A syngas compositional database with focus on trace impurities was established. For this work, ammonia (NH3) and benzene (C6H6) effects on cell growth, enzymatic activities of hydrogenase and alcohol dehydrogenase (ADH), and product formation were studied. NH3, after entering media, will be converted rapidly to NH4+, which will raise the total osmolarity of the media. NH3, as a common nutrient for the cell growth, is not the real culprit for cell growth inhibition. In essence, it is the high osmolarity resulting from the accumulation of NH4+ in the media which disrupts the normal regulation of the cells. It was concluded that at NH4+ concentration above 250 mM, the cell growth was substantially inhibited. However, P11 cells used in this study can likely adapt to an elevated osmolarity (up to 500 mM) although the mechanism is unknown. It was also found that higher osmolarity will eventually lead to higher ethanol per cell density. In conclusion, NH3 needs to be cleaned out of syngas feeding system. The realistic C6H6 concentration in the media coming from a gasifier was simulated in bioreactors and was measured by a GC/MS. The most realistic C6H6 concentration in the media was around 0.41 mM (upper limit 0.83 mM). However, five elevated concentrations of 0.64, 1.18, 1.72, 2.33, and 3.44 mM were doped into the media. It was found that at 3.44 mM cell growth and ethanol production were significantly affected. However, there was only negligible adverse effect on cell growth and ethanol production at 0.41 mM, which is the expected concentration in bioreactors exposed to syngas. Therefore, it is unnecessary to remove C6H6 from the gas feeding stream. A kinetic model for hydrogenase activity that included inhibition effects of NH4+ and C6H6 was developed. Experimental results showed that NH4+ is a non-competitive inhibitor for hydrogenase activity with KNH4+ of (649 ± 35) mM and KH2 of (0.19 ± 0.1) mM. This KH2 value is consistent with those reported in literature. C6H6 is also a non-competitive inhibitor but a more potent one compared to NH4+ (KC6H6=11.4 ± 1.32 mM). A KH2 value of (0.196 ± 0.022) mM is also comparable with literature and also with the NH4+ study. At a realistic C6H6 concentration of 0.41 mM expected in bioreactors exposed to syngas, hydrogenase activity is expected to be reduced by less than 5%. Forward ADH activity was not adversely affected up to 200 mM [NH4+].From the current work, NH3 should be targeted for removal but it is not necessary to remove C6H6 when designing an efficient gas cleanup system.

The growing amount of landfill waste within the EU could pose a problem in the future should there not be any effective treatment methods. This study aims to investigate the performance of landfill waste in a plasma gasification process by simulating the process in ASPEN Plus. The investigation is focused on the energy recovery potential of RDF based on composition and heating value of syngas, and cold gas efficiency (CGE). The plasma gasification system consists of a shaft gasifier and a separate tar cracking reactor where high temperature plasma is used for conversion of tar compounds considered in the model, which are toluene and naphthalene. In addition, the model is divided into five sections, namely drying, pyrolysis, char gasification, melting and tar cracking. Mass and energy balance of the system was performed to better understand the system. The results show that the plasma gasification system was able to produce a syngas with a LHV of 4.66 MJ/Nm3 while improving syngas yield by attaining a higher content of hydrogen. Thus, the plasma tar cracking of tar compounds can achieve a clean syngas and improve syngas yield. Parameter study on effect of ER show that syngas has higher heating value and CGE at lower ER. On the other hand, preheated air can help recover energy from the system while lowering the ER required for the char gasification process to meet the heat demand from partial combustion. The findings implied that landfill waste has energy potential by using a suitable treatment process such as plasma gasification.

Shock-tube experiments were performed with syngas mixtures near atmospheric pressure with varying equivalence ratios behind reflected shock waves. Pressure and hydroxyl radical (OH*) emission traces were recorded and used to calculate ignition delay time for a single mixture at equivalence ratios of [phi ]=0.4, 0.7, 1.0, and 2.0 over a range of temperatures from 913-1803 K. The syngas mixture was tested at full concentration as well as with 98% dilution in Argon. The full concentration mixtures were used to compare ignition delay time measurements with the theoretical calculations obtained through the use of chemical kinetics modeling using the Davis et al. mechanism. The dilute mixtures were used to study the OH* emission profiles compared to those of the kinetics model. The model was in poor agreement with the experimental data especially at lower temperatures with an ignition delay difference of more than an order of magnitude. These ignition delay time data supplement the few existing data and are in relative agreement. The species profile comparison of OH* compared to the model also showed poor agreement, with the worst agreement at the highest temperatures. While the disagreements with ignition delay time and profile comparisons cannot be explained at this time, the data presented support other findings. The data provide additional information towards understanding this disagreement relative to syngas mixtures despite the relatively well known kinetics of the primary constituents Hydrogen and Carbon Monoxide.

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No / The emission of greenhouse gases on a global scale is predominantly caused by the utilization of fossil fuels. Various methods have been explored to address the recycling of CO2, which among, the CO2 conversion into high-value chemicals become so promising. The purpose of this book chapter evaluation is CO2 reduction and H2 evolution reactions for producing syngas. A comprehensive analysis shall highlight (i) the technical advantages and impediments of various reactor classifications, (ii) the effect of electrolytes on electrolyzers in the liquid phase, and (iv) the catalysts that are viable for the creation of important products such as CO.

Syngas, a gaseous mixture of H2, CO and diluents such as N2, CO2, is a clean fuel generated via gasification of coal or biomass. Syngas produced via gasification typically has low calorific values due to very high dilution levels (~60% by volume). It has been recognized as an attractive energy source for stationary power generation applications. The present work focuses on experimental and numerical investigation of syngas-air counterflow diffusion flames with varying composition of syngas. Laser-based diagnostic techniques such as Particle Imaging Velocimetry, Rayleigh thermometry and Laser-induced fluorescence have been used to obtain non-intrusive measurements of local extinction strain rates, temperature, quantitative OH and NO concentrations, respectively, for three different compositions of syngas. Complementing the experiments, numerical simulations of the counterflow diffusion flame have been performed to assess the performance of five H2/CO chemical kinetic mechanisms from the literature. The first part of the work involved determination of local extinction strain rates for six H2 /CO mixtures, with H2:CO ratio varying from 1:4 to 1:1. The extinction strain rates were observed to increase from 600 sec-1 to 2400 sec-1 with increasing H2:CO ratio owing to higher diffusivity and reactivity of the H2 molecule. Numerical simulations showed few mechanisms predicting extinction conditions within 5% of the measurements for low H2:CO ratios, however, deviations of 25% were observed for higher H2 :CO ratios. Sensitivity analyses revealed that the chain branching reactions, H+O2 <=>O+OH, O+H2 <=>H+OH and the third body reaction H+O2 +M<=>HO2 +M are the key reactions affecting extinction limits for higher H2:CO mixtures. The second phase of work involved quantitative measurement of OH species concentration in the syngas-air diffusion flames at strain rates varying from 35 sec-1 to 1180 sec-1. Non-intrusive temperature measurements using Rayleigh thermometry were made in order to provide the temperature profile necessary for full quantification of the species concentrations. The [OH] is observed to show a non-monotonous trend with increasing strain rates which is attributed to the competition between the effect of increased concentrations of H2 and O2 in the reaction zone and declining flame temperatures on the overall reaction rate. Although the kinetic mechanisms successfully captured this trend, significant deviations were observed in predictions and measurements in flames with H2:CO ratios of 1:1 and 4:1, at strain rates greater than 800 sec-1 . The key reactions affecting [OH] under these conditions were found to be the same reactions identified earlier during extinction studies, thus implying a need for the refinement of their reaction-rate parameters. Significant disagreements were observed in the predictions made using the chemical kinetic mechanisms from the literature in flames with high H2 content and high strain rate. The final phase of work focused on measurement of nitric oxide (NO) species concentrations followed by a comparison with predictions using various mechanisms. NO levels as high as ~ 48 ppm were observed for flames with moderate to high H2 content and low strain rate. Quantitative reaction pathway diagrams (QRPDs) showed thermal-NO, NNH and prompt-NO pathways to be the major contributors to NO formation at low strain rates, while the NNH pathway was the dominant route for NO formation at high strain rates. The absence of an elaborate CH chemistry in some of the mechanisms has been identified as the reason for underprediction of [NO] in the low strain rate flames. Overall, the quantitative measurements reported in this work serve as a valuable reference for validation of H2/CO chemical kinetic mechanisms, and the detailed numerical studies while providing an insight to the H2:CO kinetics and reaction pathways, have identified key reactions that need further refinement.

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