Ni-Co bimetallic catalysts on coconut shell activated carbon prepared using solid-phase method for highly efficient dry reforming of methane

Ni-Co bimetallic catalysts supported on coconut shell activated carbon are synthesized using solid-phase method and investigated for dry reforming of methane, to explore the impact of Ni:Co ratio on the catalyst activity and stability. The catalyst performances are evaluated under the temperature varying from 600 to 900 °C and gas hourly space velocity (GHSV) of 7200 mL/h·g-cat. The characterization results show that metal nanoparticles are produced on the support, and the bimetallic catalyst with an explicit Ni:Co ratio (2:1) is the most beneficial for metal particle dispersion and acquires the minimum particle size of 4.41 nm. The bimetallic catalysts with an explicit Ni:Co ratio of 1:2 and 1:1 exhibit a synergistic effect towards the conversions of CH₄ and CO₂, respectively. The experimental results reveal that the highest CH₄ and CO₂ conversions rise to 94.0% and 97.5% within 12 h at 900 °C on average, respectively, assisted with the two bimetallic catalysts. The intensity of disordered carbon and thermal stability are enhanced with the extension of reforming process, contributing to a long-term catalytic stability. Besides, no obvious carbon deposition is detected, leading to a highly catalytic stability for the bimetallic catalysts.

     

Recent advances in the application of silica nanostructures for highly improved water treatment: a review

The demand for high-quality safe and clean water supply has revolutionized water treatment technologies and become a most focused subject of environmental science. Water contamination generally marks the presence of numerous toxic and harmful substances. These contaminants such as heavy metals, organic and inorganic pollutants, oil wastes, and chemical dyes are discharged from various industrial effluents and domestic wastes. Among several water treatment technologies, the utilization of silica nanostructures has received considerable attention due to their stability, sustainability, and cost-effective properties. As such, this review outlines the latest innovative approaches for synthesis and application of silica nanostructures in water treatment, apart from exploring the gaps that limit their large-scale industrial application. In addition, future challenges for improved water remediation and water quality technologies are keenly discussed.

     

A high-resolution non-invasive approach to quantify oxygen transport across the capillary fringe and within the underlying groundwater

Oxygen transport across the capillary fringe is relevant for many biogeochemical processes. We present a non-invasive technique, based on optode technology, to measure high-resolution concentration profiles of oxygen across the unsaturated/saturated interface. By conducting a series of quasi two-dimensional flow-through laboratory experiments, we show that vertical hydrodynamic dispersion in the water-saturated part of the capillary fringe is the process limiting the mass transfer of oxygen. A number of experimental conditions were tested in order to investigate the influence of grain size and horizontal flow velocity on transverse vertical dispersion in the capillary fringe. In the same setup, analogous experiments were simultaneously carried out in the fully water-saturated zone, therefore allowing a direct comparison with oxygen transfer across the capillary fringe. The outcomes of the experiments under various conditions show that oxygen transport in the two zones of interest (i.e., the unsaturated/saturated interface and the saturated zone) is characterized by very similar transverse dispersion coefficients. An influence of the capillary fringe morphology on oxygen transport has not been observed. These results may be explained by the narrow grain size distribution used in the experiments, leading to a steep decline in water saturation at the unsaturated/saturated interface and to the absence of trapped gas in this transition zone. We also modeled flow (applying the van Genuchten and the Brooks-Corey relationships) and two-dimensional transport across the capillary fringe, obtaining simulated profiles of equivalent aqueous oxygen concentration that were in good agreement with the observations.     

Influence of surfactant concentration on foliar retention of pesticides used in forestry

Abstract

Aqueous tank mixes of permethrin, fenitrothion, Bacillus thuringiensis (B.t.), diflubenzuron (DFB), and glyphosate containing different amounts of Triton® X‐114, a nonionic surfactant, were prepared. Glyphosate formed clear solutions, permethrin and fenitrothion formed emulsions, DFB and B.t provided suspensions. Emulsion stability of permethrin and fenitrothion increased with increasing surfactant level, while the emulsion drop size decreased.

Foliage of white oak, trembling aspen, white spruce and balsam fir were dipped in tank mixes of pesticides (except B.t.) labelled with ¹⁴carbon. The amount of pesticide retained on foliage was determined by liquid scintillation counting. Foliage was also dipped in non‐radioactive B.t. tank mixes, and the protein retained was determined colorimetrically. With all tank mixes, a direct relationship was observed between the mass of liquids retained on foliage and liquid viscosity. In contrast, the amount of pesticide retained was unaffected by viscosity, but was influenced by emulsion drop size. Initially, the amount of pesticide retained on foliage increased with increasing surfactant concentration. Beyond an optimum surfactant level, the emulsion drop sizes were too small and the emulsions became too stable to allow maximum retention of pesticides on foliage. With the glyphosate solutions, however, no optimum surfactant level was indicated because foliar concentrations continued to increase with increasing surfactant levels.     

The assessment of electromigration as a new technique to study diffusion of radionuclides in clayey soils

For the performance assessment study of a geological disposal of High Level Waste (HLW) in clayey formations, migration studies are essential. For low permeability soils (clays), classical diffusion studies take a very long time. In order to reduce the experimental time, we propose an electrical field as driving force to accelerate the migration of ionic species. This paper reports the assessment of the electromigration technique as a powerful new and fast technique for migration studies. The apparent molecular diffusion coefficient can be derived by two independent methods using the migration parameters obtained from an electromigration experiment, namely the apparent dispersion coefficient and the apparent convection velocity. First, it can be calculated from the velocity of the migrating species by the Einstein relation. But, corrections are necessary for electroosmotic flow. The apparent electroosmotic mobility is experimentally determined as 2.2·10⁻⁹ m²/Vs. Second, it can be calculated from the relation between the apparent dispersion coefficient and the total apparent convection velocity. But it is necessary to know the dispersion length of the medium. The dispersion length for Boom Clay is experimentally determined as 8·10⁻⁵ m. Because of the serious reduction in time, it becomes possible to run series of experiments at different electrical fields to obtain averaged values for the apparent molecular diffusion coefficient according to the two methods. Experiments at different electrical fields have another advantage: the intercept of the linear relationship between the total apparent convection velocity and the apparent dispersion coefficient gives the apparent molecular diffusion coefficient. The apparent molecular diffusion coefficients obtained for ⁸⁵Sr, ¹³¹I and HTO are respectively 0.8·10⁻¹¹, 15·10⁻¹¹, and 24·10⁻¹¹ m²/s. These values are confirmed by pure diffusion experiments. The excellent agreement with the apparent molecular diffusion coefficients obtained by classical diffusion tests clearly demonstrates the feasibility of the electromigration technique for the determination of diffusion coefficients.     

Comparison of the droplet size spectra produced by rotary atomizers and hydraulic nozzles under simulated aerial application conditions

Abstract

A wind tunnel was used to characterize the droplet size spectra of liquid sprays from several different atomizers and nozzles used under simulated aerial application conditions. The atomizers included a D8–46 nozzle, a Through Valve Boom (TVB) nozzle, and rotary cage and drum atomizers.

The D8–46 hydraulic nozzle was evaluated, using water, at orientations of 0, 10, 20, 30, 40, 50, 60, 70, 80 and 90° relative to 145 and 180 km/h airstreams. The TVB nozzle was evaluated using water, water with isopropyl alcohol, and water with a non‐ionic surfactant at airstream velocities between 130 and 180 km/h. The rotary atomizers were evaluated at different rotation rates, flow rates of water and an insecticide, in 130 and 180 km/h airstreams.

The volumetric droplet size spectra parameters (D_vo.x) decreased as the angle of the D8–46 nozzle and the airstream velocity increased. Empirical models were developed to predict these values for different windspeed and nozzle angle conditions. The TVB nozzle produced larger droplets than the other atomizers under similar conditions, with a decrease in the D_vo.x parameter values as the airstream velocity increased.

The D_vo.x parameter values produced by the rotary atomizers increased as the liquid flow rate increased, and as the rotation rate and airstream velocity decreased, and were lower for the insecticide than for water. The slotted rotary drum atomizer gave the best control over droplet size, generally producing mono‐modal droplet size spectra where the other atomizers often produced bi‐ and multimodal spectra.     

Development and Evaluation of the PRIME Plume Rise and Building Downwash Model

ABSTRACT

A new Gaussian dispersion model, the Plume Rise Model Enhancements (PRIME), has been developed for plume rise and building downwash. PRIME considers the position of the stack relative to the building, streamline deflection near the building, and vertical wind speed shear and velocity deficit effects on plume rise. Within the wake created by a sharp-edged, rectangular building, PRIME explicitly calculates fields of turbulence intensity, wind speed, and streamline slope, which gradually decay to ambient values downwind of the building. The plume trajectory within these modified fields is estimated using a numerical plume rise model. A probability density function and an eddy diffusivity scheme are used for dispersion in the wake. A cavity module calculates the fraction of plume mass captured by and recirculated within the near wake. The captured plume is re-emitted to the far wake as a volume source and added to the uncaptured primary plume contribution to obtain the far wake concentrations.

The modeling procedures currently recommended by the U.S. Environmental Protection Agency (EPA), using SCREEN and the Industrial Source Complex model (ISC), do not include these features. PRIME also avoids the discontinuities resulting from the different downwash modules within the current models and the reported overpredictions during light-wind speed, stable conditions. PRIME is intended for use in regulatory models. It was evaluated using data from a power plant measurement program, a tracer field study for a combustion turbine, and several wind-tunnel studies. PRIME performed as well as or better than ISC/SCREEN for nearly all of the comparisons.     

The Development of a Sampling System for the Determination of Odor Emission Rates from Areal Surfaces: Part II. Mathematical Model

Abstract

An improved design for an odor emission hood was examined in the laboratory using ammonia emission from a water surface. The experimental ammonia convective mass transfer coefficients from a diluted ammonia solution were determined at velocities of 0.3 m/s to 0.8 m/s using the odor emission hood. The theoretical ammonia convective mass transfer coefficients were also predicted by boundary layer theory under laminar flow conditions. It was found that experimental data were only 10% below theoretical predictions at an air velocity of 0.3 m/s to 0.6 m/s. The maximum velocity was limited to 0.6 m/s by the geometric size, shape and aerodynamic stability of the hood. At 0.33 m/s, the smallest variation of mass transfer coefficients was measured. The odor emission rate was found to be a function of air velocity to the power 0.5 in accordance with boundary layer theory. An odor sampling system based upon the odor emission hood provides a way to quantify the potential odor emission strength in sewage treatment plants, for odor dispersion modeling and odor control.     

Simulation of the evolution of particle size distributions containing coarse particulate in the atmospheric surface layer with a simple convection-diffusion-sedimentation model

The Fugitive Dust Model (FDM) and Industrial Source Complex (ISC), widely used coarse particulate dispersion models, have been shown inaccurate due to the neglect of vertical variations in atmospheric wind speed and turbulent diffusivity (Vesovic et al., 2001), omission of the gravitational advection velocity, and an underestimation of the ground deposition velocity (Kim and Larson, 2001). A simple, transient two-dimensional convection-diffusion-sedimentation model is proposed to simulate the evolution in particle size distribution of an aerosol ‘puff’ containing coarse particulate in the atmospheric surface layer. Monin-Okhubov similarity theory, accompanied by empirical observations made by Businger et al. (1971), is adopted to characterize the surface layer wind speed and turbulent diffusivity profiles over a wide range of atmospheric conditions. A first order analysis of the crossing trajectories effect suggests simulation data presented here are not significantly affected by particle inertia. The model is validated against Suffield experimental data in which coarse particulate deposition was measured out to a distance of 800 m from the source (Walker, 1965). Good agreement is found for the decay in ground deposits with distance from the source for stable atmospheres. Deposition data was also simulated for unstable atmospheric stratification and the current model was determined to modestly underestimate the peak concentration with increasing accuracy further downwind of the release. The current model's effective deposition velocity was compared to that suggested by Kim et al. (2000) and shows improvement with respect to FDM. Lastly, the model was used to simulate the dispersion of nine lognormal aerosol puffs in the lowest 50 m of the atmospheric surface layer for four classes of atmospheric stability. The simulated mass median aerodynamic diameters (MMAD) at multiple downwind sampling locations were calculated and plotted with distance from the source. The first 50 m from the source was found to have a substantial impact on the evolution of MMAD for stable atmospheric conditions. Away from the source, it was observed that particle size distributions were truncated by removal of all particles larger than about 60 μm. A particle Peclet number was also defined to quantify the relative importance of turbulent dispersion and sedimentation on particle motion in the vertical direction.     

Modelling of atrazine transport in the presence of surfactants

Laboratory experiments were conducted to examine the effect of detergents on transport of atrazine [2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine] through loam and sandy loam soils under saturation conditions. The Convection Dispersion Equation (CDE) was used to model and quantify the effects of detergents on atrazine model parameters: the retardation factor (R), pore velocity (v) and dispersion coefficient (D). The transport parameters were estimated using moment technique and partition coefficient obtained from batch experiments and compared with best-fitted parameters, R and D, keeping pore velocity constant. Results indicated the CDE model was not successful in predicting atrazine transport in the presence of surfactants at high concentrations. In the case of anionic surfactant with Elora loam, the average predicted R and D from moment technique of 3.4 and 11.1 cm2/h, respectively were significantly different than fitted parameters (R = 39 and D = 227 cm2/h). The poor performance of CDE in the presence of surfactants results from physiochemical changes in herbicide solubility and retention to the soil matrix rather than changes in soil hydraulic properties since the predicted pore water velocities from moment technique were similar to those measured during leaching experiments. Nevertheless, BTC analysis with CDE showed that land application of anionic surfactant (sulphonic) significantly increased R and D and decrease v for both soils. Addition of sulphonic increased R of atrazine by 12 and 26 folds for loam and sandy loam soils, respectively. On the other hand non-ionic surfactants seemed to decrease R, especially in sandy loam soil, thus facilitating atrazine leaching through soil. Non-equilibrium conditions seemed to govern atrazine transport in the presence of surfactants; double peaks in breakthrough curves were observed, indicating a need for mathematical models to account for such phenomena. Atrazine dispersion and tailing seemed to be higher through Elora loam compared to Caledon sandy loam due to higher aggregation of the Elora soil.     

微气泡曝气中氧传质特性研究

气泡曝气过程中氧传质对于好氧生物处理过程具有重要意义。采用水力旋转剪切微气泡发生装置,考察了运行条件和水质特性对微气泡曝气中氧传质特性的影响。结果表明,微气泡曝气可获得较高的气含率和气泡停留时间;表面活性剂十二烷基磺酸钠(SDS)可以提高微气泡曝气的气含率和气泡停留时间。微气泡曝气中氧的总体积传质系数明显高于传统气泡曝气。总体积传质系数随着空气流量的增加而增加;氧传质效率随着空气流量的增加而减小,且对空气流量的变化更为敏感。在温度15~35℃范围内,微气泡曝气中氧的总体积传质系数随着温度的增加而增加,变化关系与传统气泡曝气基本相同,但对温度的变化更为敏感。微气泡曝气中,表面活性剂SDS会使氧的总体积传质系数略有降低,其不利影响明显小于传统气泡曝气;氧的总体积传质系数随盐度(NaC l浓度)增加而逐渐增加,并在NaC l浓度5 000 mg/L后趋于稳定。     

Experimental analysis of particle concentration heterogeneity in a ventilated scale chamber

The mixing processes of the aerosol particles from an outdoor environment in a ventilated scale chamber were experimentally studied. The particles were classified into five groups by size: 0.3–0.5 μm, 0.5–1.0 μm, 1.0–3.0 μm, 3.0–5.0 μm and 5.0–10.0 μm. The developing process for the concentration of each particle group was measured in different kinds of flow fields.The results show that the flow field configuration can effectively influence the dispersion time rate of the particles at certain positions. The increase in particle diameter can decrease the dispersion time rate. When the gas flow velocity is high, the particle dispersion time rate is independent of particle size; but when the gas flow velocity is low, particle size can significantly affect the particle dispersion time rate because the turbulent diffusion becomes important in the air and particle transport. The uniformity of the particle concentration for certain positions in steady state tends to be controlled by the inflow velocity, flow field configuration and the particle diameters.     

A model for the maximum credible hourly impact on any ground receptor from point sources with thermal plume rise

A pollutant dispersion model is developed, allowing fast evaluation of the maximum credible 1-h average concentration on any given ground-level receptor, along with the corresponding critical meteorological conditions (wind speed and stability class) for stacks with buoyant plumes in urban or rural areas. Site-specific meteorological data are not required, as the computed concentrations are maximized against all credible combinations of wind speed, stability class, and mixing height. The analysis is based on the dispersion relations of Pasquill-Gifford and Briggs for rural and urban settings, respectively, the buoyancy induced dispersion correlation of Pasquill, the wind profile exponent values suggested by Irwin, the buoyant plume rise relations of Briggs, as well as the Benkley and Schulman's model for the minimum mixing heights. The model is particularly suited for air pollution management studies, as it allows fast screening of the maximum impact on any selected receptor and evaluation of the ways to have this impact reduced. It is also suited for regulatory purposes, as it can be used to define the minimum stack size requirements for a given source as a function of the exit gas volume and temperature, the pollutant emission rates and their hourly concentration standards, as well as the source location relative to sensitive receptors.     

developing a practical dispersion model for an air quality region

A series of computer models have been developed to predict air quality in the New York/New Jersey/Connecticut Air Quality Region. Efforts have been directed at models which have a shorter time scale than climatological models, and which are capable of providing better recommendations for effective abatement and planning, but use input data presently available.

The basic dispersion model for these investigations is a steady-state,nondivergent Gaussian-type model. A modified inventory of SO₂ sources,based on published data for the New York/New Jersey/Connecticut Air Quality Region, was prepared for use with the model. The basic model has been subjected to various internal sensitivity analyses, in which was isolated the variation produced in the pollutant concentration by a given change in each of the factors that contribute, e.g., wind speed, wind direction,mixing depth, stability conditions, source strengths, and grid size for the area sources.

To date, validation tests of the model have been made against the July and August 1969 data for the ten telemetering stations of the New York City Aerometric Network. Hourly as well as averaged concentrations were considered. Various sets of meteorological data from the network stations and the three area airports, were compared and tested. Additional tests, particularly for the winter season, are needed to substantiate the preliminary conclusions suggested by the results to date.

Considerable insight into the relative importance of model components has been acquired from the sensitivity studies. Furthermore the validation results lend support to the belief that a reasonably simple, practical dispersion model can be developed for the region.     

Plume rise in a shear layer with neutral stability

Several solutions have been published to predict the rise of buoyant plumes in a shear layer with a power-law velocity profile. Each of these solutions is either a special case or is based on oversimplifying assumptions. In this paper, solutions to the plume-rise equations are given for buoyant and nonbuoyant plumes with initial vertical momentum. Solutions are given for both point sources and sources with a finite initial size under neutral stability. For a constant wind speed, these solutions simplify to the conventional plume-rise equations.     

The effect of surfactants on oxygen mass-transfer through the air-water interface

The aim of the current study was to investigate the oxygen transfer rate through the water-air interface in the presence of different concentrations of various surfactants. The surfactants used in the current study were methanol, ethanol, 1-propanol and 1-butanol. The measurements were performed with an apparatus based on the electrochemical oxygen sensor. Theresults obtained showed that the impediment to oxygen mass-transfer through the water-air interface depends on the molecular structure and concentration of the surfactant used. A simple mathematical model was proposed, which allowed us to calculate the characteristic constants of surfactantsK’ and δk starting from the experimental results.K’ is the reciprocal of the equilibrium constant of adsorption process and δk characterizes the influence of the surfactant to oxygen mass-transfer through the air-water interface.     

Water flume study of the enhancement of buoyant rise in pairs of merging plumes

When multiple stacks are grouped or ganged together at a site, the effluent plumes are often observed to merge downwind, forming a single buoyant plume whose rate of rise is enhanced relative to the rise of the plumes individually. The magnitude of this rise enhancement depends on many factors, and the few available models for rise enhancement do not always agree with one another. In the present study the rise behaviour of pairs of merging, buoyant plumes was studied by physical modelling in a water flume at 1:500 scale. The experiments were conducted at several stack separation distances and various exit velocity ratios for stack pairs aligned with, or perpendicular to, the ambient flow. Limited experiments were also done with the stacks aligned at other angles to the flow. The stack releases were made buoyant by heating the source water, and the resulting plumes were measured with an array of sensitive temperature probes. From these measurements it was possible to determine the plume structure and rise rates. For small stack separations when the stacks are aligned with the ambient flow, the experimental results show that the enhanced rise is close to, and sometimes above, the maximum theoretical rise enhancement factor of 2^1/3. For the perpendicular orientation there is little or no rise enhancement. The rise enhancement for other stack orientations is somewhere between these two extremes. A plausible physical explanation for the observed behaviour is given, based on initial momentum shielding and line vortex dynamics in the merging plumes.     

An efficient Lagrangian stochastic model of vertical dispersion in the convective boundary layer

We consider the one-dimensional case of vertical dispersion in the convective boundary layer (CBL) assuming that the turbulence field is stationary and horizontally homogeneous. The dispersion process is simulated by following Lagrangian trajectories of many independent tracer particles in the turbulent flow field, leading to a prediction of the mean concentration. The particle acceleration is determined using a stochastic differential equation, assuming that the joint evolution of the particle velocity and position is a Markov process. The equation consists of a deterministic term and a random term. While the formulation is standard, attention has been focused in recent years on various ways of calculating the deterministic term using the well-mixed condition incorporating the Fokker–Planck equation. Here we propose a simple parameterisation for the deterministic acceleration term by approximating it as a quadratic function of velocity. Such a function is shown to represent well the acceleration under moderate velocity skewness conditions observed in the CBL. The coefficients in the quadratic form are determined in terms of given turbulence statistics by directly integrating the Fokker–Planck equation. An advantage of this approach is that, unlike in existing Lagrangian stochastic models for the CBL, the use of the turbulence statistics up to the fourth order can be made without assuming any predefined form for the probability distribution function (PDF) of the velocity. The main strength of the model, however, lies in its simplicity and computational efficiency. The dispersion results obtained from the new model are compared with existing laboratory data as well as with those obtained from a more complex Lagrangian model in which the deterministic acceleration term is based on a bi-Gaussian velocity PDF. The comparison shows that the new model performs well.     

The Mass Distribution of Large Atmospheric Particles

This paper describes the results of a study to determine the total mass and the mass distribution of atmospheric aerosols, especially that mass associated with particles greater than 10 μm diameter. This study also determined what fraction of the total aerosol mass a standard high-volume air sampler collects and what fraction and size interval settle out on a dust fall plate. A special aerosol sampling system was designed for this study to obtain representative samples of large airborne particles. A suburban sampling site was selected because no local point sources of aerosols existed nearby. Samples were collected under various conditions of wind velocity and direction to obtain measurements on different types of aerosols.

Study measurements show that atmospheric particulate matter has a bimodal mass distribution. Mass associated with large particles mainly ranged from 5 to 100 μm in size, while mass associated with small particles ranged from an estimated 0.03 to 5 μm in size. Combined, these two distributions produced a bimodal mass distribution with a minimum around 5 μm diameter. The high-volume air sampler was found to collect most of the total aerosol mass, not just that fraction normally considered suspended particulate. Dust fall plates did not provide a good or very useful measure of total aerosol mass. The two fundamental processes of aerosol formation, condensation and dispersion appear to account for the formation of a bimodal mass distribution in both natural and anthropogenic aerosols. Particle size distribution measurements frequently are in error because representative samples of large airborne particles are not obtained. Considering this descrepancy, air pollution regulations should specify or be based upon an upper particle size limit.     

Enhanced sludge solubilization by microbubble ozonation

A microbubble ozonation process for enhancing sludge solubilization was proposed and its performance was evaluated in comparison to a conventional ozone bubble contactor. Microbubbles are defined as bubbles with diameters less than several tens of micrometers. Previous studies have demonstrated that microbubbles could accelerate the formation of hydroxyl radicals and hence improve the ozonation of dyestuff wastewater. The results of this study showed that microbubble ozonation was effective in increasing ozone utilization and improving sludge solubilization. For a contact time of 80 min, an ozone utilization efficiency of more than 99% was obtained using the microbubble system, while it gradually decreased from 94% to 72% for the bubble contactor. The rate of microbial inactivation was obviously faster in the microbubble system. At an ozone dose of 0.02 g O₃ g⁻¹ TSS, about 80% of microorganisms were inactivated in the microbubble system, compared with about 50% inactivation for the bubble contactor. Compared to the bubble contactor, more than two times of COD and total nitrogen, and eight times of total phosphorus content were released from the sludge into the supernatant by using the microbubble system at the same ozone dosage. The application of microbubble technology in ozonation processes may provide an effective and low cost approach for sludge reduction.