Thermochemical formation of dioxins promoted by chromium chloride: In situ Cr- and Cl-XAFS analysis.

Chromium is commonly found in the flue gases and ashes of Municipal Solid Waste Incineration. It has been reported as an active catalyst for the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) during de novo tests, yet its specific mode of action has remained unclear. This study aims to identify the effects of chromium chloride on the formation of PCDD/F and other chloro-aromatics and to elucidate the underlying reaction mechanisms.

Mechanical activation of fly ash from MSWI for utilization in cementitious materials.

In the present study, the physicochemical characteristics of municipal solid waste incineration fly ashes (FA) from circulating fluidized bed (CFB) or grate furnaces are studied in detail. It is identified that the CFB FA, containing high amount of Si and Al, has better potential and properties for utilization than the grate FA, which is much richer in chlorides. Mechanical activation (MA) allows amending the properties of CFB FA, thus preparing for its subsequent utilization in cementitious materials.

Mechanochemical degradation of PCDD/Fs in fly ash within different milling systems.

Two distinct mechanochemical degradation (MCD) methods are adopted to eliminate the polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs) from fly ash in municipal solid waste incinerators. First, experiments are conducted in a planetary ball mill for selecting suitable additives, and an additive system of SiO-Al is chosen for its high-efficiency, low-price, and good practicability. The I-TEQ value of PCDD/Fs in washed fly ash decreases dramatically from 6.

Parameters affecting the formation mechanisms of dioxins in the steel manufacture process.

With the implementation of the new national standards in the steel industry, dioxins (polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs)) emission and control have attracted more and more attention in China. The PCDD/Fs levels and signatures of nine steelmaking materials and by-products were experimentally analysed and compared, including five kinds of steelmaking fly ash (sintering fly ash, basic oxygen furnace fly ash, electric arc furnace fly ash and two kinds of blast furnace fly), three kind of steel sludge (continuous casting sludge, hot rolling sludge and cold rolling sludge) and sintering raw material. Dioxin formation from the sintering fly ash was highest of all 9 materials.

Characterising boiler ash from a circulating fluidised bed municipal solid waste incinerator and distribution of PCDD/F and PCB.

In this study, ash samples were collected from five locations situated in the boiler of a circulating fluidised bed municipal solid waste incinerator (high- and low-temperature superheater, evaporator tubes and upper and lower economiser). These samples represent a huge range of flue gas temperatures and were characterised for their particle size distribution, surface characteristics, elemental composition, chemical forms of carbon and chlorine and distribution of polychlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and biphenyls (PCB). Enrichment of chlorine, one of the main elements of organochlorinated pollutants, and copper, zinc and lead, major catalytic metals for dioxin-like compounds, was observed in lower-temperature ash deposits.

Mechanochemical treatment of fly ash and de novo testing of milled fly ash.

Mechanochemical (MC) treatment has been widely proposed to degrade chlorinated organics in various matrix materials. In this study, fly ash from municipal solid waste incineration was grinded without any addition, using an all-dimensional planetary ball mill. The treated fly ash samples were characterised using X-ray diffraction, Raman spectra, scanning electron microscopy and X-ray energy-dispersive spectroscopy.

Low temperature degradation of polychlorinated dibenzo-p-dioxins and dibenzofurans over a VO-CeO/TiO catalyst with addition of ozone.

In order to find a catalyst to destroy polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) with high efficiency, a homemade VO-CeO/TiO catalyst was prepared, and then tested in the flue gas of a waste incinerator at temperatures of 180-240 °C. The results shows the best removal efficiency (93.4%) was attained already at 200 °C, yet degradation efficiency further raised with temperature, until 240 °C.

Molten salt oxidation of organic hazardous waste with high salt content.

Organic hazardous waste often contains some salt, owing to the widespread use of alkali salts during industrial manufacturing processes. These salts cause complications during the treatment of this type of waste. Molten salt oxidation is a flameless, robust thermal process, with inherent capability of destroying the organic constituents of wastes, while retaining the inorganic ingredients in the molten salt.

Iron chloride catalysed PCDD/F-formation: Experiments and PCDD/F-signatures.

Iron chloride is often cited as catalyst of PCDD/F-formation, together with copper chloride. Conversely, iron chloride catalysis has been less studied during de novo tests. This paper presents such de novo test data, derived from model fly ash incorporating iron (III) chloride and established over a vast range of temperature and oxygen concentration in the gas phase.

Waste-to-energy: A review of life cycle assessment and its extension methods.

This article proposes a comprehensive review of evaluation tools based on life cycle thinking, as applied to waste-to-energy. Habitually, life cycle assessment is adopted to assess environmental burdens associated with waste-to-energy initiatives. Based on this framework, several extension methods have been developed to focus on specific aspects: Exergetic life cycle assessment for reducing resource depletion, life cycle costing for evaluating its economic burden, and social life cycle assessment for recording its social impacts.

Energy transfer and kinetics in mechanochemistry.

Mechanochemistry (MC) exerts extraordinary degradation and decomposition effects on many chlorinated, brominated, and even fluorinated persistent organic pollutants (POPs). However, its application is still limited by inadequate study of its reaction kinetic aspects. In the present work, the ball motion and energy transfer in planetary ball mill are investigated in some detail.

Catalytic oxidation of PCDD/F on a VO-WO/TiO catalyst: Effect of chlorinated benzenes and chlorinated phenols.

Catalytic oxidation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) is a well-proven technique, applied in a rising number of Municipal Solid Waste Incineration plants, yet the simultaneous and possibly competitive co-oxidation of other compounds, such as chlorinated benzenes (CBz) or phenols (CP), is still poorly documented. In this study, a grinded commercial catalyst (vanadium-tungsten supported on titanium dioxide) was submitted to exploratory testing: the PCDD/F present in a gas test flow were catalytically oxidised (200°C, 10,000h), either as such or in the presence of benzene (Bz), monochlorobenzene (MCBz), and 1,2-dichlorobenzene (DCBz) and the effect of these additions on the catalytic destruction of PCDD/F was verified experimentally. Both removal efficiency (RE) and destruction efficiency (DE) declined during the exploratory testing and, importantly, some DCBz even converted into supplemental PCDD/F.

PCDD/F formation during thermal desorption of chlorobenzene contaminated soil.

Unintentional formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) is observed and investigated during the thermal desorption in an airflow of a sandy soil, doped artificially with either 1,2-dichlorobenzene (1,2-DiCBz) or hexachlorobenzene (HCBz) using a lab-scale experimental set-up. At all temperatures investigated (200, 250, 300, 350 and 400 °C), this thermal treatment creates significant amounts of PCDD, PCDF and polychlorinated biphenyls (PCB), starting from 1,2-DiCBz. The highest yield of PCDD/F formed from 1,2-DiCBz occurs at 250 °C, with a total (gas + residual soil) output of 117 and 166 pg/g PCDD and PCDF, respectively.

De novo formation of dioxins from milled model fly ash.

Municipal solid waste incineration (MSWI) fly ash has been classified as hazardous waste and needs treatment in an environmentally safe manner. Mechanochemical (MC) treatment is such a detoxification method, since it destroys dioxins and solidifies heavy metals. Milling, however, also introduces supplemental metals (Fe, Ni, Cr, Mn…), following wear of both steel balls and housing.

PCDD/F-isomers signature - Effect of metal chlorides and oxides.

A recent paper presented the results from de novo tests, involving 11 distinct catalytic systems (oxides and chlorides of Cd, Cr, Cu, Ni, and Zn, as well as a blank sample). Their PCDD and PCDF formation activity was shown. This paper further assesses their isomer signature, with special emphasis on those congeners associated with chlorophenol precursor routes, and on 2,3,7,8- and 1,9-substituted congeners.

Dioxins degradation and reformation during mechanochemical treatment.

Mechanochemical dechlorination and destruction of polychlorinated dibenzo-p-dioxins and -furans (PCDD/F) on fly ash from Municipal Solid Waste Incineration was tested with and without additives (CaO and CaO/aluminium powder). The first results disappointed because of obvious PCDD/F-reformation and a second test series was conducted after removing soluble salts (NaCl, KCl …) by thorough two-stage water washing. This second test series was successful and demonstrated good destruction results, especially with combined CaO/aluminium powder as additive.

PCDD/F formation during thermal desorption of p,p'-DDT contaminated soil.

Thermal treatment of polychlorinated biphenyls (PCB) contaminated soil was shown in earlier work to generate polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF). In this study, the PCDD/F were studied arising during the remediation of p,p'-DDT contaminated soil by thermal desorption. Three kinds of soil (sandy, clayey and lateritic soil) were tested to investigate the effect of soil texture on PCDD/F formation.

Suppression of PCDD/Fs during thermal desorption of PCBs-contaminated soil.

Thermal treatment of polychlorinated biphenyls (PCBs) contaminated soil was shown in earlier work to generate new PCBs, as well as polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). In this study, this thermal desorption was conducted with addition of three distinct inhibitors, including ammonium sulphate, urea and calcium oxide, to inhibit the formation of PCDDs and PCDFs when remediating PCBs-contaminated soil. Experiments were conducted for 40 min at 400 °C after adding 1 wt.

Effects of bypass system on PCDD/F emission and chlorine circulation in cement kilns.

A bypass at the kiln inlet allows the effective reduction of alkali chloride cycles and thus perhaps affects the emission of PCDD/Fs. Effects of bypass system on PCDD/F emission and chlorine circulation were studied in two typical dry cement kilns with 5000 ton/day clinker capacity in China and named CK1 and CK2, respectively. Firstly, the emission level of PCDD/Fs with the operation of bypass system was estimated in CK1, to certify that bypass system has a perfect adaption to the cement kiln regarding the PCDD/F emission even with the refuse derived fuel (RDF) as the replacement of fuel.

Recycling ash into the first stage of cyclone pre-heater of cement kiln.

Fly ash collected from the bag filter could be recycled into the first stage of the cyclone pre-heater of the cement kiln, resulting in the possible enrichment of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). In this study, soxhlet fly ash (SFA) and raw meal (RM) were selected as the basis for the PCDD/F formation experiments. The levels of 2,3,7,8-PCDD/Fs formed on the SFA and RM were observed to be 2550pg/g (157pg I-TEQ/g) and 1142pg/g (55pg I-TEQ/g), respectively.

PCDD/F catalysis by metal chlorides and oxides.

Model fly ash (MFA) samples were composed of silica, sodium chloride, and activated carbon, and doped with metal (0.1 wt% Cu, Cr, Ni, Zn and Cd) chloride or oxide. Each sample was de novo tested at 350 °C for 1 h, in a flow of gas (N2, N2 + 10% O2, +21% O2 or +10% H2) to investigate the effect of metal catalyst and gas composition on PCDD/F formation.

Suppression of dioxins after the post-combustion zone of MSWIs.

Thiourea was selected as representative of combined S- and N-inhibitors and injected after the post-combustion zone of two full-scale municipal solid waste incinerators (MSWIs) using a dedicated feeder. Firstly, the operating conditions were scrutinised by monitoring the concentrations of SO2, NH3 and HCl in the clean flue gas. The suppression experiment showed that in MSWI A thiourea could reduce the total I-TEQ value in flue gas by 73.

Suppression of dioxins by S-N inhibitors in pilot-scale experiments.

S-N inhibitors like thiourea and sewage sludge decomposition gases (SDG) are relatively novel dioxins suppressants and their efficiencies are proven in numerous lab-scale experiments. In this study, the suppression effects of both thiourea and SDG on the formation of dioxins are systematically tested in a pilot-scale system, situated at the bypass of a hazardous waste incinerator (HWI). Moreover, a flue gas recirculation system is used to get high dioxin suppression efficiencies.

Suppression of chlorinated aromatics by nitrogen and sulphur inhibitors in iron ore sintering.

Dioxins generated by iron and steel industry account for the majority of industrial dioxins emissions. This study compares the performance of different additives (including calcium sulphate dehydrate CaSO4·2H2O; calcium polysulphide CaSx; ammonium sulphate (NH4)2SO4; 4-methylthiosemicarbazide H3C-SC(NH)2NH2 and thiourea H2NCSNH2) as suppressant of chlorinated aromatics in iron ore sintering. The formation of chlorobenzenes (CBz) and polychlorinated biphenyls (PCBs), used as surrogates for dioxins, was suppressed significantly in the present of various inhibitors (1 wt%) except for CaSO4·2H2O.