Chemical kinetics mechanism for oxy-fuel combustion of mixtures of hydrogen sulfide and methane

Oxy-fuel combustion of sour gas, a mixture of natural gas (essentially methane (CH[subscript 4])), carbon dioxide (CO[subscript 2]), and hydrogen sulfide (H[subscript 2]S), could enable the utilization of large natural gas resources, especially when combined with enhanced oil recovery. In this work, a detailed chemical reaction mechanism for oxy-fuel combustion of sour gas is presented. To construct the mechanism, a CH[subscript 4] sub-mechanism was chosen based on a comparative validation study for oxy-fuel combustion. This mechanism was combined with a mechanism for H[subscript 2]S oxidation, and the sulfur sub-mechanism was then optimized to give better agreement with relevant experiments. The optimization targets included predictions for the laminar burning velocity, ignition delay time, and pyrolysis of H[subscript 2]S, and H[subscript 2]S oxidation in a flow reactor. The rate parameters of 15 sulfur reactions were varied in the optimization within their respective uncertainties. The optimized combined mechanism was validated against a larger set of experimental data over a wide range of conditions for oxidation of H[subscript 2]S and interactions between carbon and sulfur species. Improved overall agreement was achieved through the optimization and all important trends were captured in the modeling results. The optimized mechanism can be used to make qualitative and some quantitative predictions on the combustion behavior of sour gas. The remaining discrepancies highlight the current uncertainties in sulfur chemistry and underline the need for more accurate direct determination of several important rate constants as well as more validation data.Siemens Corporatio

Vortex-scalar element calculations of a diffusion flame stabilized on a plane mixing layer

The vortex-scalar element method, a scheme which utilizes vortex elements to discretize the region of high vorticity and scalar elements to represent species or temperature fields, is utilized in the numerical simulations of a two-dimensional reacting mixing layer. Computations are performed for a diffusion flame at high Reynolds and Peclet numbers without resorting to turbulence models. In the nonreacting flow, the mean and fluctuation profiles of a conserved scalar show good agreement with experimental measurements. Results for the reacting flow indicate that for temperature independent kinetics, the chemical reaction begins immediately downstream of the splitter plate where mixing starts. Results for the reacting flow with Arrhenius kinetics show an ignition delay, which depends on reactant temperature, before significant chemical reaction occurs. Harmonic forcing changes the structure of the layer, and concomitantly the rates of mixing and reaction, in accordance with experimental results. Strong stretch within the braids in the nonequilibrium kinetics case causes local flame quenching due to the temperature drop associated with the large convective fluxes

Emergence of Thermodynamics from Darwinian Dynamics

Darwinian dynamics is manifestly stochastic and nonconservative, but has a profound connection to conservative dynamics in physics. In the present paper the main ideas and logical steps leading to thermodynamics from Darwinian dynamics are discussed in a quantitative manner. A synthesis between nonequilibrum dynamics and conservative dynamics is outlined.Comment: latex, 8 page

Impact of Equivalence Ratio on the Macrostructure of Premixed Swirling CH4/Air and CH4/O2/CO2 Flames

Premixed CH[subscript 4]/O[subscript 2]/CO[subscript 2] flames (oxy-flames) and CH[subscript 4]/air flames (air-flames) were experimentally studied in a swirl-stabilized combustor. For comparing oxy and air flames, the same equivalence ratio and adiabatic flame temperature were used. CO[subscript 2] dilution was adjusted to attain the same adiabatic temperature for the oxy-flame and the corresponding air-flame while keeping the equivalence ratio and Reynolds number (=20,000) the same. For high equivalence ratios, we observed flames stabilized along the inner and outer shear layers of the swirling flow and sudden expansion, respectively, in both flames. However, one notable difference between the two flames appears as the equivalence ratio reaches 0.60. At this point, the outer shear layer flame disappears in the air-flame while it persists in the oxy-flame, despite the lower burning velocity of the oxy-flame. Prior PIV measurements (Ref. 9) showed that the strains along the outer shear layer are higher than along the inner shear layer. Therefore, the extinction strain rates in both flames were calculated using a counter-flow premixed twin flame configuration. Calculations at the equivalence ratio of 0.60 show that the extinction strain rate is higher in the oxy than in the air flame, which help explain why it persists on the outer shear layer with higher strain rate. It is likely that extinction strain rates contribute to the oxy-flame stabilization when air flame extinguish in the outer shear layer. However, the trend reverses at higher equivalence ratio, and the cross point of the extinction strain rate appears at equivalence ratio of 0.64.King Abdullah University of Science and Technology (Grant KUS- 110-010-01

The Second Law and Cosmology

I use cosmology examples to illustrate that the second law of thermodynamics is not old and tired, but alive and kicking, continuing to stimulate interesting research on really big puzzles. The question "Why is the entropy so low?" (despite the second law) suggests that our observable universe is merely a small and rather uniform patch in a vastly larger space stretched out by cosmological inflation. The question "Why is the entropy so high" (compared to the complexity required to describe many candidate "theories of everything") independently suggests that physical reality is much larger than the part we can observe.Comment: Transcript of talk at the MIT Keenan Symposium; video available at http://mitworld.mit.edu/video/513, including slides and animation

Design of a rotary reactor for chemical-looping combustion. Part 2: Comparison of copper-, nickel-, and iron-based oxygen carriers

Chemical-looping combustion (CLC) is a novel and promising option for several applications including carbon capture (CC), fuel reforming, H2 generation, etc. Previous studies demonstrated the feasibility of performing CLC in a novel rotary design with micro-channel structures. Part 1 of this series studied the fundamentals of the reactor design and proposed a comprehensive design procedure, enabling a systematic methodology of designing and evaluating the rotary CLC reactor with different OCs and operating conditions. This paper presents the application of the methodology to the designs with three commonly used OCs, i.e., copper, nickel, and iron. The physical properties and the reactivities of the three OCs are compared at operating conditions suitable for the rotary CLC. Nickel has the highest reduction rate, but relatively slow oxidation reactivity while the iron reduction rate is most sensitive to the fuel concentration. The design parameters and the operating conditions for the three OCs are selected, following the strategies proposed in Part 1, and the performances are evaluated using a one-dimensional plug-flow model developed previously. The simulations show that for all OCs, complete fuel conversion and high carbon separation efficiency can be achieved at periodic stationary state with reasonable operational stabilities. The nickel-based design includes the smallest dimensions because of its fast reduction rate. The operation of nickel case is mainly limited to the slow oxidation rate, and hence a relatively large share of air sector is used. The iron-based design has the largest size, due to its slow reduction reactivity near the exit or in the fuel purge sector where the fuel concentration is low. The gas flow temperature increases monotonically for all the cases, and is mainly determined by the solid temperature. In the periodic state, the local temperature variation is within 40 K and the thermal distortion is limited. The design of the rotary CLC is also scaled to different pressures and inlet temperatures. The method of scaling is discussed and desirable operational performances are obtained.King Abdullah University of Science and Technology (KAUST) (Investigator Award)Masdar Institute of Science and Technology (Grant

Techno-economic assessment of sour gas oxy-combustion water cycles for CO2 capture

Growing energy demand coupled with the threat of global warming call for investigating alternative and unconventional energy sources while reducing CO2 emissions. One of these unconventional fuels is sour gas, which consists of methane, hydrogen sulfide and carbon dioxide. Using this fuel poses many challenges because of the toxic and corrosive nature of its combustion products. A promising technology for utilizing it is oxy-fuel combustion with carbon capture and storage, including the potential of enhanced oil recovery for added economic benefits. Although methane oxy-fuel cycles have been studied in the literature, using sour gas as the fuel has not been investigated or considered. In this paper, water is used as the diluent to control the flame temperature in the combustion process, and the associated cycle type is modeled to examine its performance. As the working fluid condenses, sulfuric acid forms which causes corrosion. Therefore, either expensive acid resistant materials should be used, or a redesign of the cycle is required. These different options are explored. A cost analysis of the proposed systems is also conducted to provide preliminary estimates for the levelized cost of electricity (LCOE). The results show the acid resistance cycle with a 4.5% points increase in net efficiency over the cycle with SO[subscript x] removal. However there is nearly a 9% decrease in the cycle's LCOE for the latter case.Aspen Technology, Inc

Biomass torrefaction: Modeling of reaction thermochemistry

Based on the evolution of volatile and solid products predicted by a previous model for willow torrefaction (Bates and Ghoniem, 2012) a thermochemical model has been developed to describe their thermal, chemical, and physical properties as well as the rates of heat release. The first stage of torrefaction, associated with hemicellulose decomposition, is exothermic releasing between 40 and 280 kJ/kginitial. The second stage is associated with the decomposition of the remaining lignocellulosic components, completes over a longer period, and is predicted to be either endothermic or exothermic depending on the temperature and assumed solid properties. Cumulative heat release increases with the degree of torrefaction quantified by the mass loss. The rate of mass loss and rate of heat release increase with higher temperatures. The higher heating value of volatiles produced during torrefaction was estimated to be between 4.4 and 16 MJ/kg increasing with the level of mass loss.BP (Firm

Mixing dynamics in bubbling fluidized beds

Solids mixing affects thermal and concentration gradients in fluidized bed reactors and is, therefore, critical to their performance. Despite substantial effort over the past decades, understanding of solids mixing continues to be lacking because of technical limitations of diagnostics in large pilot and commercial‐scale reactors. This study is focused on investigating mixing dynamics and their dependence on operating conditions using computational fluid dynamics simulations. Toward this end, fine‐grid 3D simulations are conducted for the bubbling fluidization of three distinct Geldart B particles (1.15 mm LLDPE, 0.50 mm glass, and 0.29 mm alumina) at superficial gas velocities U/Umf = 2–4 in a pilot‐scale 50 cm diameter bed. The Two‐Fluid Model (TFM) is employed to describe the solids motion efficiently while bubbles are detected and tracked using MS3DATA. Detailed statistics of the flow‐field in and around bubbles are computed and used to describe bubble‐induced solids micromixing: solids upflow driven in the nose and wake regions while downflow along the bubble walls. Further, within these regions, the hydrodynamics are dependent only on particle and bubble characteristics, and relatively independent of the global operating conditions. Based on this finding, a predictive mechanistic, analytical model is developed which integrates bubble‐induced micromixing contributions over their size and spatial distributions to describe the gross solids circulation within the fluidized bed. Finally, it is shown that solids mixing is affected adversely in the presence of gas bypass, or throughflow, particularly in the fluidization of heavier particles. This is because of inefficient gas solids contacting as 30–50% of the superficial gas flow escapes with 2–3× shorter residence time through the bed. This is one of the first large‐scale studies where both the gas (bubble) and solids motion, and their interaction, are investigated in detail and the developed framework is useful for predicting solids mixing in large‐scale reactors as well as for analyzing mixing dynamics in complex reactive particulate systems.British Petroleum CompanyNational Energy Technology Laboratory (U.S.)United States. Department of Energ

Redox reforming based, integrated solar-natural gas plants: Reforming and thermodynamic cycle efficiency

As demand for energy continues to rise, the concern over the increase in emissions grows, prompting much interest in using renewable energy resources such as solar energy. However, there are numerous issues with using solar energy including intermittency and the need for storage. A potential solution is the concept of hybrid solar-fossil fuel power generation. Previous work has shown that utilizing solar reforming in conventional power cycles has higher performance compared to other integration methods. Most previous studies have focused on steam or dry reforming and on specific component analysis rather than a systems level analysis. In this article, a system analysis of a hybrid cycle utilizing redox reforming is presented. Important cycle design and operation parameters such as the oxidation temperature and reformer operating pressure are identified and their effect on both the reformer and cycle performance is discussed. Simulation results show that increasing oxidation temperature can improve reformer and cycle efficiency. Also shown is that increasing the amount of reforming water leads to a higher reformer efficiency, but can be detrimental to cycle efficiency depending on how the reforming water is utilized.Center for Clean Water and Clean Energy at MIT and KFUPM (Project Number R12-CE-10)King Abdullah University of Science and Technology (KAUST