Liquid phase heterogeneous photocatalytic ozonation of phenol in liquid–solid fluidized bed: Simplified kinetic modeling

The isotherms of original AC (activated carbon) and photocatalysts (TiO₂-AC) calcined at 500 °C for phenol were measured. The results showed a reversible adsorption of phenol onto both kinds of particles at 25 °C, and could be fitted well to the Freundlich adsorption equation for the dilute solution. Five oxidation processes, namely O₃, O₃/UV, O₃/UV/AC, O₂/UV/TiO₂ and O₃/UV/TiO₂, for phenol degradation in fluidized bed were evaluated and compared, and the photocatalytic ozonation was found to give the highest phenol conversion because of the combined actions of homogenous ozonation in the liquid phase, heterogeneous ozonation on the surface of the catalyst support, i.e. activated carbon, and heterogeneous photocatalytic oxidation on the TiO₂ catalyst surface. With the simplified kinetic model, photolytic ozonation was confirmed to predominantly take place on the particle surface in comparison with the heterogeneous and homogeneous photolytic ozonation. Additionally, the heterogeneous photocatalytic oxidation constant was found to be enhanced by 3.73 times in photocatlaytic ozonation process with ozone as the scavenger compared to the photocatalytic oxidation process with oxygen as the scavenger.     

Nitrogen release characteristics of polyethylene-coated controlled-release fertilizers and their dependence on membrane pore structure

In this study, controlled-release fertilizers (CRFs) with five different nitrogen release periods were prepared by coating large urea particles with polyethylene (PE) membranes under various experimental conditions. The preliminary and differential solubility rates, release periods, and membrane pore sizes of the obtained CRFs were measured using water immersion, scanning electron microscopy, and mercury porosimetry. For all CRF samples, the median pore diameters of the membranes were equal to 4.5–5.3 nm and pores with sizes smaller than 10 nm accounted for 86–96% of the total pore surface area. The obtained pore diameter distributions differed for the five studied types of CRF, having release periods of 1, 2, 4, 6, and 8 months. Thus, for the CRFs with a 1-month release period, the maximum pore diameter reached a magnitude of 4000 nm, while this value did not exceed 30 nm for the CRFs with a release period of 8 months. Hence, we have established a relationship between the release period of CRFs and their effective maximum pore sizes.     

Synthesis of mesoporous γ-AlOOH@Fe3O4 magnetic nanomicrospheres

Mesoporous γ-AlOOH@Fe₃O₄ magnetic nanomicrospheres were synthesized using superparamagnetic Fe₃O₄ nanoparticles as the core and aluminum isopropoxide (AIP) as the aluminum source. The obtained magnetic nanomicrospheres were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), N₂ adsorption–desorption and vibrating sample magnetometry (VSM). The effects of preparation parameters such as hydrolysis time of AIP, concentration of AIP and coating layer number on microspheres were investigated. The results indicated that the mesoporous γ-AlOOH@Fe₃O₄ magnetic nanomicrospheres consisted of a mesoporous γ-AlOOH shell and a Fe₃O₄ magnetic core. The diameter of γ-AlOOH@Fe₃O₄ nanomicrospheres was about 200 nm, the thickness of mesoporous γ-AlOOH shell was about 5 nm and the average pore size was 3.8 nm. The thickness of the mesoporous γ-AlOOH shell could be controlled via layer-by-layer coating times. The formation mechanism of the mesoporous γ-AlOOH shell involved a “chemisorption–hydrolysis” process.     

Green synthesis and enhanced photocatalytic activity of Ce-doped TiO2 nanoparticles supported on porous glass

A facile and green method to prepare Ce-doped TiO₂ nanoparticles supported on porous glass beads is reported. An ion exchange process and subsequent calcination yielded Ce-doped TiO₂ nanoparticles with a mean size of 4.8 ± 0.3 nm. The nanoparticles were dispersed on the surface of porous glass beads. The addition of Ce enhanced the visible light absorption of the TiO₂ nanoparticles in the 400–500 nm spectral window. The band gap of the as-prepared catalyst was 2.80 eV. The Ce-doped TiO₂ nanoparticles immobilized on porous glass beads exhibited excellent photocatalytic activity for the visible-light-degradation of methyl orange (MO) and rhodamine B (RhB); with rate constants of 0.095 and 0.230 min⁻¹; respectively. The effects of Ce dosage; reaction duration; and initial solution pH on the conversion of MO and RhB dyes were investigated. The green synthesis and favorable photocatalytic activity makes the Ce-doped TiO₂ nanoparticles immobilized on porous glass an attractive alternative for the efficient degradation of organic pollutants.     

Immobilization of Ti02 nanoparticles on activated carbon fiber and its photodegradation performance for organic pollutants

The immobilization of titanium dioxide （TiO2） on activated carbon fiber （ACF）, （TiO2/ACF）, was accomplished by sol-gel-adsorption method followed by calcination at temperatures varying from 300 to 600℃ in an argon atmosphere. The material properties were determined by scanning electron microscope （SEM）, X-ray diffraction （XRD） and nitrogen adsorption. The photodegradation behavior of TiO2 /ACF was investigated in aqueous solutions using phenol and methyl orange （MO） as target pollutants. The effects of calcination temperature, photocatalyst dosage, initial solution pH and radiation time on the degradation of organic pollutants were studied. It was found that organic pollutants could be removed rapidly from water by the TiO2/ACF photocatalyst and the sample calcined at 500℃ exhibited the highest removal efficiency. Kinetics analysis showed that the photocatalytic degradation reaction can be described by a first-order rate equation. In addition, the possibility of cyclic usage of the photocatalyst was also confirmed. Moreover, TiO2 is tightly bound to ACF and can be easily handled and recovered from water. It can therefore be potentially applied for the treatment of water contaminated by organic pollutants.     

Fabrication of nano-sized Ca(OH)2 with excellent adsorption ability for N2O4

Uniform nano-sized calcium hydroxide (Ca(OH)₂) monocrystal powder was synthesized from calcium oxide in a surfactant solution via a digestion method by decreasing the surface tension of the reaction system to control the growth of crystalline Ca(OH)₂. The Ca(OH)₂ monocrystal powder samples were characterized by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), and Fourier transform-infrared spectroscopy (FT-IR). The NO_x adsorption ability of the samples was evaluated, and the influence of various types and concentrations of surfactants on powder agglomeration and then the specific surface area in the precipitation process were studied. The specific surface area of the samples was found as high as 58 m²/g and 92 m²/g and the particle size, 300–400 nm and 200–300 nm in the presence of 10 wt% PEG600 and 0.086 mL/L SDS at a reaction time of 5 h, respectively. The product has an exceptionally strong adsorption ability for NO_x, which makes it a highly promising adsorbent for emission control and air purification.     

Energy loss at bends in the pneumatic conveying of fly ash

An accurate estimation of the total pressure drop of a pipeline is important to the reliable design of a pneumatic conveying system. The present paper presents results from an investigation into the modelling of the pressure drop at a bend in the pneumatic conveying of fly ash. Seven existing bend models were used (in conjunction with solids friction models for horizontal and vertical straight pipes, and initial acceleration losses) to predict the total pipeline pressure drop in conveying fly ash (median particle diameter: 30 μm; particle density: 2300 kg/m³; loose-poured bulk density: 700 kg/m³) in three test rigs (pipelines with dimensions of 69 mm inner diameter (I.D.) × 168 m length; 105 mm I.D. × 168 m length; 69 mm I.D. × 554 m length). A comparison of the pneumatic conveying characteristics (PCC) predicted using the seven bend models and experimental results shows that the predicted total pipeline PCC and trends depend on the choice of bend model. While some models predict trends that agree with the experimental results, other models predicted greater bend pressure drops for the dense phase of fly ash than for the dilute phase. Models of Pan, R. (1992). Improving scale-up procedures for the design of pneumatic conveying systems. Doctoral dissertation, University of Wollongong, Australia, Pan, R., & Wypych, P.W. (1998). Dilute and dense phase pneumatic conveying of fly ash. In Proceedings of the sixth International Conference on Bulk Materials Storage and Transportation (pp. 183–189), Wollongong, NSW, Australia and Chambers, A.J., & Marcus, R.D. (1986). Pneumatic conveying calculations. In Proceedings of the second International Conference on Bulk Materials Storage and Transportation (pp. 49–52), Wollongong, Australia reliably predicted the bend losses for systems conveying fly ash over a large range of air flows.     

Particle number size distribution and new particle formation （NPF） in Lanzhou,Western China

Particle number size distribution from 10 to 10,000 nm was measured by a wide-range particle spectrometer (WPS-1000XP) at a downwind site north of downtown Lanzhou, western China, from 25 June to 19 July 2006. We first report the pollution level, diurnal variation of particle concentration in different size ranges and then introduce the characteristics of the particle formation processes, to show that the number concentration of ultrafine particles was lower than the values measured in other urban or suburban areas in previous studies. However, the fraction of ultrafine particles in total aerosol number concentration was found to be much higher. Furthermore, sharp increase of ultrafine particle concentration was frequently observed at noon. An examination of the diurnal pattern suggests that the burst of the ultrafine particles was mainly due to nucleation process. During the 25-day observation, new particle formation (NPF) from homogeneous nucleation was observed during 33% of the study period. The average growth rate of the newly formed particles was 4.4 nm/h, varying from 1.3 to 16.9 nm/h. The needed concentration of condensable vapor was 6.1 × 10⁷ cm^?3, and its source rate was 1.1 × 10⁶ cm^?3 s^?1. Further calculation on the source rate of sulphuric acid vapor indicated that the average participation of sulphuric acid to particle growth rate was 68.3%.     

Pore-structure-mediated hierarchical SAPO-34: Facile synthesis,tunable nanostructure,and catalysis applications for the conversion of dimethyl ether into olefins

Hierarchical cross-like SAPO-34 catalysts with different pore size distributions were obtained via hydrothermal synthesis with polyethylene glycol (PEG) as the mesopore-generating agent. The hierarchical SAPO-34 molecular sieves were characterized using X-ray diffraction, scanning electron microscopy, N₂ adsorption–desorption, thermogravimetric analysis, and temperature-programmed NH₃ desorption. The cross-like SAPO-34 catalysts exhibited enriched multi-porosity, and the sizes of their mesopores ranged from 10 to 50 nm. Both the mesoporous structures and morphologies of the hierarchical SAPO-34 could be further tuned through adjustments of the amount of PEG used. The as-obtained SAPO-34 showed dramatic catalytic performance in the conversion of dimethyl ether into olefins. A maximum selectivity of olefins of 96% was achieved, which was attributed to the rapid transport of the reactants and products in zeolitic micropores through mesopores.     

Optical characterization of nano-sized organic carbon particles emitted from a small gasoline engine

The nano-sized organic carbon (NOC) particles emitted from a small gasoline engine were characterized using various ex situ optical techniques to assess their hazardous impact. The exhaust gas was sampled iso-kinetically by a quartz probe and passed through de-ionized water to gather the hydrophilic carbonaceous particulates as hydrosol. The hydrodynamic diameter of the particles ranged between 1.7 and 3.6 nm at no load, with a mean diameter of 2.4 nm. The particle size in the engine exhaust was found to increase at higher loads, which is attributed to coagulation of the particles. The chemical structure of the particles was analyzed using UV–vis and infra-red spectroscopy. Both the band gap energy and oscillator strength data evaluated from the UV–vis absorbance showed that the NOC particles contained polyaromatic hydrocarbon structures with three to five aromatic rings. Infra-red spectroscopy analysis further confirmed the presence of aliphatic and carbonyl functionalities in the aromatic structures of the particles. The fine size of the particles, their high number concentration for the type of the engine under study and their structural features, make the particles extremely hazardous for environment and health.     

Dry modification of electrode materials by roller vibration milling at room temperature

For the first time dry roller vibration milling at room temperature was used to prepare active carbon （AC） nano-particles and to modify MnO2 powder as electrode materials. In 30 min AC was milled to a mean particle size of 30-50 nm with increased crystallinity and higher specific surface area, predominantly mesoporous and with improved pore diameter distribution. Then, AC nano-particles were incorporated with MnO2 or bismuth-doped MnO2 nano-particles synthesized by sol-gel methods to prepare nano-composite electrode materials for studying their electrochemical performance. The AC nano-particles combined with 10 wt.% bismuth-doped MnO2 nano-particles were found to possess excellent electrochemical property with specific capacitance up to 308 F/g and without obvious attenuation with increasing current. Our method seems to ooen a new way to imorove AC based electrode materials used for clean energy such as suner capacitors.     

On air-chemistry reduction for hypersonic external flow applications

In external hypersonic flows, viscous and compressibility effects generate very high temperatures leading to significant chemical reactions among air constituents. Therefore, hypersonic flow computations require coupled calculations of flow and chemistry. Accurate and efficient computations of air-chemistry kinetics are of much importance for many practical applications but calculations accounting for detailed chemical kinetics can be prohibitively expensive. In this paper, we investigate the possibility of applying chemical kinetics reduction schemes for hypersonic air-chemistry. We consider two chemical kinetics sets appropriate for three different temperature ranges: 2500 K to 4500 K; 4500 K to 9000 K; and above 9000 K. By demonstrating the existence of the so-called the slow manifold in each of the chemistry sets, we show that judicious chemical kinetics reduction leading to significant computational savings is possible without much loss in accuracy.     

Influences of ions and temperature on performance of carbon nano-particulates in supercapacitors with neutral aqueous electrolytes

A commercial product of carbon nano-particles, Cabot MONACH 1300 pigment black (CMPB), was studied for basic structural information and electrochemical performance in neutral aqueous electrolytes, aiming at applications in supercapacitors. As confirmed by SEM and HRTEM, the CMPB had a hierarchical structure, containing basic 10 nm nano-spheres which combined into ca. 50 nm agglomerates which further aggregated into larger particles of micrometres. The capacitance of this commercial material was found to increase with decreasing the size of hydrous cation (Li⁺ → Na⁺ → K⁺), instead of the cation crystal radius (K⁺ → Na⁺ → Li⁺) when coupled with the same anion (Cl⁻). In electrolytes with the same cation concentration (K⁺), changing the anion from the larger dianion (SO₄²⁻) to the smaller monoanion (Cl⁻) also increased the capacitance at high potential scan rates (>50 mV/s). Increasing electrolyte concentration produced expected effect, including raising the electrode capacitance, but lowering the equivalent series resistance (ESR), charge transfer resistance (CTR), and the diffusion resistance. At higher temperatures, the CMPB exhibited slightly higher capacitance, which does not agree with the Gouy–Chapman theory on electric double layer (EDL). A hypothesis is proposed to account for the capacitance increase with temperature as a result of the CMPB opening up some micro-pores for more ions to access in response to the temperature increase.     

Periodic group crack problems in an infinite plate

This paper investigates periodic group crack problems in an infinite plate. The periodic group crack is composed of infinite groups with numbering from j = −∞, …, −2, −1, 0, 1, 2, …, to j = ∞, and the groups are placed periodically. The same loading condition and the same geometry are assumed for cracks in all groups. A singular integral equation is used to solve the problems. The singular integral equation is formulated on cracks of the 0th group (or the central group) with the collection of influences from the infinite groups. The influences of many neighboring groups to the central group are evaluated exactly. Meantime, the influences of many remote groups to the central group can be summed up into one term approximately. The stress intensity factors at crack tips can be evaluated from the solution of the singular integral equation. It is found from some sample problems that the obtained results are very accurate. Finally, several numerical examples are presented and interaction among the group cracks is addressed.     

Large-scale synthesis of hierarchical MnO2 for benzene catalytic oxidation

Hierarchical sea-urchin-shaped manganese oxide microspheres were synthesized via a facile method based on the reaction between KMnO₄ and MnSO₄ in HNO₃ solution at 50 °C. The average diameter of the microspheres is ∼850 nm. The microspheres consist of a core of diameter of ∼800 nm and nanorods of width ∼50 nm. The nanorods exist at the edge of the core. The Brunauer–Emmett–Teller surface area of the sea-urchin-shaped microspheres is 259.4 m²/g. A possible formation mechanism of the hierarchical sea-urchin-shaped microspheres is proposed. The temperature for 90% conversion of benzene (T_90%) on the hierarchical urchin-shaped MnO₂ microspheres is about 218 °C.     

Diagnosing laser-driven,shock-heated foam target with Al absorption spectroscopy on OMEGA EP

Results on diagnoses of laser-driven, shock-heated foam plasma with time-resolved Al 1s-2p absorption spectroscopy are reported. Experiments were carried out to produce a platform for the study of relativistic electron transport. In cone-guided Fast Ignition (FI), relativistic electrons generated by a high-intensity, short-pulse igniter beam must be transported through a cone tip to an imploded core. Transport of the energetic electrons could be significantly affected by the temperature-dependent resistivity of background plasmas. The experiment was conducted using four UV beams of the OMEGA EP laser at the Laboratory For Laser Energetics. One UV beam (1.2 kJ, 3.5 ns square) was used to launch a shock wave into a foam package target, consisting of 200 mg/cm³ CH foam with aluminum dopant and a solid plastic container surrounding the foam layer. The other three UV beams with the total energy of 3.2 kJ in 2.5 ns pulse duration were tightly focused onto a Sm dot target to produce a point X-ray source in the energy range of 1.4–1.6 keV. The quasi-continuous X ray signal was transmitted through the shock-heated Al-doped, foam layer and recorded with an X-ray streak camera. The measured 1s-2p Al absorption features were analyzed using an atomic physics code FLYCHK. Electron temperature of 40 eV inferred from the spectral analysis is consistent with 2-D DRACO Radiation-hydrodynamic simulations.     

One-dimensional titania nanotubes annealed at various temperatures for the photocatalytic degradation of low concentration gaseous pollutants

In this study, one-dimensional titania nanotubes (TNTs) were synthesized using a combined process of chemical and hydrothermal treatments, and their activities for the photocatalytic reactions of selected gaseous pollutants at sub-ppm levels were determined. Additionally, the properties of the TNTs were examined using selected spectroscopic methods. The annealed TNTs showed higher photocatalytic activities for the four target compounds than did the unannealed TNTs. For all the target compounds except benzene, the effect of the annealing temperature on the degradation efficiency was difficult to determine because all degradation efficiencies were very high. However, for benzene, which decomposed with a low efficiency, the degradation activities of the TNTs increased as the treatment temperature was increased from 250 to 300 °C, while they decreased slightly when the temperature was increased from 300 to 400 °C. These findings confirm the presence of an optimal annealing temperature for the synthesis of TNTs. Moreover, the average degradation extents for benzene, toluene, ethylbenzene, and o-xylene decreased from 92%, 96%, 99%, and 98% to 77%, 86%, 92%, and 94%, respectively, as the airstream flow rate increased within the range of 1–4 L/min. The average degradation extents decreased from 12%, 75%, 87%, and 88% to 3%, 29%, 46%, and 51%, respectively, as the input concentration increased from 0.4 to 1.9 ppm. Overall, these findings suggest that one-dimensional TNTs can be effectively utilized for the degradation of gaseous pollutants under optimal operational conditions.     

A solids mixing rate correlation for small scale fluidized beds

A new first degree solids mixing rate is proposed to evaluate the mixing of solids in small scale fluidized beds. Particle mixing experiments were carried out in a 2D fluidized bed with a cross-section of 0.02 m × 0.2 m and a height of 1 m. White and black particles with average diameters of 850 and 450 μm were used in our experiments. Image processing was used to measure the concentration of the tracers at different times. The effects of four representative operating parameters (superficial gas velocity, ratio of tracer particles to bed particles, tracer particle position, and particle size) on mixing are discussed with reference to the mixing index. We found that the Lacey index depends on the concentration of the tracers. The position of the tracers affects the initial mixing rate but not the final degree of mixing. However, the new mixing rate equation does not depend on the initial configuration of the particles because this situation is considered to be the initial condition. Using the data obtained in this work and that found in literature, an empirical correlation is proposed to evaluate the mixing rate constant as a function of dimensionless numbers (Archimedes, Reynolds, and Froude) in small scale fluidized beds. This correlation allows for an estimation of the mixing rate under different operating conditions and for the detection of the end point and/or the time of mixing.     

Removal of inhalable particles from coal and refuse combustion by agglomeration with solid nuclei

Airborne inhalable particles are a potent environmental pollutant. Formed via industrial processes, separation of these particles is difficult using conventional clean up techniques. In this work, solid nuclei particles of different chemical compositions were introduced into an agglomeration chamber with simulated flue gases to investigate their ability to remove these particles. Organic nuclei were able to capture more inhalable particles from coal-derived fly ash than inorganic nuclei, though these proved more effective for the agglomeration of inhalable particles in refuse-derived fly ash. Increasing the diameter of the solid nuclei benefitted the agglomeration process for both types of ash. Varying the local humidity changed adhesion between the particles and encouraged them to aggregate. Increasing the relative humidity consistently increased particle agglomeration for the refuse-derived ash. For coal-derived fly ash, the removal efficiency increased initially with relative humidity but then further increases in humidity had no impact on the relatively high efficiencies. After agglomeration in an atmosphere of 62% relative humidity, the mean mass diameter of inhalable particles in the coal-derived fly ash increased from 3.3 to 9.2 μm. For refuse-derived fly ash, agglomeration caused the percentage of particles that were less than 2 μm to decrease from 40% to 15%. After treatment at a relative humidity of 61%, the mean size of inhalable particles exceeded 10 μm.     

Capuli cherry-mediated green synthesis of silver nanoparticles under white solar and blue LED light

In this article, the Capuli (Prunus serotina Ehrh. var. Capuli) cherry extract was used for the synthesis of silver nanoparticles (AgNPs) in the presence of white/visible solar and blue light-emitting diode (LED) light. For the characterization of the extract and the AgNPs, Fourier transform infrared spectroscopy and ultraviolet–visible spectroscopy were employed, along with hydrodynamic particle size analysis, transmission electron microscopy and X-ray diffraction. The Ag nanospheres obtained using white light were 40–100 nm in diameter and exhibited an absorption peak at λ_max = 445 nm, whereas those obtained using blue LED light were 20–80 nm in diameter with an absorption peak at λ_max = 425 nm. Thermal analysis revealed that the content of biomolecules surrounding the AgNPs was about 55–65%, and it was also found that blue LED light AgNPs (56.28%, 0.05 mM) had a higher antioxidant efficacy than the white solar light AgNPs (33.42%, 0.05 mM) against 1,1-diphenyl-2-picrylhydrazyl. The results indicate that obtaining AgNPs using a blue LED light may prove to be a simple, cost-effective and easily reproducible method for creating future nanopharmaceuticals.