Degradation of Hydrazine and Monomethylhydrazine for Fuel Waste Streams using Alpha-ketoglutaric Acid
Hydrazine, monomethylhydrazine, pca, mpca, second order formation kinetics, optimization, interferences, scrubber liquor
Alpha-ketoglutaric acid (AKGA) is an organic acid important for the metabolism of essential amino acids as well as for the transfer of cellular energy. It is a precursor of glutamic acid which is produced by the human body during the Krebs Cycle. AKGA has a specific industrial interest as it can be taken as a dietary supplement and is also widely used as a building block in chemical synthesis. Collectively termed as hydrazine (HZs), hydrazine (HZ) and monomethylhydrazine (MMH) are hypergolic fuels that do not need an ignition source to burn. Because of the particular HZs' characteristics the National Aeronautics and Space Administration (NASA) at Kennedy Space Center (KSC) and the US Air Force at Cape Canaveral Air Force Station (CCAFS) consistently use HZ and MMH as hypergolic propellants. These propellants are highly reactive and toxic, and have carcinogenic properties. The handling, transport, and disposal of HZ waste are strictly regulated under the Resource Conservation and Recovery Act (RCRA) to protect human health and the environment. Significant quantities of wastewater containing residuals of HZ and MMH are generated at KSC and CCAFS that are subsequently disposed off-site as hazardous waste. This hazardous waste is shipped for disposal over public highways, which presents a potential threat to the public and the environment in the event of an accidental discharge in transit. NASA became aware of research done using AKGA to neutralize HZ waste. This research indicated that AKGA transformed HZ in an irreversible reaction potentially leading to the disposal of the hypergols via the wastewater treatment facility located at CCAFS eliminating the need to transport most of the HZ waste off-site. New Mexico Highlands University (NMHU) has researched this transformation of HZ by reaction with AKGA to form stabilized pyridazine derivatives. NMHU's research suggests that the treatment of HZ and MMH using AKGA is an irreversible reaction; once the reaction takes place, HZ and/or MMH cannot re-form from the byproducts obtained. However, further knowledge relating to the ultimate end products of the reaction, and their effects on human health and the environment, must still be addressed. The known byproduct of the AKGA/HZ neutralization reaction is 6-oxo-1,4,5,6-tetrahydro-pyridazine-3-carboxylic acid (PCA), and the byproduct of the AKGA/MMH reaction is 1-methyl-6-oxo-4,5-dihydro-pyridazine-3-carboxylic acid (mPCA). This research addressed several primary areas of interest to further the potential use of AKGA for HZ and MMH neutralization: 1) isolation of the end-product of the MMH-AKGA degradation process, 1-methyl-6-oxo-4,5-dihydro-pyridazine-3-carboxylic acid (mPCA), and determination of several physical properties of this substance, 2) evaluation of the kinetics of the reaction of AKGA with HZ or MMH, 3) verification of the chemical mechanism for the reaction of the individual hypergols with AKGA, 4) determination of whether the addition of a silicone-based antifoaming agent (AF), citric acid (CA) and/or isopropyl alcohol (IPA) to the AKGA and HZ or MMH solution interferes with the degradation reaction, 4) application of laboratory bench scale experiments in field samples, and 5) determination of the reaction enthalpy of these reactions.
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Doctor of Philosophy (Ph.D.)
College of Sciences
Length of Campus-only Access
Doctoral Dissertation (Open Access)
Dissertations, Academic -- Sciences; Sciences -- Dissertations, Academic
Franco, Carolina, "Degradation of Hydrazine and Monomethylhydrazine for Fuel Waste Streams using Alpha-ketoglutaric Acid" (2014). Electronic Theses and Dissertations. 4605.