Optical and photocatalytic properties of nanocrystalline TiO2 synthesised by solid-state chemical reaction

Nanoparticulate TiO₂ is of interest for a variety of technological applications, including optically transparent UV-filters and photocatalysts for the destruction of chemical waste. The successful use of nanoparticulate TiO₂ in such applications requires an understanding of how the synthesis conditions effect the optical and photocatalytic properties. In this study, we have investigated the effect of heat treatment temperature on the properties of nanoparticulate TiO₂ powders that were synthesised by solid-state chemical reaction of anhydrous TiOSO₄ with Na₂CO₃. It was found that the photocatalytic activity increased with the heat treatment temperature up to a maximum at 600 °C and thereafter declined. In contrast, the optical transparency decreased monotonically with the heat treatment temperature. These results indicate that solid-state chemical reaction can be used to prepare powders of nanoparticulate TiO₂ with properties that are optimised for use as either optically transparent UV-filters or photocatalysts.

Tailoring the photocatalytic activity of nanoparticulate zinc oxide by transition metal oxide doping

The successful use of nanoparticulate ZnO in applications such as UV-screening agents or photocatalyst for the destruction of chemical waste requires the development of techniques for controlling its photocatalytic activity. In this study, we have investigated transition metal doping as a means of achieving this goal. Powders of ZnO, Mn_xZn_1−xO, and Co_xZn_1−xO were synthesised by a three-stage process consisting of high-energy mechanical milling, heat treatment, and washing. The photocatalytic activity of these powders was evaluated using the spin-trapping technique with electron paramagnetic resonance spectroscopy. It was found that the photocatalytic activity of Co_xZn_1−xO progressively decreased with the doping level. In contrast, the activity of Mn_xZn_1−xO initially increased with doping up to a level of 2 mol% and thereafter declined. These results demonstrate that doping with transition metal oxides can be used to tailor the photocatalytic properties of nanoparticulate ZnO.

Chemical and physical speciation of arsenic in a small pond receiving gold mine waste effluent

The chemical and physical speciation of arsenic in a small pond that receives wastewater from a gold mine operation in western Victoria, Australia was studied using differential pulse polarography. By using different sample pretreatments, distinction between the physical states (dissolved or particulate As), between the oxidation states (As(III) or As(V)), and between the degrees of lability (labile or strongly bound) was achieved. The results are interpreted in terms of the physicochemical properties with reference to the use of the pond as a settlement dam for gold mining effluent. The speciation of arsenic was found to vary markedly with the physicochemical properties of the water. A model for the behavior of arsenic in the pond is proposed.

Raw materials and process chemical recovery in industrial wastewater pollution control

This article illustrates the different methods employed to recover raw materials and process chemicals in various industries. Although only a few industries such as car painting, metal cutting, electroplating, textile, abattoir and pesticide formulation have been illustrated in case studies, almost all the industries can recover raw materials and process chemicals from their waste streams. The case studies show that the investments on new processes or systems used to recover raw materials and process chemicals have a short payback period and hence bring huge savings to those industries. Thus, each industry should try to recover raw material and process chemicals from waste streams.

Harvesting waste thermal energy using a carbon-nanotube-based thermo-electrochemical cell

Low efficiencies and costly electrode materials have limited harvesting of thermal energy as electrical energy using thermo-electrochemical cells (or “thermocells”). We demonstrate thermocells, in practical configurations (from coin cells to cells that can be wrapped around exhaust pipes), that harvest low-grade thermal energy using relatively inexpensive carbon multiwalled nanotube (MWNT) electrodes. These electrodes provide high electrochemically accessible surface areas and fast redox-mediated electron transfer, which significantly enhances thermocell current generation capacity and overall efficiency. Thermocell efficiency is further improved by directly synthesizing MWNTs as vertical forests that reduce electrical and thermal resistance at electrode/substrate junctions. The efficiency of thermocells with MWNT electrodes is shown to be as high as 1.4% of Carnot efficiency, which is 3-fold higher than for previously demonstrated thermocells. With the cost of MWNTs decreasing, MWNT-based thermocells may become commercially viable for harvesting low-grade thermal energy.

Estimating hydrogen sulphide dissipation rate constant under the influence of different chemical dosing

Sewer odour and corrosion is caused by the reduction of sulphide ions and the release of hydrogen sulphide gas (H2S) into the sewer atmosphere. The reduction of sulphide is determined by its dissipation rate which depends on many processes such as emission, oxidation and precipitation that prevail in wastewater environments. Two factors that mainly affect the dissipation of sulphide are sewer hydraulics and wastewater characteristics; modification to the latter by dosing certain chemicals is known as one of the mitigation strategies to control the dissipation of sulphide. This study investigates the dissipation of sulphide in the presence of NaOH, Mg(OH)2, Ca(NO3)2 and FeCl3 and the dissipation rate is developed as a function of hydraulic parameters such as the slope of the sewer and the velocity gradient. Experiments were conducted in a 18m experimental sewer pipe with adjustable slope to which, firstly no chemical was added and secondly each of the above mentioned chemicals was supplemented in turn. A dissipation rate constant of 2×10^-6 for sulphide was obtained from experiments with no chemical addition. This value was then used to predict the sulphide concentration that was responsible for the emission of H2S gas in the presence of one of the above mentioned four chemicals. It was found that the performance of alkali substances (NaOH and Mg(OH)2) in suppressing the H2S gas emission was excellent while ferric chloride showed a moderate mitigating effect due to its slow reaction kinetics. Calcium nitrate was of little value since the wastewater used in this study experienced almost no biological growth. Thus the effectiveness of selected chemicals in suppressing H2S gas emission had the following order: NaOH ≥ Mg(OH)2 ≥ FeCl3 ≥ Ca(NO3)2.

Pyrolysis of municipal green waste: a modelling, simulation and experimental analysis

Pyrolysis is the thermo-chemical conversion of carbonaceous feedstock in the absence of oxygen to produce bio-fuel (bio-oil, bio-char and syn-gas). Bio-fuel production from municipal green waste (MGW) through the pyrolysis process has attracted considerable attention recently in the renewable energy sector because it can reduce greenhouse gas emissions and contribute to energy security. This study analyses properties of MGW feedstock available in Rockhampton city of Central Queensland, Australia, and presents an experimental investigation of producing bio-fuel from that MGW through the pyrolysis process using a short sealed rotary furnace. It was found from the experiment that about 19.97% bio-oil, 40.83% bio-char and 29.77% syn-gas can be produced from the MGW. Then, a four-stage steady state simulation model is developed for pyrolysis process performance simulation using Aspen Plus software. In the first stage, the moisture content of the MGW feed is reduced. In the second stage, the MGW is decomposed according to its elemental constituents. In the third stage, condensate material is separated and, finally, the pyrolysis reactions are modelled using the Gibbs free energy minimisation approach. The MGW's ultimate and proximate analysis data were used in the Aspen Plus simulation as input parameters. The model is validated with experimentally measured data. A good agreement between simulation and experimental results was found. More specifically, the variation of modelling and experimental elemental compositions of the MGW was found to be 7.3% for carbon, 15.82% for hydrogen, 7.04% for nitrogen and 5.56% for sulphur. The validated model is used to optimise the biofuel production from the MGW as a function of operating variables such as temperature, moisture content, particle size and process heat air-fuel ratio. The modelling and optimisation results are presented, analysed and discussed.

The effect of triacetin as a fuel additive to waste cooking biodiesel on engine performance and exhaust emissions

This study investigates the effect of oxygenated fuels on engine performance and exhaust emission under a custom cycle using a fully instrumented 6-cylinder turbocharged diesel engine with a common railinjection system. A range of oxygenated fuels based on waste cooking biodiesel with triacetin as an oxygenated additive were studied. The oxygen ratio was used instead of the equivalence ratio, or air to fuelratio, to better explain the phenomena observed during combustion. It was found that the increased oxygen ratio was associated with an increase in the friction mean effective pressure, brake specific fuel consumption, CO, HC and PN. On the other hand, mechanical efficiency, brake thermal efficiency, CO2, NOx and PM decreased with oxygen ratio. Increasing the oxygen content of the fuel was associated with a decrease in indicated power, brake power, indicated mean effective pressure, brake mean effective pressure, friction power, blow-by, CO2, CO (at higher loads), HC, PM and PN. On the other hand, the brakespecific fuel consumption, brake thermal efficiency and NOx increased by using the oxygenated fuels. Also, by increasing the oxygen content, the accumulation mode count median diameter moved toward the smaller particle sizes. In addition to the oxygen content of fuel, the other physical and chemical properties of the fuels were used to interpret the behavior of the engine.