Heterogeneous Surface Reactions Research Articles

A pore-scale lattice Boltzmann model for solute transport coupled with heterogeneous surface reactions and mineral dissolution

In this paper, we propose a pore-scale lattice Boltzmann model to simulate fluid flow coupled with heterogeneous surface reactions and mineral dissolution. The primary innovation lies in the transformation of surface reactions, originally treated as a boundary condition, into a volume-source term through dimensional augmentation within the framework of sharp liquid–solid interfaces. This significantly simplifies the implementation, particularly for reactions occurring in porous media with intricate geometric structures. Several benchmark tests were performed to validate the accuracy of this model, including a reaction–diffusion problem in a rectangular domain, a two-dimensional reaction and dissolution of a circular grain, as well as a three-dimensional calcite crystal dissolution in a micro-channel. All the obtained simulation results agree well with the reference solutions. In addition, a dissolution problem in a three-dimensional porous medium built with the sand pack is then investigated. Cases with different Péclet numbers (Pe) and Damköhler numbers (Da) were simulated, and five dissolution modes were obtained, which were finally summarized in a diagram of Pe and Da.

Comprehensive modeling of ignition and combustion of multiscale aluminum particles under various pressure conditions

The ignition and combustion of aluminum particles are crucial to achieve optimal energy release in propulsion and power systems within a limited residence time. This study seeks to develop theoretical ignition and combustion models for aluminum particles ranging from 10 nm to 1000 μm under wide pressure ranges of normal to beyond 10 MPa. Firstly, a parametric analysis illustrates that the convective heat transfer and heterogeneous surface reaction are strongly influenced by pressure, which directly affects the ignition process. Accordingly, the ignition delay time can be correlated with pressure through the pb relationship, with b increasing from –1 to –0.1 as the system transitions from the free molecular regime to the continuum regime. Then, the circuit comparison analysis method was used to interpret an empirical formula capable of predicting the ignition delay time of aluminum particles over a wide range of pressures in N2, O2, H2O, and CO2 atmospheres. Secondly, an analysis of experimental data indicates that the exponents of pressure dependence in the combustion time of large micron-sized particles and nanoparticles are –0.15 and –0.65, respectively. Further, the dominant combustion mechanism of multiscale aluminum particles was quantitatively demonstrated through the Damköhler number (Da) concept. Results have shown that aluminum combustion is mainly controlled by diffusion as Da > 10, by chemical kinetics when Da ≤ 0.1, and codetermined by both diffusion and chemical kinetics when 0.1 < Da ≤ 10. Finally, an empirical formula was proposed to predict the combustion time of multiscale aluminum particles under high pressure, which showed good agreement with available experimental data.

Development of a multiphase chemical mechanism to improve secondary organic aerosol formation in CAABA/MECCA (version 4.7.0)

Abstract. During the last few decades, the impact of multiphase chemistry on secondary organic aerosols (SOAs) has been demonstrated to be the key to explaining laboratory experiments and field measurements. However, global atmospheric models still show large biases when simulating atmospheric observations of organic aerosols (OAs). Major reasons for the model errors are the use of simplified chemistry schemes of the gas-phase oxidation of vapours and the parameterization of heterogeneous surface reactions. The photochemical oxidation of anthropogenic and biogenic volatile organic compounds (VOCs) leads to products that either produce new SOA or are taken up by existing aqueous media like cloud droplets and deliquescent aerosols. After partitioning, aqueous-phase processing results in polyols, organosulfates, and other products with a high molar mass and oxygen content. In this work, we introduce the formation of new low-volatility organic compounds (LVOCs) to the multiphase chemistry box model CAABA/MECCA. Most notable are the additions of the SOA precursors, limonene and n-alkanes (5 to 8 C atoms), and a semi-explicit chemical mechanism for the formation of LVOCs from isoprene oxidation in the gas and aqueous phases. Moreover, Henry's law solubility constants and their temperature dependences are estimated for the partitioning of organic molecules to the aqueous phase. Box model simulations indicate that the new chemical scheme predicts the enhanced formation of LVOCs, which are known for being precursor species to SOAs. As expected, the model predicts that LVOCs are positively correlated to temperature but negatively correlated to NOx levels. However, the aqueous-phase processing of isoprene epoxydiols (IEPOX) displays a more complex dependence on these two key variables. Semi-quantitative comparison with observations from the SOAS campaign suggests that the model may overestimate methylbutane-1,2,3,4-tetrol (MeBuTETROL) from IEPOX. Further application of the mechanism in the modelling of two chamber experiments, one in which limonene is consumed by ozone and one in which isoprene is consumed by NO3 shows a sufficient agreement with experimental results within model limitations. The extensions in CAABA/MECCA are transferred to the 3D atmospheric model MESSy for a comprehensive evaluation of the impact of aqueous- and/or aerosol-phase chemistry on SOA at a global scale in a follow-up study.

Multiscale modeling of reactive flow in heterogeneous porous microstructures

This paper presents a multiscale reactive flow model to simulate in-situ leaching of copper in heterogeneous porous microstructures. The introduced workflow combines fluid flow simulation with advection-diffusion-reaction simulation, both required to model reactive flow. The proposed workflow can include the fluid flow in resolved and unresolved pore structures and utilizes required parameters from molecular simulation (ionic diffusivity) and reaction databases (reaction rate parameters). The modeling approach is validated by comparing results to other open-source codes for a model calcite dissolution on acid injection. This model is applied to copper mining by leaching to analyze the reactive flow through a fractured digital rock model of a subsurface sample. Results are analyzed by tracking the concentration distribution along the pore space structure and calculating the outlet concentration of copper to conform the leaching path. Several sensitivity studies are performed to show the robustness of the modeling framework as well as to investigate the importance of each of these parameters on copper production. The complexity of the model is systematically increased from a single scale surface reaction model, to consider the influence of competitive bulk solution reactions, and finally to include flow through porous media to model multiscale reactive flow. This study shows that a multi-scale flow model with homogeneous bulk and heterogeneous surface reactions is required to accurately model copper leaching.

Deciphering heterogeneous enzymatic surface reactions on xylan using surface plasmon resonance spectroscopy

Xylans' unique properties make it attractive for a variety of industries, including paper, food, and biochemical production. While for some applications the preservation of its natural structure is crucial, for others the degradation into monosaccharides is essential. For the complete breakdown, the use of several enzymes is required, due to its structural complexity. In fact, the specificity of enzymatically-catalyzed reactions is guided by the surface, limiting or regulating accessibility and serving structurally encoded input guiding the actions of the enzymes. Here, we investigate enzymes at surfaces rich in xylan using surface plasmon resonance spectroscopy. The influence of diffusion and changes in substrate morphology is studied via enzyme surface kinetics simulations, yielding reaction rates and constants. We propose kinetic models, which can be applied to the degradation of multilayer biopolymer films. The most advanced model was verified by its successful application to the degradation of a thin film of polyhydroxybutyrate treated with a polyhydroxybutyrate-depolymerase. The herein derived models can be employed to quantify the degradation kinetics of various enzymes on biopolymers in heterogeneous environments, often prevalent in industrial processes. The identification of key factors influencing reaction rates such as inhibition will contribute to the quantification of intricate dynamics in complex systems.

New Indole Derivative Heterogeneous System for the Synergistic Reduction and Oxidation of Various Per-/Polyfluoroalkyl Substances: Insights into the Degradation/Defluorination Mechanism.

The hydrated electron (eaq-) system is typically suitable for degrading perfluoroalkyl substances (PFASs). To enhance eaq- utilization, we synthesized a new indole compound (DIHA) that forms stable nanospheres (100-200 nm) in water via a supramolecular assembly. Herein, the DIHA nanoemulsion system exhibits high degradation efficiencies toward a broad category of PFASs, regardless of the headgroup, chain length, and branching structure, under UV (254 nm) irradiation. The strong adsorption of PFAS on the DIHA surface ensures its effective degradation/defluorination. Quenching experiments further demonstrated that the reaction took place on the surface of DIHA nanospheres. This specific heterogeneous surface reaction unveiled novel PFAS degradation and defluorination mechanisms that differ from previously reported eaq- systems. First, the photogenerated surface electrons nonselectively attacked multiple C-F bonds of the -CF2- chain. This plays a dominant degrading/defluorinating role in the DIHA system. Second, abundant hydroxyl radicals (•OH) were also produced, leading to synergistic reduction (by surface electron) and oxidation (by surface •OH) in a single system. This facilitates faster and deeper defluorination of different structured PFASs through multiple pathways. The new mechanism inspires the design of innovative organo-heterogeneous eaq- systems possessing synergistic reduction and oxidation functions, thereby making them potentially effective for treating PFAS-contaminated water.

Phase change and combustion of iron particles in premixed CH[formula omitted]/O[formula omitted]/N[formula omitted] flames

Metal powder is a promising carbon-free and recyclable energy carrier. Direct combustion of the micron-sized iron particles involves complex physical and chemical processes, such as heat transfer, surface reaction, and phase change. In this work, computational modelling of these processes is investigated and validated against experiments. A single iron particle combustion and phase change model is proposed in an Eulerian–Lagrangian framework. The new phenomenological model considers five stages, i.e., solid phase oxidation, melting of iron oxides and raw iron, liquid phase oxidation, cooling of liquid iron oxides, and solidification of super-cooled liquid iron oxides. The proposed model is first validated and then adopted in simulations of micron-sized iron particle combustion in premixed CH4/O2/N2 flames to study the effects of ambient temperature and oxygen concentration on single iron combustion. Results show that the new model is capable of replicating the melting, heterogeneous surface reaction, cooling, and solidification processes. Two-stage solidification is observed in experiments and modelled in simulations. This two-stage solidification includes a fast solidification with a significant temperature rise (∼150–200 K) and a thermal equilibrium solidification featuring a constant temperature and a slight particle radiant intensity decrease. In addition, a diffusion-controlled mechanism is identified during the melting process, in which the oxygen concentration dominates the melting time and the subsequent burning time. Furthermore, it is found that the reaction between iron and CH4/O2/N2 flame products, such as CO2 and H2O, plays a non-negligible role in the iron combustion process.

The Fabrication of Halogen-Doped FeWO4 Heterostructure Anchored over Graphene Oxide Nanosheets for the Sunlight-Driven Photocatalytic Degradation of Methylene Blue Dye.

Rapid industrialization and urbanization are the two significant issues causing environmental pollution. The polluted water from various industries contains refractory organic materials such as dyes. Heterogeneous photocatalysis using semiconductor metal oxides is an effective remediation technique for wastewater treatment. In this research, we used a co-precipitation-assisted hydrothermal method to synthesize a novel I-FeWO4/GO sunlight-active nanocomposite. Introducing dopant reductive iodine species improved the catalytic activity of FeWO4/GO. I- ions improved the catalytic performance of H2O2 by doping into FeWO4/GO composite. Due to I- doping and the introduction of graphene as a support medium, enhanced charge separation and transfer were observed, which is crucial for efficient heterogeneous surface reactions. Various techniques, like FTIR, SEM-EDX, XRD, and UV-Vis spectroscopy, were used to characterize composites. The Tauc plot method was used to calculate pristine and iodine-doped FeWO4/GO bandgap. Iodine doping reduced the bandgap from 2.8 eV to 2.6 eV. The degradation of methylene blue (MB) was evaluated by optimizing various parameters like catalyst concentration, oxidant dose, pH, and time. The optimum conditions for photocatalysts where maximum degradation occurred were pH = 7 for both FeWO4/GO and I-FeWO4/GO; oxidant dose = 9 mM and 7 mM for FeWO4/GO and I-FeWO4/GO; and catalyst concentration = 30 mg and 35 mg/100 mL for FeWO4/GO and I-FeWO4/GO; the optimum time was 120 min. Under these optimum conditions, FeWO4/GO and I-FeWO4/GO showed 92.0% and 97.0% degradation of MB dye.

Distinguishing homogeneous advanced oxidation processes in bulk water from heterogeneous surface reactions in organic oxidation

Clarifying the reaction pathways at the solid-water interface and in bulk water solution is of great significance for the design of heterogeneous catalysts for selective oxidation of organic pollutants. However, achieving this goal is daunting because of the intricate interfacial reactions at the catalyst surface. Herein, we unravel the origin of the organic oxidation reactions with metal oxide catalysts, revealing that the radical-based advanced oxidation processes (AOPs) prevail in bulk water but not on the solid catalyst surfaces. We show that such differing reaction pathways widely exist in various chemical oxidation (e.g., high-valent Mn3+ and MnOX) and Fenton and Fenton-like catalytic oxidation (e.g., Fe2+ and FeOCl catalyzing H2O2, Co2+ and Co3O4 catalyzing persulfate) systems. Compared with the radical-based degradation and polymerization pathways of one-electron indirect AOP in homogeneous reactions, the heterogeneous catalysts provide unique surface properties to trigger surface-dependent coupling and polymerization pathways of a two-electron direct oxidative transfer process. These findings provide a fundamental understanding of catalytic organic oxidation processes at the solid-water interface, which could guide the design of heterogeneous nanocatalysts.

The Effect of Lithium Ion Leaching from Calcined Li-Al Hydrotalcite on the Rapid Removal of Ni2+/Cu2+ from Contaminated Aqueous Solutions.

A layered double hydroxide (LDH) calcined-framework adsorbent was investigated for the rapid removal of heavy metal cations from plating wastewater. Li-Al-CO3 LDH was synthesized on an aluminum lathe waste frame surface to prepare the sorbent. The calcination treatment modified the LDH surface properties, such as the hydrophilicity and the surface pH. The change in surface functional groups and the leaching of lithium ions affected the surface properties and the adsorption capacity of the heavy metal cations. A zeta potential analysis confirmed that the 400 °C calcination changed the LDH surface from positively charged (+10 mV) to negatively charged (-17 mV). This negatively charged surface contributed to the sorbent instantly bonding with heavy metal cations in large quantities, as occurs during contact with wastewater. The adsorption isotherms could be fitted using the Freundlich model. The pseudo-second-order model and the rate-controlled liquid-film diffusion model successfully simulated the adsorption kinetics, suggesting that the critical adsorption step was a heterogeneous surface reaction. This study also confirmed that the recovered nickel and/or copper species could be converted into supported metal nanoparticles with a high-temperature hydrogen reduction treatment, which could be reused as catalysts.

Heterogeneous Surface Reaction Analysis of Non-Thermal Plasma-Enhanced Spherical MOx/(Ce0.7Ti0.3)O2 Catalyst Desulfurization: Effects of Plasma and MOx Loading on Surface Oxygen Defects

Homogeneous gas-phase plasma reactions and heterogeneous surface reactions are involved in non-thermal plasma-enhanced catalysis, along with a very complicated strengthening mechanism. In this study, we supported CuO, Co3O4, Fe2O3, or NiO on a hydrothermally synthesized spherical (Ce0.7Ti0.3)O2 catalyst, analyzed its active sites, and examined how plasma affects the catalyst surface and influences heterogeneous surface reactions. Loading CuO onto the catalyst led to increases of 5.85 and 13.51% in the proportions of surface Ce3+ and surface O vacancies, respectively. The CuO-loaded catalyst exhibited a significantly higher redox capacity than the other catalysts at 250–290 °C, which promotes SO2 desorption and surface reactions at low temperatures. Treatment with plasma led to increases in the active-to-lattice-oxygen ratio on the catalyst surface (by 19.12%), the defect-induced D-band to F2g band (ID/IF2g) ratio (by 0.443), and the D-band intensity (by a factor of 3.5). Significantly more defects that adsorb plasma-generated oxygen radicals (O* and O2*) and O3, which subsequently oxidize adsorbed pollutant molecules, are present on the catalyst surface. In general, the special surface properties of the spherical CuO/(Ce0.7Ti0.3)O2 catalyst are applicable to a broad number of non-thermal plasma-enhanced catalytic oxidation scenarios.

Anchoring catalytically active species on alumina via surface hydroxyl group for durable surface reaction

Ensuring durable catalyst structure is crucial for heterogeneous surface reactions. Particularly, exhaust gas treatment catalyst needs exceptional durability at very high temperature (≥ 800 ºC) and low-temperature activity. Here, a hierarchical catalyst structure consisting of alumina, ceria, and Pt was synthesized to achieve high activity and durability. The alumina surface was modified to have surface hydroxyl groups by hydrothermal pre-treatment at various temperatures, then this alumina was used to anchor catalytically active species to form a highly durable surface structure. Whereas Pt and ceria on bare alumina suffered from significant sintering after aging at 800 ºC, the same species formed on the pre-treated alumina hardly presented change in surface structure after aging. This durable Pt/CeO2/Al2O3 catalyst showed no degradation for the simultaneous oxidation of CO, C3H6, and C3H8 with water vapor for repeated reactions or long-term reactions. This work can provide a useful guideline in designing a durable heterogeneous catalyst.

Influence of the solid titanium source on the activity of La1−xTixFeO3 photo-CWPO catalysts under UV-A light

In the search for more efficient low-temperature catalysts able to oxidise biorecalcitrant pollutants in water, the selective substitution of La3+ by Ti3+ cations was reported to boost the UV-A light driven activity of LaFeO3 orthoferrites as H2O2-mediated photo-CWPO catalysts. La1−xTixFeO3 catalysts with 0 < x < 0.11 were obtained by a modified Pechini sol–gel route via the addition of a solid source of titanium during the synthesis. By using a span of crystallized and amorphous TiO2, the influence of the titanium source on the substitution rate in the orthoferrite network and on the performances of the catalysts under UV-A light was demonstrated using the degradation of 4-chlorophenol as test reaction. The amorphous content of the TiO2 precursor is proposed to be the key factor driving the substitution of La3+, the largest substitution of 11 % being obtained using a dried sol-gel TiO2 precursor. We suggest that the substitution proceeds during the thermal treatment via a solid-solid diffusion between TiO2 and the amorphous LaFeO3 before it crystallises. The catalyst robustness was influenced by the TiO2 nature. Small size Ti-LaFeO3 crystallites strongly lowered or blocked the Fe release, while no improvement was observed for large size crystallites vs. the pristine material, what was associated to a poor homogenization of the titanium in the network. We showed that the mineralization activity was proportional to the substitution rate of La1−xTixFeO3 catalysts, while a similar relationship could be drawn for the degradation activity only in the case of highly robust catalysts with pure heterogeneous surface reactions.

Turbulent premixed hydrogen/air flame-wall interaction with heterogeneous surface reactions

A premixed H2/air flame impinging onto a flat surface in statistically stationary state is studied for both reactive and inert wall cases to gain insights into the effects of the heterogeneous surface reactions. Direct numerical simulation (DNS) results with detailed gas-phase chemistry and surface adsorption and desorption mechanisms indicate differences in the flame front topology and near-wall flame dynamics between these two cases. In the reactive surface case, gas-phase free radicals are inclined to be adsorbed with much reduced near-wall concentration. Consequently, the gas-phase heat release rate (HRR) close to the wall decreases as well because of the low availability of free radicals. However, extra heat released from the reactive surface partially compensates for such difference. Moreover, wall reactions will intensify the turbulent fluctuations of the wall temperature and wall heat flux, while for these two cases the mean temperature profile along the flame propagating direction remains similar.

Sensitivity of flame structure and flame speed in numerical simulations of laminar aluminum dust counterflow flames

Aluminum dust counterflow flames are investigated numerically using a two-stage model including the effects of interphase heat transfer, phase change, heterogeneous surface reaction (HSR), oxide cap growth, homogeneous combustion and radiation. The numerical model is first validated by simulating the aluminum dust counterflow flames of McGill University [Julien et al., 2017]. The results show that the particle velocity profile is consistent with the experimental results, and the error in the gas phase velocity caused by the use of aluminum particles as tracers in the experiment is analyzed. Then, further validation is conducted by comparison of the flame speed, and the predicted results agree well with the measurements. The flame structure of the aluminum dust counterflow flame is analyzed, and intermediate product (AlO) is observed to present a discrete distribution in space due to the nature of heterogeneous combustion. Different terms in the particle energy equation are analyzed, and the results indicate that the HSR plays an important role in the late preheating stage, while the interphase heat transfer dominates the rest of the conversion process. Under the assumption of unity Lewis number, the interphase heat/mass transfer models are found to have a great impact on the flame for a particle size smaller than 10 µm. With increasing particle sizes, the flame speed decreases, and most particles with a diameter of 12 µm cannot be fully burnt in the flame under the studied conditions. The effect of the strain rate on the flames is investigated with different particle sizes and unstretched reference flame speeds are obtained by linear extrapolation of the predicted results. Finally, a sensitivity analysis of the parameters of the heterogeneous surface reaction model is conducted.

Elemental sulfur generated in situ from Fe(III) and sulfide promotes sulfidation of microscale zero-valent iron for superior Cr(VI) removal

Herein, we compared the effect of different extra iron and sulfur precursors on the sulfidation efficiency, physicochemical properties, and reactivity of post-sulfidated microscale zero-valent iron (S-ZVI). S0@ZVI was synthesized from in situ S0 generated via reaction of Fe(III) with S2-, which resulted in 23-fold higher Cr(VI) removal compared with S0com/ZVI synthesized using commercial S0. The direct formation of FeSx film via reaction between S0 and ZVI played a crucial role in enhancing the removal of Cr(VI) by S0@ZVI, with 16- and 12-fold faster rates compared with FeS@ZVI and FeS2@ZVI prepared via precipitated reaction of Fe(II) with S2- and sulfur mixtures, respectively. The incorporated sulfur, sulfidation sequence, and sulfidation time determined the performance of S0@ZVI. A combination of batch experiments and kinetic models was used to determine the chemical composition of reduced Cr(VI) products. S0@ZVI immobilized Cr(VI) as Fe0.5Cr0.5(OH)3 via surface heterogeneous reactions, and partial Cr(VI) was homogeneously reduced to soluble Cr(acetate)3 or Fe0.75Cr0.25(OH)3(aq) by dissolved Fe(II). The insights gained from this study will facilitate the fabrication of highly reactive S-ZVI and elucidate the mechanism of Cr(VI) removal.

Plasmonic effect and bandgap tailoring of Ag/Ag2S doped on ZnO nanocomposites for enhanced visible-light photocatalysis

Ag/Ag2S-ZnO nanocomposites were prepared via a simple hydrothermal process followed by a plasmonic Ag+ reduction through a photo-deposition method. Ag2S was introduced to narrow the overall composite bandgap and activate the surface plasmon resonance (SPR) effect of the Ag+ cation present. The physicochemical properties of the as-synthesised catalysts were characterised by X-ray diffraction (XRD), scanning and transmission electron microscopies (SEM and TEM), Brunauer-Emmett-Teller (BET) analysis. Fourier-transform infrared spectroscopy (FTIR), Ultraviolet diffuse reflectance spectroscopy (UV–vis DRS), photoluminescence emission spectra (PL) and X-ray photoelectron spectroscopy (XPS) was conducted to investigate the photo-absorption and emission spectra of the nanocomposites. The degradation efficiency of all the synthesised catalysts (ZnO, Ag2S, Ag/ZnO and Ag2S/ZnO) prior to the final product, Ag/Ag2S/ZnO was tested and compared. Results showed that the ternary Ag/Ag2S/ZnO achieved a 98 % phenol removal compared to 50 %, 11 %, 64 % and 93 % for ZnO, Ag2S, Ag/ZnO and binary Ag2S/ZnO, respectively. The degradation kinetics followed the Langmuir-Hinshelwood model, which typically describes heterogeneous photocatalytic surface reactions. The linear fits had R2 values higher than 0.97, which confirms the degree of accuracy or statistical fitness to the kinetic model. Degradation scavenger test confirmed the holes (h+) as the main inhibitor and identified the superoxide O2•¯ radical as the main active specie responsible for the degradation. Total organic carbon analysis using the ternary Ag/Ag2S-ZnO catalyst only achieved a 74% phenol mineralization after 24 h of photocatalysis. Recyclability tests showed good phenol removal stability of Ag/Ag2S-ZnO at 41 % after five recycle runs. Hence, a synergistic degradation mechanism responsible for the efficient photo-degradation performance was proposed.

Combustion characteristics of aluminum particle jet flames in a hot co-flow

Aluminum(Al) powder has been proposed as a promising dense energy carrier to store and transport abundant renewable power for a future carbon-neutral society. In this work, a detailed model for simulating Al particle cloud combustion with multiple oxidizers in the context of large eddy simulation is developed. The Al particles are tracked in the lagrangian framework with various sub-models including phase change, heterogeneous surface reaction, evaporation and radiation. The model is then employed to simulate turbulent jet flames with Al particles(d32=25μm) in a hot co-flow. Tunable diode laser absorption spectroscopy(TDLAS) is used to measure the temperature and H2O distribution. The present model is first validated by comparing the predicted condensed Al2O3 distribution with the measured Mie scattering signals. The results indicate that the simulation results are in good agreement with the experimental measurements. Further comparisons of the temperature and H2O profile are then conducted. The numerical simulation predicts weaker mass and heat transport in the upstream and middle of the flame along the centerline of the burner, compared with the reconstructed TDLAS results, but the downstream scalar profiles of the jet flame agree well with the measurements. Discrete characteristics are observed in the simulated instantaneous temperature and condensed Al2O3 snapshots, which are due to the nature of heterogeneous combustion of metal fuel particles under fuel-lean conditions. Finally, the influence of the oxidizer mole fraction and the initial temperature of the primary jet on the ignition distance is analyzed. The results demonstrate that the ignition distance can be decreased effectively by increasing the oxidizer concentration of the hot co-flow or the initial temperature of the Al particles and carrier gas.

Coupling mesoscale transport to catalytic surface reactions in a hybrid model.

In heterogeneous catalysis, reactivity and selectivity are not only influenced by chemical processes occurring on catalytic surfaces but also by physical transport phenomena in the bulk fluid and fluid near the reactive surfaces. Because these processes take place at a large range of time and length scales, it is a challenge to model catalytic reactors, especially when dealing with complex surface reactions that cannot be reduced to simple mean-field boundary conditions. As a particle-based mesoscale method, Stochastic Rotation Dynamics (SRD) is well suited for studying problems that include both microscale effects on surfaces and transport phenomena in fluids. In this work, we demonstrate how to simulate heterogeneous catalytic reactors by coupling an SRD fluid with a catalytic surface on which complex surface reactions are explicitly modeled. We provide a theoretical background for modeling different stages of heterogeneous surface reactions. After validating the simulation method for surface reactions with mean-field assumptions, we apply the method to non-mean-field reactions in which surface species interact with each other through a Monte Carlo scheme, leading to island formation on the catalytic surface. We show the potential of the method by simulating a more complex three-step reaction mechanism with reactant dissociation.

Numerical simulation of aluminum dust counterflow flames

&lt;sec&gt;Aluminum is widely used as an additive in solid rocket propellants and pyrotechnics due to its outstanding characteristics such as high energy density and combustion temperature, environmentally benign products, and good stability. Recently, aluminum powders are found to present great potential serving as alternative fuel in a low-carbon economy. In this paper, a detailed model including the effects of interphase heat transfer, phase change, heterogeneous surface reactions, homogeneous combustion and radiation is employed to investigate aluminum dust counterflow flames.&lt;/sec&gt;&lt;sec&gt;The numerical model is first validated by simulating the aluminum dust counterflow flames of McGill University. The results indicate that the particle velocity profile is in very good agreement with the experimental measurements. A detailed analysis of estimating the gas phase velocity based on the particle velocity is performed by using Stoke time &lt;i&gt;τ&lt;/i&gt;&lt;sub&gt;s&lt;/sub&gt;. The results show that a correct value of &lt;i&gt;τ&lt;/i&gt;&lt;sub&gt;s&lt;/sub&gt; is the key to this method, and using a single value of &lt;i&gt;τ&lt;/i&gt;&lt;sub&gt;s&lt;/sub&gt; can bring a notable bias to the results, which may also affect the evaluation of flame speed from the counterflow flame. It is suggested that model validation should be carried out by directly comparing the particle velocity profiles from the simulations with those from the experiments. The flame structure of the aluminum dust counterflow flame is discussed, and the interphase heat transfer model is found to have a great influence on the flame for particle sizes smaller than 10 μm. Therefore, when simulating the aluminum dust flames with small particle sizes, the interphase heat transfer model should be selected carefully so that it can cover the transition heat transfer regime. The effect of particle diameter is examined. With the increase of the particle size, the flame speed continues to decrease, and most particles with a diameter of 15 μm cannot be fully burnt in the present configuration. The strain rate is found to be an important factor affecting the dust flame. As the strain rate increases, the residence time of the particles in the flame zone decreases, which ultimately leads the particles to be combusted incompletely. Moreover, the reaction zone of the counterflow flame, marked as AlO, is observed to be shrunk from a large double-peak structure into a small single-peak one along the burner centerline when strain increases. The reference flame speed increases with strain rate, and an unstretched reference flame speed of roughly 29 cm/s can be obtained by linear extrapolation of the predicted results. The effect of radiation is investigated by comparing two cases with and without radiative heat transfer. The results show that the heat loss caused by radiation can lead the temperature to decrease greatly in the gas phase, but the heating effect on the particles by radiation is relativelysmall.&lt;/sec&gt;