ABSTRACT
Dimethyl methylphosphonate (DMMP) is often used as a chemical surrogate for organophosphate nerve agents, as it exhibits similar physiochemical properties while having significantly lower toxicity. Continuous hydrolysis of DMMP in hot-compressed water is performed at temperatures from 200 to 300 °C, pressures of 20 and 30 MPa, and residence times from 30 to 80 s to evaluate the effects of pressure and temperature on reaction kinetics. DMMP hydrolysis is observed to follow pseudo-first-order reaction behavior, producing methylphosphonic acid and methanol as the only detectable reaction products. This is significant for the practical implementation of a continuous hydrothermal reactor for chemical warfare agent neutralization, as the process only yields stable, less-toxic compounds. Pressure has no discernible effect on the hydrolysis rate in compressed liquid water. Pseudo-first-order Arrhenius parameters are determined, with an activation energy of 90.17 ± 5.68 kJ/mol and a pre-exponential factor of 107.51±0.58 s-1.
ABSTRACT
The spectra presented correspond with the research article entitled "Kinetics of Formic Acid Decomposition in Subcritical and Supercritical Water - A Raman Spectroscopic Study" [1]. Data set contains in situ Raman spectra of the quenched effluent stream, which includes varied concentrations of formic acid, water, CO, CO2, and H2 as reaction products. Each spectrum is collected downstream of the subcritical or supercritical water gasification of formic acid, which occurs at a specified temperature, residence time, a constant pressure of 25 MPa, and a constant initial feedstock concentration of 3.6 wt% formic acid. Additionally, calibration spectra of formic acid in water, and spectra of pure carbon dioxide and high concentration formic acid are provided for model development. Finally, a MATLAB code used for baseline subtraction of raw data files is included with the dataset. The full dataset is hosted in Mendeley Data, https://doi.org/10.17632/hjn8xwskng.1.
ABSTRACT
Optimizing an industrial-scale supercritical water gasification process requires detailed knowledge of chemical reaction pathways, rates, and product yields. Laboratory-scale reactors are employed to develop this knowledge base. The rationale behind designs and component selection of continuous flow, laboratory-scale supercritical water gasification reactors is analyzed. Some design challenges have standard solutions, such as pressurization and preheating, but issues with solid precipitation and feedstock pretreatment still present open questions. Strategies for reactant mixing must be evaluated on a system-by-system basis, depending on feedstock and experimental goals, as mixing can affect product yields, char formation, and reaction pathways. In-situ Raman spectroscopic monitoring of reaction chemistry promises to further fundamental knowledge of gasification and decrease experimentation time. High-temperature, high-pressure spectroscopy in supercritical water conditions is performed, however, long-term operation flow cell operation is challenging. Comparison of Raman spectra for decomposition of formic acid in the supercritical region and cold section of the reactor demonstrates the difficulty in performing quantitative spectroscopy in the hot zone. Future designs and optimization of continuous supercritical water gasification reactors should consider well-established solutions for pressurization, heating, and process monitoring, and effective strategies for mixing and solids handling for long-term reactor operation and data collection.
