Transport and deposition of CeO2 nanoparticles in water-saturated porous media

Ceria nanoparticles are used for fuel cell, metal polishing and automobile exhaust catalyst; however, little is known about the impact of their release to the environment. The stability, transport and deposition of engineered CeO₂ nanoparticles through water-saturated column packed with sand were studied by monitoring effluent CeO₂ concentration. The influence of solution chemistry such as ionic strength (1-10 mM) and pH (3-9) on the mobility and deposition of CeO₂ nanoparticles was investigated by using a three-phase (deposition-rinse-reentrainment) procedure in packed bed columns. The results show that water chemistry governs the transport and deposition of CeO₂ nanoparticles. Transport is significantly hindered at acidic conditions (pH 3) and high ionic strengths (10 mM and above), and the deposited CeO₂ particles may not be re-entrained by increasing the pH or lowering the ionic strength of water. At neutral and alkaline conditions (pH6 and 9), and lower ionic strengths (below 10 mM), partial breakthrough of CeO₂ nanoparticles was observed and particles can be partially detached and re-entrained from porous media by changing the solution chemistry. A mathematical model was developed based on advection-dispersion-adsorption equations and it successfully predicts the transport, deposition and re-entrainment of CeO₂ nanoparticles through a packed bed. There is strong agreement between the deposition rate coefficients calculated from experimental data and predicted by the model. The successful prediction for attachment and detachment of nanoparticles during the deposition and re-entrainment phases is unique addition in this study. This work can be applied to access the risk of CeO₂ nanoparticles transport in contaminated ground water.     

Vapor phase oxidation of dimethyl sulfide with ozone over V2O5/TiO2 catalyst

The removal of volatile and odorous emissions from pulp and paper industrial processes usually generates secondary pollution which is treated further by scrubbing, adsorption, and catalytic incineration. Studies using a flow reactor packed with 10% vanadia/titania (V₂O₅/TiO₂) catalyst showed complete conversion of dimethyl sulfide (DMS) in the presence of ozone. The molar yields of partial oxidation products were only 10–20%. Small amounts of partial oxidation products, such as and dimethyl sulfone (DMSO₂), dimethyl disulfide (DMDS), and dimethyl sulfoxide (DMSO), were also formed. The results of the oxidation of DMS using ozone only, ozone plus catalyst, and oxygen plus catalyst suggest that the combined use of O₃ with catalyst is essential for the complete destruction of DMS to CO₂ and SO₂. A Box-Behnken design was used to determine the factors that have a significant effect on the conversion and selectivity of the products. It was concluded that product selectivity is strongly influenced by temperature, gas hourly space velocity (GHSV), and ozone concentration. The catalysts were characterized using XRD, surface area measurements, and SEM techniques. Time-on-stream studies carried out in a 500 ppmv gas stream held at 150 °C for 6 h, using 2 g of the catalyst, an ozone-to-DMS molar ratio of 0.9, and a GHSV of 37,000 h⁻¹, yielded 99.9% conversion of DMS. A plausible reaction mechanism has been proposed for the oxidation of DMS based on reaction product distribution and possible intermediates formed.     

Transport of nanoparticles with dispersant through biofilm coated drinking water sand filters

This article characterizes, experimentally and theoretically, the transport and retention of engineered nanoparticles (NP) through sand filters at drinking water treatment plants (DWTPs) under realistic conditions. The transport of four commonly used NPs (ZnO, CeO_2, TiO_2, and Ag, with bare surfaces and coating agents) through filter beds filled with sands from either acid washed and calcined, freshly acquired filter media, and used filter media from active filter media, were investigated. The study was conducted using water obtained upstream of the sand filter at DWTP. The results have shown that capping agents have a determinant importance in the colloidal stability and transport of NPs through the different filter media. The presence of the biofilm in used filter media increased adsorption of NPs but its effects in retaining capped NPs was less significant. The data was used to build a mathematical model based on the advection-dispersion equation. The model was used to simulate the performance of a scale-up sand filter and the effects on filtration cycle of traditional sand filtration system used in DWTPs.     

Comparison of Liquid and Gas-Phase Photooxidation of MTBE: Synthetic and Field Samples

The feasibility of photooxidation treatment of methyl tert-butyl ether (MTBE) in water was investigated using two systems: (1) a slurry falling film photoreactor and (2) an integrated air stripping with gas phase photooxidation system. Methyl tert-butyl ether-contaminated synthetic water and field samples from contaminated sites were used for these studies. Using a TiO2 slurry (0.1 g/L; Degussa P25) flowing down at a rate of up to 0.26 L/min over the inner surface of a glass tube surrounding a 1-kW medium pressure mercury lamp, more than 99% of MTBE in the synthetic samples, initially at 1 mg/L, was degraded within 90 min. The major degradation products from MTBE were tert-butyl alcohol, tert-butyl formate, and small amounts of acetone. However, the degradation of MTBE and its byproducts in contaminated groundwater samples was hindered significantly by dissolved metals such as Fe2+, chloride ions, and aromatic organic species. Integrating air stripping with gas-phase photocatalysis is an an effective alternative that would not be affected by the water chemistry. The reaction rates for MTBE degradation in the gas phase are orders of magnitude faster than in aqueous solution.     

Methanol oxidation using ozone on titania-supported vanadia catalyst

Ozone-enhanced catalytic oxidation of methanol has been conducted at mild temperatures of 100-250 degrees C using a V2O5/ TiO2 catalyst prepared by the sol-gel method. The catalyst was characterized using XRD, surface area measurements, and temperature-programmed desorption of methanol. The oxidation of methanol with ozone in the absence of a catalyst gave about 30% conversion at 100 degrees C. Methanol oxidation over a V2O5/TiO2 catalyst at 100 degrees C gave very little conversion with oxygen, whereas the conversion increased to 80% with ozone. Methanol, having an inlet stream concentration of 15 000 ppmv, can be completely oxidized to CO(x) with an ozone-to-methanol ratio of 1.2, a temperature of 150 degrees C, and a gas hourly space velocity (GHSV) of 60 000 h(-1). The apparent activation energy with ozone was calculated to be ca. 40 kJ/mol, which is much lower than that calculated with oxygen (60 kJ/mol). At low methanol conversion methyl formate was the main product, whereas higher conversions favored oxidation to CO(x). The results imply a consecutive reaction of adsorbed methanol species, favoring selectivity toward methyl formate at lower temperatures and ozone-to-methanol ratios and CO(x) at higher temperatures and ozone-to-methanol ratios. Langmuir-Hinshelwood kinetics was used to model the reaction with and without ozone in the feed. The model parameters were obtained using least-squares fit to a selected set of experimental data, and the model was subsequently compared to all experimental data obtained in this study.