Shengyong Lu

Photocatalytic decomposition on nano-TiO2: Destruction of chloroaromatic compounds

Photocatalysis is applied increasingly in addressing and solving environmental and energy-related problems. Especially the TiO₂-derived catalysts attract attention because of their catalytic efficiency, wide range of applications, ease in use, and low cost (it costs about 150 Yuan a kilogram in China). This review first describes the principles of photocatalytic destruction by semiconductors and then focuses on degradation rates and reaction mechanisms in a variety of photocatalytic uses of modified TiO(2). Finally, these concepts are illustrated by selected examples relating to the photocatalytic degradation of organic persistent pollutants, such as polychlorinated benzenes (PCBz), biphenyls (PCB) and dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). And some approaches towards industrial application are analyzed.

Decomposition of naphthalene by dc gliding arc gas discharge.

Gliding arc discharge has been proved to be effective in treatment of gas and liquid contaminants. In this study, physical characteristics of dc gliding arc discharge and its application to naphthalene destruction are investigated with different external resistances and carrier gases. The decomposition rate increases with increasing of oxygen concentration and decreases with external resistance. This value can be achieved up to 92.3% at the external resistance of 50 kOmega in the oxygen discharge, while the highest destruction energy efficiency reaches 3.6 g (kW h)(-1) with the external resistance of 93 kOmega. Possible reaction pathways and degradation mechanisms in the plasma with different gases are proposed by qualitative analysis of postdestructed products. In the air and oxygen gliding arc discharges, the naphthalene degradation is mainly governed by reactions with oxygen-derived radicals.

Emission characteristics of volatile compounds during sludges drying process.

The emission characteristics of volatile compounds (VCs) during municipal sewage sludge (MSS) and paper mill sludge (PMS) drying process were investigated through experiments conducted on a lab-scale tubular drying furnace and a pilot-scale paddle dryer, respectively. The result indicated that five kinds of VCs, i.e. CO(2), NH(3), C(7)H(16) (n-heptane), volatile fatty acids (VFAs) and CH(4) were emitted during the drying process. It was found that the NH(3) and CO(2) were the primary compound released from the MSS drying process. In the case of the PMS, the VFAs and CO(2) were the main compounds released. The temperature and water content of sludge had great effects on the emission rates of NH(3), C(7)H(16), CO(2) and VFAs. The pH and chemical oxygen demand (COD) of condensate from the paddle dryer were also studied. It showed that pH and COD of condensate from MSS were much higher than that from the PMS, and that the higher COD value of the MSS condensate interrelated to the higher ammonium and sulfur content of it.

Combustion and inorganic bromine emission of waste printed circuit boards in a high temperature furnace

High temperature combustion experiments of waste printed circuit boards (PCBs) were conducted using a lab-scale system featuring a continuously-fed drop tube furnace. Combustion efficiency and the occurrence of inorganic bromine (HBr and Br(2)) were systematically studied by monitoring the main combustion products continuously. The influence of furnace temperature (T) was studied from 800 to 1400°C, the excess air factor (EAF) was varied from 1.2 to 1.9 and the residence time in the high temperature zone (RT(HT)) was set at 0.25, 0.5, or 0.75 s. Combustion efficiency depends on temperature, EAF and RT(HT); temperature has the most significant effect. Conversion of organic bromine from flame retardants into HBr and Br(2) depends on temperature and EAF. Temperature has crucial influence over the ratio of HBr to Br(2), whereas oxygen partial pressure plays a minor role. The two forms of inorganic bromine seem substantially to reach thermodynamic equilibrium within 0.25s. High temperature is required to improve the combustion performance: at 1200°C or higher, an EAF of 1.3 or more, and a RT(HT) exceeding 0.75 s, combustion is quite complete, the CO concentration in flue gas and remained carbon in ash are sufficiently low, and organobrominated compounds are successfully decomposed (more than 99.9%). According to these results, incineration of waste PCBs without preliminary separation and without additives would perform very well under certain conditions; the potential precursors for brominated dioxins formation could be destroyed efficiently. Increasing temperature could decrease the volume percentage ratio of Br(2)/HBr in flue gas greatly.

Thermal removal of PCDD/Fs from medical waste incineration fly ash--effect of temperature and nitrogen flow rate.

The fly ash used in this study was collected from a bag filter in a medical waste rotary kiln incineration system, using lime and activated carbon injection followed by their collection as mixed fly ash. Experiments were conducted on fly ash in a quartz tube, heated in a laboratory-scale horizontal tube furnace, in order to study the effect of temperature and nitrogen flow rate on the removal of PCDD/Fs. Results indicated that in this study PCDD/Fs in the fly ash mostly were removed and desorbed very little into the flue gas under thermal treatment especially when the heating temperature was higher than 350 °C, and dechlorination and destruction reactions took important part in the removal of PCDD/Fs. However, in terms of flow rate, when flow rate was higher than 4 cm s(-1), destruction efficiency of PCDD/Fs decreased dramatically and the main contributors were P(5)CDF, H(6)CDF and H(7)CDF desorbed to flue gas, the PCDD/Fs in the fly ash decreased with enhanced flow rate.

A review on black carbon emissions, worldwide and in China

Black carbon (BC) produced from open burning (OB) and controlled combustion (CC) is a range of carbonaceous products of incomplete combustion of biomass and fossil fuel, and is deemed as one of the major contributors to impact global environment and human health. BC has a strong relationship with POPs, in waste combustion, BC promotes the formation of POPs, and then the transport of POPs in the environment is highly influenced by BC. However less is known about BC formation, measurement and emissions estimation especially in developing countries such as China. Different forms of BC are produced both in CC and OB. BC emission characteristics and combustion parameters which determine BC emissions from CC and OB are discussed. Recent studies showed a lack of common methodology and the resulting data for describing the mechanisms related to BC formation during combustion processes. Because BC is a continuum carbonaceous combustion product, different sampling and measuring methods are used for measuring their emissions with great quantitative uncertainty. We discuss the commonly used BC sampling and measuring methods along with the causes for uncertainty and measures to minimizing the uncertainty. Then, we discuss the estimations of BC emission factors and emission inventory for CC and OB sources. The total emissions of BC from CC and OB in China are also estimated and compared with previous BC emission inventories in this review and we find the inventories tend to be overestimated. As China becomes the largest contributor to global BC emissions, studies for characterizing BC emissions from OB and CC sources are absent in China. Finally, we comment on the current state of BC emission research and identify major deficiencies that need to overcome. Moreover, the advancement in research tools, measuring technique in particular, as discussed in this review is critical for researchers in developing countries to improve their capability to study BC emissions for addressing the growing climate change and public health concerns.

Experimental and theoretical study of agitated contact drying of sewage sludge under partial vacuum conditions.

Agitated contact drying experiments were carried out in a cylindrical lab-scale paddle dryer to study the drying kinetics of sewage sludge under partial vacuum conditions. To explore the drying mechanisms, the penetration model for vacuum contact drying of agitated particulate materials, developed by Schlünder and Mollekopf, was applied to simulate the experimental results. The influence of the drying parameters (system pressure, heating temperature, stirrer speed, and dryer load) on the drying kinetics was studied both experimentally and theoretically. The results indicate that pressure and temperature significantly influence the drying rates of sewage sludge, whereas stirring speed and dryer load have no obvious effects on drying rates in the examined range. The experimental and simulated drying rates were in acceptable agreement as long as the temperature difference between dryer and sludge was small. A crust is likely to form on the dryer surface, however, when the temperature difference becomes large; this crust leads to markedly lower drying rates than the calculated ones. Furthermore, a comparison between partial vacuum contact drying and atmospheric contact drying is presented. The results indicate that the mass transfer resistance increases with rising drying potential in the examined experimental range.

Inhibition of PCDD/F by adding sulphur compounds to the feed of a hazardous waste incinerator.

Sulphur compounds, including (NH(4))(2)SO(4) and pyrite, were tested as suppressants in a hazardous waste incineration facility. The test results suggested that adding sulphur compounds only slightly reduced PCDD/F stack emissions; this restricted effect was attributed to the release of fly ash in large amounts during the sulphur adding experiments, i.e., it was due to a malfunctioning of the baghouse filter. Nevertheless, for the combined flow of flue gas+fly ash a reduction of more than 50% was achieved for the total PCDD/F concentrations and the total toxic concentrations, and an even higher inhibition capability was observed for PCDD. Also, a simulation of the thermodynamic equilibrium conditions by sulphur dioxide was conducted in the domain of experimental interest. Deactivation of catalysts, which promote PCDD/F formation, was found to be the dominant inhibition mechanism in low temperature PCDD/F formation. SO(2) could also inhibit the formation of molecular Cl(2) via the Deacon reaction, but that was not the main reason for inhibition.

Experimental study on the effects of H2O on PCDD/Fs formation by de novo synthesis in carbon/CuCl2 model system.

The effects of H(2)O vapor on de novo synthesis of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and biphenyls (PCB) were investigated at two levels (none and 10 vol.%) in various model systems containing five different carbons, CuCl(2), and quartz, exposed to a flow of 10% O(2)/N(2) at 300 degrees Celsius. The influence of H(2)O was studied on (1) speciation and behavior of copper compounds, (2) catalytic oxidation of carbons of distinct reactivity, and (3) formation of organic chlorine compounds, with the aim to investigate any effects on de novo synthesis. It is found that H(2)O converts CuCl(2) to CuCl(2) x CuO, and finally to CuO in a flow of 10% O(2)/N(2) at 300 degrees Celsius and that it decreases of organic chlorine (C-Cl) formation. When CuCl(2) is supported on carbon, the addition of H(2)O promotes the catalytic oxidation of this carbon. When CuCl(2) is supported on quartz, however, H(2)O inhibits carbon oxidation. A decrease in chlorination level of PCDD/Fs and PCBs with water addition is observed for all (six) model ashes; yet this addition affects the yields of PCDD/Fs and PCBs differently. Under the experimental conditions tested H(2)O does not react with Cu(2)Cl(2), which is the catalyst of carbon oxidation. On the basis of the experimental results, the following mechanism is proposed: conversion of CuCl(2) into CuO which is less reactive in de novo synthesis and promotion of catalytic oxidation of carbon by Cu(2)Cl(2).

Activated carbon treatment of municipal solid waste incineration flue gas

Activated carbon injection is widely used to control dioxins and mercury emissions. Surprisingly little attention has been paid to its modelling. This paper proposes an expansion of the classical Everaerts–Baeyens model, introducing the expression of fraction of free adsorption sites, fs, and asserting the significant contribution of fly ash to dioxins removal. Moreover, the model monitors dioxins partitioning between vapour and particulate phase, as well as removal efficiency for each congener separately. The effects of the principal parameters affecting adsorption are analysed according to a semi-analytical, semi-empirical model. These parameters include temperature, contact time during entrained-flow, characteristics (grain-size, pore structure, specific surface area) and dosage of activated carbon, lignite cokes or mineral adsorbent, fly ash characteristics and concentration, and type of incinerator plant.