Ethylene Diffusion Research Articles

Dynamics of Water, CO₂, Ethane and Their Mixtures in ZSM-22 Zeolite: The Role of Polarity and Hydrogen Bonding

Abstract Understanding the interplay between confinement effects and intermolecular interactions is essential for predicting molecular diffusion in zeolites. In this study, we investigate the diffusion behavior of ethane, CO₂, and water in ZSM-22 molecular sieves, focusing on the effects of mixing these fluids. Our results reveal that while CO₂ has minimal impact on ethane diffusion, water significantly slows ethane’s motion by forming molecular bridges across the pore structure, reducing ethane's diffusion by up to 30%. Ethane, in turn, restricts water’s mobility, and reduces the water-water coordination number from 2.22 to 0.73 depending on concentration. The diffusion of CO₂ in mixtures shows a 40% increase in pure state under confinement. The role of polarity and hydrogen bonding is crucial, with water molecules exhibiting 1.2 hydrogen bonds in the confined state—much lower than the 3.4 bonds in bulk water. Molecular rotation in ZSM-22 of all fluids occurs at two distinct time scales: the short-time fast rotation dominated by molecular inertia and the long-time rotation hindered by fluid-zeolite interactions. For water, hydrogen bonding further restricts full rotational freedom. These findings provide a comprehensive understanding of how ethane, water, and CO₂ interact and diffuse in nanoporous materials.

Understanding retention and intra-particle diffusivity of alkylsulfobetaine-bonded Ethylene Bridged Particles with different mesopore sizes for hydrophilic interaction liquid chromatography applications

The role of the average pore diameter (APD) of 1.7μm AtlantisTM Premier BEHTM Particles derivatized with a zwitterionic group (propylsulfobetaine) on the efficiency of their 2.1 × 50 mm hydrophilic interaction liquid chromatography (HILIC) packed columns is investigated experimentally. Van Deemter plots for toluene (neutral, hydrophobic), cytosine (neutral, polar), tosylate (negatively charged), bretylium and atenolol (positively charged) were measured on three HILIC columns packed with BEH Z-HILIC Particles having APDs of 95 Å, 130 Å, and 300 Å. The intraparticle diffusivities of the analytes across these three BEH Z-HILIC Particles were measured by the peak parking method.The experimental data reveal that the slope of the C-branch of the van Deemter plots can be reduced by factors of about 15 for toluene, 2.5 for cytosine, 6 for atenolol, 5 for tosylate, and 14 for bretylium with increasing the APD from 95 Å to 300 Å. This observation is explained by: (1) the reduced amount of the highly viscous water diffuse layer and subsequent increase of the amount of acetonitrile-rich eluent in the mesopores, (2) the localized electrostatic adsorption of the retained analytes onto the zwitterion-bonded BEH Particles, and (3) depletion/excess of the analytes into the water diffuse layer. A general model of intraparticle diffusivity was then proposed to account for the impact of the APD of Z-HILIC Particles on the solid-to-liquid mass transfer resistance of small molecules. The model highlights the relevance of the thickness of the water diffuse layer, the access of the bulk eluent into the mesopore, the localized electrostatic adsorption, and the partitioning constant of the retained analyte between the bulk eluent and the water diffuse layer.

Effects of Oxygen Concentration on Soot Formation in Ethylene and Ethane Fuel Laminar Diffusion Flames

In studying the effects of oxygen concentration and molecular structure on the morphologies of the soot particles produced by hydrocarbon fuels, ethylene and ethane were chosen as experimental fuels. With a Gülde laminar coaxial diffusion flame device, a soot particle device was used to sample soot particles at different oxygen concentrations (21%, 24%, 26%, 28%, and 31%) and at different heights above a burner (HABs = 10 mm, 20 mm, 30 mm, 40 mm, and 50 mm). High-resolution transmission electron microscopy (HRTEM) was used to scrutinize and analyze the soot particles at varying oxygen concentrations. The findings suggest that at the same oxygen concentration, ethylene produces brighter and taller flames. With an increase in the oxygen concentration, ethylene flames and ethane flames gradually decrease in height and become brighter. With an increase in the HAB, the average primary soot particle diameter (Dp) increases initially and then decreases, the fractal dimension (Df) increases, and the aggregates transition from strips and chains to clusters. At the same flame height (HAB = 30 mm), the Dp decreases, the Df increases, the carbon layer torsion resistance (Tf) and the carbon layer spacing (Ds) increase, and the carbon layer changes from a parallel arrangement to a curved arrangement to form denser network aggregations.

Effect of H2/CO addition on soot formation in ethylene diffusion flame

Coupling the San Diego gas phase reaction mechanism and the Moss Brookes soot model using FLUENT14.0 software, the effect of adding H2/CO on the fuel side on soot formation in an ethylene/air laminar diffusion flame was studied. A specific analysis was conducted on the effects of H2, CO and its chemical effects on flame temperature, soot volume fraction, mole fractions of important intermediate products OH, H, and C2H2, as well as rate of soot mass nucleation, surface growth, and oxidation. In the numerical calculation, the virtual substances FH2 and FCO are set to separate the chemical effect of H2 and CO and to analyze the chemical effect of adding H2 and CO on soot formation. The results show that the flame temperature increases slightly, and the soot volume fraction decreases monotonically with adding H2 and CO. The chemical effect of H2 increases the temperature, the mole fraction of C2H2 and H, the soot nucleation rate, and the surface growth rate, and finally, it promotes soot formation. The chemical effect of CO increases the temperature and H mole fraction, reduces the OH mole fraction, and then increases the soot surface growth rate and reduces the soot oxidation rate. The higher soot nucleation, surface growth rate, and lower oxidation rate jointly promote soot formation.

Physical and Chemical Effects of Ammonia on Gas Emissions and Soot Formation in Laminar Coflow Ethylene Diffusion Flames

Physical and Chemical Effects of Ammonia on Gas Emissions and Soot Formation in Laminar Coflow Ethylene Diffusion Flames

Synthesis of hierarchically porous Cu-BTC through phase-controlled etching

To enhance diffusion channels and boost active sites within microporous metal–organic frameworks, hierarchically porous structures are indispensable. This study pioneered phase-controlled acetic acid etching techniques, encompassing solution etching and steam etching resulting in the successful synthesis of a series of hierarchically porous Cu-BTC (HP-Cu-BTC). In contrast to etching with an acetic acid solution, acetic acid steam etching offers advantages in terms of reduced etchant usage and minimized damage to the original microporous structure. Noteworthy, by employing steam-controlled recovery etching technology, it is possible to regulate both the steam concentration and the etching degree, while also facilitating the recovery of etchant. The prepared HP-Cu-BTC exhibits adjustable pore sizes (15–45 nm), and mesopore volume (0.14–0.23 cm3/g). Compared to the original Cu-BTC, the well-engineered HP-Cu-BTC demonstrates an 81 % increase in ethylene diffusion rates. The phase-controlled synthesis of HP-MOFs serves as a valuable source of inspiration for the future preparation of hierarchical porous structures.

Characterization of the evolution of leakage and variation of in-pipe parameters in a full-size ethane high-pressure pipeline

There is a risk of leakage of ethane during high-pressure pipeline transportation. In order to investigate the effects of leakage conditions on the free-field ethane concentration distribution, temperature and pressure evolution, a full-size ethane high-pressure gas pipeline experimental platform was constructed, and high-pressure ethane leakage experiments were carried out with different diameters and leakage directions to investigate the effects of different leakage directions and diameters on the free-field ethane diffusion, temperature and pressure inside the pipeline. The experiment results show that in the free field, when the leakage direction is ≥45° to the horizontal plane, the near-surface ethane concentration is close to 0. When the horizontal leakage occurs, compared with the 15 mm leak diameters, the peak concentration of the 25 mm leak diameters rises by 17.7%, and the explosion danger range rises by 75%, and the explosion danger time is extended by 78.6%. It is worth mentioning that the initial pressure drop rate and the overall temperature drop in the pipeline increase and then decrease with the increase of leak diameters during the high-pressure ethane leakage process, and there is a critical diameter, which is 15 mm in this experiment. The results of the study provide a reference for the safe operation of the high-pressure ethane gas pipeline.

The kinetics and warm flame chemistry associated with radiative extinction of spherical diffusion flames

Several studies have found that microgravity diffusion flames with sufficient heat loss cool until they extinguish at a critical temperature near 1130 K. In this work, the associated chemical kinetics are explored for spherical diffusion flames burning ethylene. The flames are simulated with a transient numerical model with detailed chemistry, transport, and radiation. This incorporates the UCSD mechanism with 57 species and 270 reactions. Species concentrations, reaction rates, and heat release rates are examined. Upon ignition, the peak temperature is above 2000 K, but this decreases until extinction due to radiative losses. This allows the chemistry to be studied over a wide range of peak temperatures for the same fuel and oxidiser. When the peak temperature is high, the dominant chemistry is similar to that for typical normal-gravity ethylene diffusion flames. There are two distinct zones: an ethylene pyrolysis zone and an oxidation zone, and negligible reactant leakage. The ethylene mainly reacts with H and OH. The concentration of OH in the ethylene pyrolysis zone is high due to the long residence times and reactions of CO2 and H2O with H. As the flame cools and the peak temperature approaches the critical extinction temperature, there is increased reactant leakage leading to higher O, OH, and HO2 concentrations on the fuel side. Most reactions shift towards the oxidiser side and there is large overlap between the two zones. Reactions involving HO2 become more significant and the large consumption rates of H by HO2 increase the concentrations of OH and O on the fuel side. The appearance of warm flame chemistry delays extinction but is not sufficiently exothermic to prevent it.

Synthesis and evaluation of mono(phenoxy-imine) titanium complexes attached to a single polystyrene chain end for ethylene polymerization

Monodisperse polystyrene (PS) chains with different lengths are synthesized by atom transfer radical polymerization (ATRP), serving as soluble supports for attaching mono(phenoxy-imine) metal complexes in the chain end. For ethylene polymerization, the PS chain-supported titanium (Ti) complexes exhibit unique catalytic features such as higher activity. Their performance in ethylene polymerization and kinetic examination is extensively investigated to uncover the influence mechanism of support chain length. Initially, the catalytic activity of the supported catalysts increases with the support chain length, but then decreases. Effective preservation by the support prevents catalyst deactivation and enhances the concentration of active sites [C*], leading to increased activity. However, the decline in activity is attributed to the exceptionally long support chain, impeding ethylene diffusion and leading to a reduction in ethylene concentration [M] around active sites. As the support chain length increases, the molecular weight (Mw) of the produced polyethylene (PE) decreases. The nascent polyethylene obtained from supported catalysts displays a uniform petal-like and shish-kebab morphology. The well-defined nature of these PS chain-supported catalysts provides a powerful tool for studying interactions between active centers and supports, offering insights that can guide the design of catalysts.

A numerical study of NOX and soot emissions in ethylene-ammonia diffusion flames with oxygen enrichment

Blending ammonia with hydrocarbon fuels is gaining interest due to its potential to significantly reduce carbon emissions from the combustion of these blends. Additionally, studies have provided strong evidence of oxygen enhanced combustion to reduce soot emissions and improve flame stability. The present work attempts to leverage the benefits of both strategies, ammonia doping and oxygen enhanced combustion, by considering ethylene diffusion flames. Simulations are performed using the CHEMKIN-Pro software. A reaction mechanism with 372 species and 13,847 reactions is developed by combining gas phase chemistries for ethylene, NH3 and NOX, along with a detailed soot mode. The mechanism is extensively validated for a range of fuel blends in terms of flame structure, intermediate hydrocarbons, soot precursors and soot. Oxygen enrichment is achieved by removing certain amount of nitrogen from oxidizer stream and adding it to fuel stream, and thereby maintaining a nearly constant flame temperature. Extensive analysis is carried out to characterize the chemical and dilution effects of ammonia doping on flame structure, soot precursors, soot, and NOX in ethylene flames with varying levels of oxygenation. Further, dominant reaction pathways for several soot precursors and NOx are identified through detailed rate of production analyses. Results indicate that ammonia doping in ethylene flames leads to substantial increase in NOX emissions, while oxygenation has negligible influence on NOX emissions. In contrast, both NH3 doping and oxygenation provide significant reduction in the formation of soot precursors and soot. Oxygenation achieves this reduction through both hydrodynamic and flame structure effects, as the flame shifts from oxidizer side to fuel side. On the other hand, NH3 doping reduces the rates of important reactions for the formation of soot precursors, as the concentrations of relevant species (C2H2, C3H3, C3H3-P, C3H3-A etc.) decrease due to their consumption through reactions with species like NCO and CN formed from NH3. Moreover, the effectiveness of NH3 doping is further enhanced when combined with oxygenation. Hence, NH3 doping and oxygenation are found to be effective and synergistic strategies in reducing soot emissions, and their proper combination could provide near zero soot emissions.

Effect of ammonia addition on nanostructure of soot in laminar coflow diffusion flames of ethylene diluted with nitrogen

The effect of ammonia addition on the nanostructure of soot particles was studied experimentally for ethylene diffusion flames. To compensate the thermal effect and nitrogen-containing species production when ammonia was added, the total mole fraction of ammonia and nitrogen was fixed in the fuel stream. Soot particle size, fringe length, and fringe tortuosity were measured through transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). A complementary X-ray photoelectron spectroscopy (XPS) analysis provided information about the chemical bonding of soot. A significant delay in soot growth was observed and the particle size increased with the addition of ammonia. While there was no obvious correlation between the fractal dimension of soot and ammonia mole fraction (XNH3) or sampling location. With the addition of ammonia, the mean fringe length increased reasonably linearly with XNH3 and the fringe tortuosity increased up to XNH3 ≈ 0.17 and then decreased with XNH3, which suggested that ammonia addition led to higher graphitization and lower oxidative activity. The soot from ammonia diluted flame exhibited lower reactivity, implying the delay of soot surface growth. With the addition of ammonia, the value of sp2/sp3 (indication of the graphitization degree of soot particles) did not change much for XNH3 from 0 to 0.17 then increased significantly, which indicated the degree of graphitization of soot particles significantly increased with ammonia addition. The intensity of the N1s peak (indication of the N-containing species in soot) increased with the addition of ammonia. This study confirmed that the addition of NH3 promotes the graphitization of soot.

An easy but quantitative assessment of soot production rate and its dependence on temperature and pressure

The challenge of soot emission persists in combustion research due to the complexities of tracking the crucial stages of growth from fuel to soot nuclei and ultimately mature particles. Studying soot formation in flames often requires a sophisticated approach, involving detailed measurements of gaseous soot precursors and soot particles using multiple complementary diagnostics. On the other end of the spectrum of studies are simpler methods that capture the sooting tendency using a single index, akin to the cetane number in compression ignition engines and the octane number in spark ignition engines. This article seeks a middle ground, aiming to quantify the soot production rate while maintaining the simplicity of single-index characterizations. The approach involves establishing counterflow diffusion flames, measuring soot volume fraction through pyrometry, and accurately computing velocity and temperature profiles using a commercial code. These data allow for the quantification of the production rate from the soot governing equation. The methodology is applied to counterflow ethylene diffusion flames to examine the temperature dependence of the soot production rate across peak temperatures varying by several hundred degrees and pressures in the 1–32 atm range. The soot production rate per unit flame area falls within the range of 10−7–10−3 g/(cm2s) range and, when normalized with respect to the carbon flux, it ranges between 10−6 and nearly 10−2. On a logarithmic scale, it linearly correlates with the peak temperature at a fixed pressure. Although this study deals only with flames of ethylene, the approach can be generalized to any fuel. The resulting database should be valuable not only for industry practitioners but also to the scientific community for the global validation of detailed soot models.

Coupled interactive effects of ammonia and hydrogen additions on ethylene diffusion flames: A detailed kinetic study

Coupled interactive effects of ammonia and hydrogen additions on ethylene diffusion flames: A detailed kinetic study

The effect of ammonia on soot formation in ethylene diffusion flames

The effect of ammonia on soot formation in ethylene diffusion flames

On the mechanisms affecting soot production in oxygen-depleted buoyant flames

The objective of this article is to apply a detailed polycyclic aromatic hydrocarbons (PAH)-based soot production model to investigate the effects of oxygen depletion on the overall soot production processes in laminar coflow ethylene diffusion flames. This task is accomplished by simulating the flames, studied experimentally by Sun et al. (Combust. Flame 211:96–111, 2020), burning under oxygen concentration in the oxidizer down to 16.8% and characterized by a constant volumetric stoichiometric air to fuel ratio to keep the residence time unchanged. This configuration allows isolating the effects of reducing oxygen on both soot formation and oxidation processes and avoiding the complex interactions between soot production and turbulence. Model predictions are in reasonable agreement with the experiments in terms of temperature, soot volume fraction, and primary particle diameter and capture quantitatively the effects of oxygen depletion on soot production. In all the flames, both the H-abstraction and acetylene addition (HACA) and PAH condensation contribute significantly to the soot mass growth, with the HACA slightly dominating the overall process. Reducing the oxygen concentration affects similarly all the formation and oxidation processes with a reduction in the range 30–40% from 21.0% to 18.9% and in the range from 60 to 70% as it is further reduced to 16.8%. Among the formation processes, the PAH condensation and surface growth by HACA have a similar sensitivity to oxygen depletion, followed by soot inception.

Effect of N2 Diluent on Soot Formation Characteristics in Ethylene Diffusion Flames

Effect of N2 Diluent on Soot Formation Characteristics in Ethylene Diffusion Flames

Effect of NH3 addition on soot morphology and nanostructure evolution in laminar ethylene diffusion flame

Ammonia, as a carbon neutral alternative fuel, has attracted wide attention. However, due to the defects in the combustion performance of pure ammonia, it is still necessary to further solve this problem in practical utilization. The purpose of this paper is to study the influence of ammonia on the morphology of soot and the evolution of nanoparticle structure in laminar flame of ethylene. In this work, the soot collected by thermophoresis probe was observed by the high resolution transmission electron microscope (HRTEM), and the image information in HRTEM images was statistically processed, and the graphitization degree of soot was measured by X-ray diffraction (XRD) spectrum of soot samples. The experimental results show that the addition of ammonia can inhibit the growth of soot nuclei and delay the formation of incipient soot, and has different effects on the evolution of soot morphology and structure in ethylene flame. It is noteworthy that the soot samples collected in the upstream part of the ammonia-doped flame show more mature core–shell structure in HRTEM images and more graphitized XRD diffraction data than those collected in pure ethylene flame. The main reason may be the chemical effect of ammonia and the thermal effect caused by the reduction of flame radiation loss, which have different effects on the nanostructure and morphology of soot at different stages of soot formation. Fringe structure model is used to describe and explain the influence of soot in flame with height before and after ammonia doped.

Experimental study on soot formation and primary particle size in oxy-combustion ethylene diffusion flames under CO2 substitution for N2

This paper reports an experimental study on the effects of O2 concentration and CO2 concentration on soot volume fraction and primary particle size of flame centre in ethylene laminar co-diffusion flame. The incandescent light was induced by a two-color band method and laser-excited by wavelength 1064 nm. Previous studies have shown that the oxygen concentration affects the soot volume fraction in the flame. However, the effects of O2 concentration on the primary particle size under CO2 atmosphere are unclear and need to be further discussed. Seven flames were optically detected, in which the oxygen concentration of the accompanying gas varied from 21% to 50% by volume. One primary flame was burned in co-flowing ethylene/air. Six ethylene flames were burned in an oxygen-rich O2/N2 or O2/CO2 atmosphere with an oxygen mole fraction from 30% to 50%. The C2H4 flow rate remained constant in all operating conditions. The results show that the SVF observed by the LII method and spectroscopy in the oxygen-enriched flame are in good agreement. Furthermore, the soot's primary particle diameter measured by the time-resolved LII method is in good agreement with the transmission electron microscope image analysis.With the increase of oxygen concentration, the flame height becomes shorter, the luminosity becomes brighter, and the soot yield increases. Compared with an N2 atmosphere with the same oxygen concentration, the soot yield in a CO2 atmosphere was significantly inhibited. In all the flames studied, the SVF along the flame axis showed a similar distribution: it first increased to the maximum value and then decreased rapidly until the flame tip. The maximum SVF on the axis appears between 0.64 and 0.78 based on the normalized height of the visible flame. In all ethylene/(O2/N2) flames, the maximum primary particle diameter and average primary particle diameter increase with oxygen content. For ethylene/(O2/CO2) flame, the maximum diameter of primary particles decreases with the increased oxygen content. The uncertainty of primary diameter is mainly caused by the thermal adaptation coefficient, the lower LII signal of smaller particles and the uncertainty of local flame temperature.

X-ray micro-CT based computation of effective diffusivity of metabolic gases in tomato fruit

The effective diffusivity is a key engineering property of fruit that affects transport of metabolic gases and, hence, ripening. It strongly depends on the microstructure of the fruit. In bulky fruit such as tomato, porosity and pore structure differ between tissues and change during maturation and ripening. Knowledge of the relationship between gas diffusivity and microstructure of tomato will aid management and control of postharvest operations. By using mathematical models of mass transport that incorporate the 3-D microscopic tissue geometry obtained from micro-computed tomography (μ-CT), the relationship between microstructural features and gas diffusivity may be computed in a direct way. In this study, a previously validated pore-scale network model (PNM) was used to simulate the effective gas diffusivity of O2, CO2 and ethylene for five types of tomato fruit tissues (i.e., outer mesocarp, inner mesocarp, septa, placenta and columella) at different maturation and ripeness stages. The effective gas diffusivity of the placenta and columella was large during the entire ripening process as these tissues contained more interconnected open intercellular spaces. The effective diffusivity of the inner mesocarp increased with increasing porosity during ripening while the microstructural changes of the outer mesocarp lagged compared to those of the inner mesocarp region, resulting in a delayed increase of the effective gas diffusivity with ripening. Regression models between the effective diffusivity of O2, CO2 and ethylene as a function of porosity, open porosity or tortuosity were established. This study provides a quantitative basis for further gas exchange modeling in intact tomato fruit to predict their ripening process.

Syntheses and Catalytic Behavior of Dendritic Macrocyclic Schiff‐Base Nickel (II) Complexes in Ethylene Oligomerization

AbstractThe functionalized dendrimers play an important role in catalytic application. A dendritic Schiff base macrocyclic compound was designed and synthesized with the 1.0 generation dendrimer polyamidoamine (1.0G PAMAM) and terephthalaldehyde for ethylene oligomerization. The role of solvent in the synthesized process of dendritic macrocyclic Schiff base ligand was studied. Surprisingly, intermolecular or intramolecular cyclization occurred and formed bicyclic Schiff base ligand (Ligand 1) and polycyclic Schiff base ligand (Ligand 2). And their corresponding nickel complexes (Catalyst 1 and Catalyst 2) were also synthesized with NiCl2(DME) as material to be used for ethylene oligomerization. The effects of the reaction parameters and the chemical structure of the ligand on the catalytic behavior were investigated with methyl‐aluminoxane (MAO) as cocatalyst, and Catalyst 1 and Catalyst 2 displayed the high catalytic activity and the high selectivity for low‐carbon olefin in ethylene oligomerization. Catalyst 2 based on Ligand 2 had a higher catalytic activity of 9.12×104 g (mol Ni h)−1 in ethylene oligomerization because of large dendritic ring in the ligand for ethylene diffusion and mass transfer. Moreover, two synthesized nickel complexes based on dendritic macrocyclic Schiff base ligand had a higher catalytic activity compared with the corresponding dendritic salicylaldehydeimine nickel (II) catalyst.