Degradation of VOCs by phototcatalytic oxidation reactor using TiO2 pellets

Volatile Organic Compounds (VOCs) are air pollutants that come from burning fossil fuels and industrial emissions. They have potentially adverse health effects being carcinogenic and highly persistent in the environment. The use of photocatalytic oxidation to remove VOCs has the potential to be applied in indoor air quality improvement and industrial emission control. A fixed bed photocatalytic reactor was designed and built. UV black light lamps were installed in the reactor to provide a source of UV radiation. A non-film titania media as pellets were placed on the three fixed beds within the reactor. Toluene and acetone were used as indicators of VOCs during the experiment. With a flow rate of 12.75l/min, the oxidation efficiencies were obtained at four different concentrations of acetone laden gas streams ranging from 40ppm to 250ppm. It was found that the lower the acetone concentration of the untreated inlet gas, the higher the oxidation efficiency. The oxidation efficiency was in the range of 40–70% for various concentrations of untreated gases. Two concentrations of toluene laden gas stream were also tested using the same reactor. The oxidation efficiencies were found as 50% for 120ppm toluene gas and 45% for 300ppm toluene gas. It was found that the times required for toluene to reach oxidization equilibrium have been halved than for acetone gas stream. Other parameters such as flow rate and UV intensity were also altered to see their effects on the oxidation efficiency. A full spectrum scan was carried out using a Bio-rad Infrared spectrometer. It was found that the main components of the treated gas stream from the outlet of the reactor were CO2 and water along with small amount of untreated acetone. The suspected intermediates of aliphatic hydrocarbons and CO were found in very minimal amounts or undetectable. The research experiments supported that the TiO2 pellets can work effectively in a fixed bed photocatalytic reactor and achieve significant oxidation efficiencies for degradation of toluene and acetone as indicators of VOCs.

Removal of VOCs by photocatalysis process using adsorption enhanced TiO2–SiO2 catalyst

Volatile organic compounds (VOCs) exist widely in both the indoor and outdoor environment. The main contributing sources of VOCs are motor vehicle exhaust and solvent utilization. Some VOCs are toxic and carcinogenic to human health, such as benzene. In this study, TiO₂–SiO₂ based photocatalysts were synthesized using the sol–gel method, with high surface areas of 274.1–421.1 m²/g obtained. Two types of pellets were used as catalysts in a fixed-bed reactor installed with a UV black light lamp. Experiments were conducted to compare their efficiencies in degrading the VOCs. Toluene was used as the VOC indicator. When the toluene laden gas stream passed through the photocatalytic reactor, the removal efficiencies were determined using a FTIR multi-gas analyser, which was connected to the outlet of the reactor to analyse the toluene concentrations. As the TiO₂–SiO₂ pellets used have a high adsorption capacity, they had dual functions as a photocatalyst and adsorbent in the hybrid photocatalysis and adsorption system. The experiments demonstrated that the porous photocatalyst with very high adsorptive capacity enhanced the subsequent photocatalysis reactions and lead to a positive synergistic effect. The catalyst can be self-regenerated by photocatalytic oxidation of the adsorbed VOCs. When the UV irradiation and feeding gas is continuous, a destruction efficiency of about 25% was achieved over a period of 20 h. Once the system was designed and operated into adsorption/regeneration mode, a higher removal efficiency of about 55% was maintained. It was found that the catalyst pellets with a higher surface area (421 m²/g) achieved higher conversion efficiency (100%) for a longer period than those with a lower surface area. A full spectrum scan was carried out using a Bio-rad Infrared spectrometer, finding that the main components of the treated gas stream leaving the reactor, along with untreated toluene, were CO₂ and water. The suspected intermediates of aliphatic hydrocarbons and CO were found in minimal amounts or were non detectable. The kinetic rate constants were calculated from the experimental results, it appeared that the stronger adsorption capacity, i.e. larger specific surface area, the higher conversion efficiency would be achieved.

The characterisation of polycyclic aromatic hydrocarbons emissions from burning of different firewood species in Australia

Four kinds of woods used for residential heating in Australia were selected and burned under two burning conditions in a domestic wood heater installed in a laboratory. The selected wood species included pine (Pinus radiata), red gum (Eucalyptus camaldulensis), sugar gum (Eucalyptus cladocalyx) and yellow box (Eucalyptus melliodora). The two different burning conditions represented fast burning and slow burning, with the air inlet of the combustion chamber respectively ‘full open’ and ‘half open’. By sampling and analysing particulate and gaseous emissions from the burning of each load of wood under defined experimental conditions, PAHs emissions and their profiles in the particulate and gaseous phases were obtained. 16 species out of the 18 selected PAHs were detected. Of these, seven species were detected in the gaseous phase and most were lower molecular weight compounds. Similarly, more than 10 species of PAHs were detected in the particulate phase and these were mostly heavier molecular weight compounds. Under both burning conditions, emission levels for total PAHs and total genotoxic PAHs were the highest for pine and lowest for sugar gum, with red gum being the second highest, followed by yellow box. Using the specific sampling method, gaseous PAHs accounted for above 90% mass fraction of total PAHs in comparison to particulate PAHs (10%). The majority of the genotoxic PAHs were present in the particulate phase. PAHs emission levels in slow burning conditions were generally higher than those in fast burning conditions.

Facilitated heterogeneous photodegradation of dissolved organic matter by particulate iron

The photochemical degradation of dissolved organic matter (DOM) derived from the leaves of River Red Gum (Eucalyptus camaldulensis) was examined, with a particular focus on the photochemical generation of CO₂, consumption of O₂, and the effect of particulate iron minerals on these photochemical reactions. Solutions of leaf leachate were irradiated with ultraviolet and visible light in the presence and absence of amorphous iron oxides. Addition of fresh iron oxide was found to increase the rate of photodegradation of the organic matter by up to an order of magnitude compared to the reactions without added iron oxide. The ratio of CO₂ produced to O₂ consumed was ~1:1 in both the presence and absence of iron oxyhydroxide. The reactivity of the iron oxides was dependent on the preparation method and decreased with increased storage time. These results suggest that photochemical reactions on particle surfaces should be considered when examining carbon transformation in aquatic ecosystems, especially at sites with potential for the production of iron oxyhydroxides.

Study of polycyclic aromatic hydrocarbons emissions from burning of local wood species in Australia

Four kinds of Australian local wood species were burned in a domestic wood heater installed in a laboratory. The selected wood species include pine, red gum, yellow box and sugar gum, that are the most popular domestic fuel wood in Australia. Particulate matter emissions from burning of each load of wood were sampled isokinetically on filter media from the flue by standard stack emission sampling train. The particle laden filters then went for Gas Chromatography/ Mass Spectrometer (GC/MS) analysis to determine polycyclic aromatic hydrocarbons (PAHs) concentrations. The sampling was conducted under two different burning conditions – air inlet of the combustion chamber fully open and half open. Approximately 15 types of PAHs were detected. Emission factors were derived as microgram of PAHs /kg of wood burned. Total particulate emission factors were also obtained from gravimetric measurement before and after the sampling. PAH emission profiles for four species were generated from the results. Comparisons of emission factors have been conducted among different species of wood, as well as under different burning conditions, ie. fast burning and slowing burning. According to the derived emission factors, pine displayed the highest level of PAHs among the four species, followed by red gum and yellow box, whereas sugar gum showed the lowest level of PAHs. Emission factors were compared between each type of wood under two different burning conditions, the slow burning condition, which was air inlet half open, clearly showed higher PAH levels compared to the fast burning condition. Total PAH fractions on particulate matter were calculated and compared among wood types under two burning conditions. During the fast burning condition, red gum and pine have the higher percentage of PAH to total particulate matter emission than sugar gum and yellow box. When changed to slow burning, the PAH fraction on particulate matter are all increased with sugar gum having the largest increase.

Baseline assessment of metals and hydrocarbons in the sediments of Lake Mulwala, Australia

An assessment of hydrocarbon and metal/metalloids (arsenic, cadmium, copper, lead, mercury, selenium, zinc) contamination in sediments from Lake Mulwala, Australia, was undertaken. The objectives of the study were: (i) to determine the extent of contamination in the lake sediments, compared to Australian and international sediment quality guidelines, and (ii) to attempt to identify the contaminant sources to the lake. With the exception of a few samples containing elevated levels of arsenic and/or mercury, the levels of all contaminants in the sediment samples taken from the lake were below the 'lower trigger' of the Australian Sediment Quality Guidelines that would warrant further investigation. High molecular weight hydrocarbons (up to 700 mg kg−1) were found in most sediment samples. Non-metric statistical analysis indicated that the contaminant distribution was different in different parts of the lake, with the lowest concentrations generally found at the influent to the lake. No definitive source(s) of contamination could be identified for either metalloids or hydrocarbons.

Photodegradation, interaction with iron oxides and bioavailability of dissolved organic matter from forested floodplain sources

Photochemical degradation of dissolved organic matter (DOM) can influence food webs by altering the availability of carbon to microbial communities, and may be particularly important following periods of high DOM input (e.g. flooding of forested floodplains). Iron oxides can facilitate these reactions, but their influence on subsequent organic products is poorly understood. Degradation experiments with billabong (= oxbow lake) water and river red gum (Eucalyptus camaldulensis) leaf leachate were conducted to assess the importance of these reactions in floodplain systems. Photochemical degradation of DOM in sunlight-irradiated quartz tubes (with and without amorphous iron oxide) was studied using gas chromatography and UV-visible spectroscopy. Photochemical reactions generated gaseous products and small organic acids. Bioavailability of billabong DOM increased following irradiation, whereas that of leaf leachate was not significantly altered. Fluorescence excitation-emission spectra suggested that the humic component of billabong organic matter was particularly susceptible to degradation, and the source of DOM influenced the changes observed. The addition of amorphous iron oxide increased rates of photochemical degradation of leachate and billabong DOM. The importance of photochemical reactions to aquatic systems will depend on the source of the DOM and its starting bioavailability, whereas inputs of freshly formed iron oxides will accelerate the processes.

Re-cycling carbon dioxide into fuel-like hydrocarbons by photocatalytic process

A new approach of heterogenous photocatalysis using titanium dioxide pellets was explored. It was found to be attractive for use in photocatalytic reduction of carbon dioxide with wavelength and temperature being crucial factors. The study also proposes a kinetic modelling for the process to simulate the product-yield profile.

Surfactant-mediated biodegradation of polycyclic aromatic hydrocarbons

Polycyclic aromatic hydrocarbons (PAHs) are toxic environmental pollutants that are known or suspected carcinogens or mutagens. Bioremediation has been used as a general way to eliminate them from the contaminated sites or aquifers, but their biodegradation is rather limited due to their low bioavailability because of their sparingly soluble nature. Surfactant-mediated biodegradation is a promising alternative. The presence of surfactants can increase the solubility of PAHs and hence potentially increase their bioavailability. However, inconclusive results have been reported on the effects of surfactant on the biodegradation of PAHs. In this work, surfactant-mediated biodegradation of PAHs is reviewed.

A novel cloud-point extraction process for preconcentrating selected polycyclic aromatic hydrocarbons in aqueous solution

A novel but simple cloud-point extraction (CPE) process is developed to preconcentrate the trace of selected polycyclic aromatic hydrocarbons (PAHs) with the use of the readily biodegradable nonionic surfactant Tergitol 15-S-7 as extractant. The concentrations of PAHs, mixtures of naphthalene and phenanthrene as well as pyrene, in the spiked samples were determined with the new CPE process at ambient temperature (23 °C) followed by high performance liquid chromatography (HPLC) with fluorescence detection. More than 80% of phenanthrene and pyrene, respectively, and 96% of naphthalene initially present in the aqueous solutions with concentrations near or below their aqueous solubilities were recovered using this new CPE process. Importantly Tergitol 15-S-7 does not give any fluorometric signal to interfere with fluorescence detection of PAHs in the UV range. No special washing step is, thus, required to remove surfactant before HPLC analyses. Different experimental conditions were studied. The optimum conditions for the preconcentration and determi nation of these selected PAHs at ambient temperature have been established as the following:  (1) 3 wt % surfactant; (2) addition of 0.5 M Na2SO4; (3) 10 min for equilibration time; and (4) 3000 rpm for centrifugal speed with duration of 10 min.