Flow reactor studies of non-equilibrium plasma assisted combustion kinetics
Open Access
- Author:
- Tsolas, Nicholas
- Graduate Program:
- Mechanical Engineering
- Degree:
- Doctor of Philosophy
- Document Type:
- Dissertation
- Date of Defense:
- June 25, 2015
- Committee Members:
- Richard A Yetter, Dissertation Advisor/Co-Advisor
Richard A Yetter, Committee Chair/Co-Chair
Robert John Santoro, Committee Member
Thomas Litzinger, Committee Member
Randy Vander Wal, Committee Member - Keywords:
- flow reactor
plasma-assisted combustion
non-equilibrium plasmas
low temperature combustion - Abstract:
- A new experimental facility was developed to study the reactive chemical kinetics associated with plasma-assisted combustion (PAC). Experiments were performed in a nearly isothermal plasma flow reactor (PFR), using reactant mixtures highly diluted in an inert gas (e.g., Ar, He, or N2) to minimize temperature changes from chemical reactions. At the end of the isothermal reaction zone, the gas temperature was rapidly lowered to terminate any continuation in reaction. Product composition as a result of any observed reaction was then determined using ex situ techniques, including non-dispersive infrared (NDIR), and by sample extraction and storage into a multi-position valve for subsequent analysis by gas chromatography (GC). Hydroxyl radical concentrations were measured in situ, using the laser induced fluorescence (LIF) technique. Reactivity maps for a given fuel system were achieved by fixing the flow rate or residence time of the reactant mixture through the PFR and varying the isothermal temperature. Fuels studied were hydrogen, ethylene and C1 to C7 alkane hydrocarbons, to examine pyrolysis and oxidation kinetics with and without the effects of a high-voltage nanosecond pulse duration plasma discharge, at atmospheric pressure from 420 K to 1250 K. In select instances, experimental studies were complimented with detailed chemical kinetic modeling analysis to determine the dominant and rate-controlling mechanisms, while elucidating the influence of the plasma chemistry on the thermal (neutral) chemistry. In the hydrogen oxidation system, no thermal reaction was observed until 860 K, consistent with the second explosion limit at atmospheric pressure, at which point all the hydrogen was rapidly consumed within the residence time of the reactor. With the plasma discharge, oxidation occurred at all temperatures examined, exhibiting a steady increase in the rate of oxidation starting from 470 K, and eventually consuming all the initial hydrogen by 840 K. For ethylene, kinetic results with the discharge indicated that pyrolysis type reactions were nearly as important as oxidative reactions in consuming ethylene below 750 K. Above 750 K, the thermal reactions coupled to the plasma reactions to further enhance the high temperature fuel consuming chemistry. Modeling analysis of plasma-assisted pyrolysis revealed that ethylene dissociation by collisional quenching with electronically-excited argon atoms formed in the presence of the plasma, resulted in the direct formation of acetylene and larger hydrocarbons by way of the ethyl radical. Similarly, during plasma-assisted oxidation, excited argon was able to directly dissociate the initial oxidizer to further enhance fuel consumption, but also facilitate low temperature oxidative chemistry due to the effective production of oxygenated species controlled by R+O2 chemistry. At the highest temperatures, the radical production by neutral thermal reactions became competitive and the effectiveness associated with the plasma coupled chemistry decreased. Under the effects of the plasma, alkane fuels exhibited extended limits of oxidation over the entire temperature range considered, compared to that of the thermal reactions alone. At atmospheric pressure, propane and butane exhibited cool flame chemistry between 420 K to 700 K, which normally occurs at higher pressures (P > 1 atm) for thermally constrained systems. This chemistry is characterized by the alkylperoxy radical formation, isomerization to the hydroperoxyalkyl radical, followed by dissociation to form aldehydes and ketones. Whereas, intermediate temperature chemistry between 700 K to 950 K, is characterized by beta-scission of the initial alkyl radical to form alkenes and smaller alkanes. The culmination of these studies demonstrate new insight into the kinetics governing PAC and provides a new experimental database to facilitate the development and validation of PAC-specific kinetic mechanisms.