Vibrational spectroscopic monitoring of CO2-O energy transfer: cooling processes in atmospheres of Venus & Mars

The vibrational excitation of CO2 by a fast-moving O atom followed by infrared emission from the vibrationally excited CO2 has been shown to be an important cooling mechanism in the upper atmospheresof Venus, Earth and Mars. We are trying to determine more precisely the efficiency (rate coefficient) of the CO2-O vibrational energy transfer. For experimental ease the reverse reaction is used, i.e. collision of a vibrationally excited CO2 with atomic O, where we are able to convert to the atmospherically relevant reaction via a known equilibrium constant. The goal of this experiment was to measure the magnitudes of rate coefficients for vibrational energy states above the first excited state, a bending mode in CO2. An isotope of CO2, 13CO2, was used for experimental ease. The rate coefficients for given vibrational energy transfers in 13CO2 are not significantly different from 12CO2 at this level of precision. A slow-flowing gas mixture was flowed through a reaction cell: 13CO2 (vibrational specie of interest), O3(atomic O source), and Ar (bath gas). Transient diode laser absorption spectroscopy was used to monitor thechanging absorption of certain vibrational modes of 13CO2 after a UV pulse from a Nd:YAG laser was fired. Ozone absorbed the UV pulse in a process which vibrationally excited 13CO2 and liberated atomic O.Transient absorption signals were obtained by tuning the diode laser frequency to an appropriate ν3 transition and monitoring the population as a function of time following the Nd:YAG pulse. Transient absorption curves were obtained for various O atom concentrations to determine the rate coefficient of interest. Therotational states of the transitions used for detection were difficult to identify, though their short reequilibration timescale made the identification irrelevant for vibrational energy transfer measurements. The rate coefficient for quenching of the (1000) state was found to be (4 ± 8) x 10-12 cm3 s-1 which is the same order of magnitude as the lowest-energy bend-excited mode: (1.8 ± 0.3) x 10-12 cm3 s-1. More data is necessary before it can be certain that the numerical difference between the two is real.

An Investigation On The Use Of Microalgae For Biogas Enrichment

There is a need for biomethane capture and carbon dioxide sequestration to mitigate evident global climate change. This research work investigated the potential for microalgae to remove CO2 from biogas as a biotechnical method for upgrading the thermal value for subsequent compression, liquification, or introduction to natural gas pipelines. Because biogas is largely methane, the effect of high methane environments on mixed microalgae was explored and found that specific carbon utilization rates were not statistically different when microalgae were exposed to biogas environments (70% v/v CH4) , relative to high CO2 environment. The uses of conventional bubbled column photobioreactors (PBR) were assessed for CO2 removal and subsequent CH4 enrichment. A continuously-bubbled biogas PBR (cB-PBR5) and intermittently-bubbled biogas PBR (iB-PBR) experienced CO2 loading rates of about 1664 and 832 mg C/L*day and showed 30.0 and 60.1 % carbon removal, respectively. However, a lack of biogas enrichment and issues associated growth inhibition due to high CO2 environments as well as stripping the dissolved gases, namely oxygen and nitrogen, from the bulk liquid and introduction to the outlet gas prompted the consideration for gas/liquid separation using nonporous hollow-fiber (HF) membranes for CO2 transfer. The potential for two non-porous HF membrane materials [polydimethylsiloxane (PDMS) and composite polyurethane (PU)] were modeled along fiber length using a mechanistic model based on polymeric material transport properties (Gilmore et al., 2009). Based on a high CO2:CH4 permeability selectivity for PU of 76.2 the model predicted gas enrichment along an 8.5 cm fiber length. Because PDMS permeability selectivity is low (3.5), evident gas transfer was not predicated along a 34.3 cm length. Both of these HF materials were implemented in hollow-fiber membrane-carbonated biofilm (HFMcB) PBRs for microalgal-mediated biogas enrichment. Phototrophic biofilm colonization occurred on the membrane, where CO2 concentration was greatest. The presence of a biofilm demonstrated greater resiliency to high CO2 environments, compared to the conventional PBRs. However, as the PDMS model predicted, the PDMS HFMcBs did not demonstrate gas enrichment. These reactors received CO2 loading rates of 200 mg C/L*day based on PDMS permeability flux and showed approximately 65% removal of the total C transferred across the membrane. Thus, the HFMcBs demonstrated controlled carbonation of the bulk liquid via a nonporous HF membrane. Likewise, the experimental PU HFMcB did not show gas enrichment yet this result should be further explored due to the high permeability selectivity of the polymeric material. Chemical stratifications, namely pH and dissolved O2, present in a PDMS membrane-carbonated biofilm were analyzed using electrochemical microsensors. Results indicated that high DO (20 mg L-1) exists at surface of the biofilm where light availability is greatest and low pH microenvironments (pH=5.40) exist deep in the biofilm where the diffusive flux of CO2 drives transfer through the biofilm. The presence of a 400-600 ¿m liquid phase boundary layer was evident from microsensor profiles. Cryosectioning of the biofilm samples showed the biofilm to be approximately 1.17 ± 0.07 mm thick, suggesting that the high localized concentration of biomass associated with the phototrophic biofilm aided in overcoming inhibition in a microenvironment dominated by CO2(aq). Challenges of biofilm detachment and PBR fouling as well as microalgal growth inhibition in the presence of high CO2 content remain for applications of microalgae for biogas enrichment.

Design and Preliminary Results of an Atmospheric-Pressure Model Gas Turbine Combustor Utilizing Varying CO2 Doping Concentration in CH4 to Emulate Biogas Combustion

Utilization of biogas can provide a source of renewable energy in both heat and power generation. Combustion of biogas in land-based gas turbines for power generation is a promising approach to reducing greenhouse gases and US dependence on foreign-source fossil fuels. Biogas is a byproduct from the decomposition of organic matter and consists primarily of CH4 and large amounts of CO2. The focus of this research was to design a combustion device and investigate the effects of increasing levels of CO2 addition to the combustion of pure CH4 with air. Using an atmospheric-pressure, swirl-stabilized dump combustor, emissions data and flame stability limitations were measured and analyzed. In particular, CO2, CO, and NOx emissions were the main focus of the combustion products. Additionally, the occurrence of lean blowout and combustion pressure oscillations, which impose significant limitations in operation ranges for actual gas turbines, was observed. Preliminary kinetic and equilibrium modeling was performed using Cantera and CEA for the CH4/CO2/Air combustion systems to analyze the effect of CO2 upon adiabatic flame temperature and emission levels. The numerical and experimental results show similar dependence of emissions on equivalence ratio, CO2 addition, inlet air temperature, and combustor residence time. (C) 2014 Elsevier Ltd. All rights reserved.