalyst at the beginning of the reaction, and minimized the risk of developing a runaway reaction. However, in real applications, the pH control must be made using the balance between the thermal risk (TMRAD) and the performance of the method (qr), because although it is possible to decrease the thermal risk (increase the value of TMRAD) by increasing the pH, this increase is accompanied by a decrease in the heat-generation rate. Thus, from the proper balance of these factors (qr and TMRAD), pH control can ensure adequate levels of heat production within an acceptable thermal risk.