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Degradation of Hydrazine and Monomethylhydrazine for Fuel Waste Streams using Alpha-ketoglutaric AcidFranco, Carolina 01 January 2014 (has links)
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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Evaluation Of The Biodegradability And Toxicity Of Pca And MpcaRueda, Juan 01 January 2013 (has links)
The main types of hypergolic propellants used at Kennedy Space Center (KSC) are hydrazine (HZ) and monomethylhydrazine (MMH). HZ and MMH are classified as hazardous materials and they are also known to be potentially carcinogenic to humans; therefore, handling these substances and their waste is strictly regulated. The wastes streams from HZ and MMH have been estimated to be the main hazardous wastes streams at KSC. Currently at KSC these wastes are first neutralized using citric acid and then they are transported on public roads for incineration as hazardous materials. A new method using alpha ketoglutaric acid (AKGA) was proposed to treat HZ and MMH wastes. From the reaction of AKGA with HZ and MMH two stable products are formed, 1,4,5,6-tetrahydro-6-oxo-3-pyridazinecarboxylic acid (PCA) and lmethyl-1,4,5,6-tetrahydro-6-oxo-3-pyridazinecarboxylic acid (mPCA), respectively. The cost of purchasing AKGA is greater than the cost of purchasing citric acid; thus, AKGA can only become a cost effective alternative for the treatment of HZ and MMH wastes if the products of the reactions (PCA and mPCA) can be safely disposed of into the sewage system without affecting the treatment efficiency and effluent quality of the wastewater treatment plant (WWTP). In this research mPCA and PCA were analyzed for acute toxicity using fish and crustaceans as well as their effect on the wastewater treatment efficiency and viability using AS microbes, and their biodegradability by AS organisms. Acute toxicity on fish and crustaceans was investigated according to the methods for acute toxicity by USEPA (USEPA Method EPA- 821-R-02-012) using Ceriodaphnia dubia (96 hours) and Pimephales promelas (96 hours) as the test organisms. The effect of mPCA and PCA in the treatment efficiency and viability were iii estimated from respiration inhibition tests (USEPA Method OCSPP 850.3300) and heterotrophic plate counts (HPCs). Lastly, the biodegradability of mPCA and PCA was assessed using the Closed Bottle Test (USEPA Method OPPTS 835.3110). For mPCA, the 96 hours LC50 for C. dubia was estimated at 0.77 ± 0.06 g/L (with a 95% confidence level) and the NOEC was estimated at 0.5 g/L. For P. promelas, the LC50 was above 1.5 g/L but it was noticed that mPCA had an effect on their behavior. Abnormal behavior observed included loss of equilibrium and curved spine. The NOEC on the fish was estimated at 0.75 g/L. PCA did not exhibit a significant mortality on fish or crustaceans. The LC50 of PCA in P. promelas and C. dubia was > 1.5 g/L and the NOEC was 1.5 g/L for both organisms. An Inhibitory effect on the heterotrophic respiration of activated sludge organisms was not observed after exposing them for 180-min to PCA and mPCA at concentrations of up to 1.5 g/L compared to the blank controls. Overall the impact of PCA and mPCA on total respiration rates was small, and only observed at 1,500 mg/L if at all. The difference was apparently caused by inhibition of nitrification rather than heterotrophic inhibition. However due to the variability observed in the measurements of the replicates, it is not possible to firmly conclude that PCA or mPCA at 1,500 mg/L was inhibitory to nitrification. Based on the results from the HPCs, mPCA and PCA did not affect the viability of heterotrophic organisms at 750 mg/L. In the BOD-like closed bottle test using a diluted activated sludge mixed liquor sample, the AS microorganisms were capable of biodegrading up to 67% of a 2 mg/L concentration of PCA (with respect to its theoretical oxygen demand, or ThOD) in 28 days. No biodegradation was observed in the samples containing 2 and 5 mg/L of mPCA after 28 days of incubation using a diluted activated sludge mixed liquor sample as inoculum. iv The results of this study show that mPCA is more toxic than PCA to Ceriodaphnia dubia and Pimephales promelas. However neither mPCA nor PCA had an effect on the heterotrophic respiration of an AS mixed liquor sample at 1.5 g/L and there was probably no significant inhibition of the nitrification respiration. Samples of PCA and mPCA at 2 and 5 mg/L could not be completely degraded (with respect to their total theoretical oxygen demand) by dilute AS biomass during a 28 day incubation period. mPCA did not show significant degradation in the two different biodegradation tests performed.
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Reversible carbon dioxide gels, synthesis and characterization of energetic ionic liquids, synthesis and characterization of tetrazole monomers and polymers, encapsulation of sodium azide for controlled releaseSamanta, Susnata 09 April 2007 (has links)
Hydrazine and monomethylhydrazine are widely used as propellants in aerospace and defense industries. However these chemicals are volatile, carcinogenic, and sensitive to impact, which impose serious threats during their usage. In this thesis, we have demonstrated two novel ways to immobilize hydrazine chemicals. In one approach hydrazine, monomethylhydrazine have been gelled using carbon dioxide. Chemical and structural properties of these gels are studied by NMR (1H, 15N, 13C), diffusion-ordered NMR spectroscopy, and Cryo-HRSEM. Thermal reversibility of these gels is also demonstrated. In another approach, hydrazine, monomethylhydrazine and 1,1-dimethylhydrazine are reacted with 5-methyltetrazole to form ionic liquids. Synthesis of novel tetrazole monomers and polymers, .and new method for encapsulating sodium azide have also reported in this thesis
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