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. Additionally, the environment-energy-economy model integrates both life cycle assessment and life cycle costing methods and judges simultaneously these three features for sustainable waste-to-energy conversion. Life cycle assessment is sufficiently developed on waste-to-energy with concrete data inventory and sensitivity analysis, although the data and model uncertainty are unavoidable. Compared with life cycle assessment, only a few evaluations are conducted to waste-to-energy techniques by using extension methods and its methodology and application need to be further developed. Finally, this article succinctly summarises some recommendations for further research.

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. In the present study, molten salt oxidation is employed for treating a typical organic hazardous waste with a high content of alkali salts. The hazardous waste derives from the production of thiotriazinone. Molten salt oxidation experiments have been conducted using a lab-scale molten salt oxidation reactor, and the emissions of CO, NO, SO2, HCl and dioxins are studied. Impacts are investigated from the composition of the molten salts, the types of feeding tube, the temperature of molten carbonates and the air factor. Results show that the waste can be oxidised effectively in a molten salt bath. Temperature of molten carbonates plays the most important role. With the temperature rising from 600 °C to 750 °C, the oxidation efficiency increases from 91.1% to 98.3%. Compared with the temperature, air factor has but a minor effect, as well as the composition of the molten salts and the type of feeding tube. The molten carbonates retain chlorine with an efficiency higher than 99.9% and the emissions of dioxins are below 8 pg TEQ g-1 sample. The present study shows that molten salt oxidation is a promising alternative for the disposal of organic hazardous wastes containing a high salt content.

Municipal solid waste incineration in China and the issue of acidification: A review.

In China, incineration is essential for reducing the volume of municipal solid waste arising in its numerous megacities. The evolution of incinerator capacity has been huge, yet it creates strong opposition from a small, but vocal part of the population. The characteristics of Chinese municipal solid waste are analysed and data presented on its calorific value and composition. These are not so favourable for incineration, since the sustained use of auxiliary fuel is necessary for ensuring adequate combustion temperatures. Also, the emission standard for acid gases is more lenient in China than in the European Union, so special attention should be paid to the issue of acidification arising from flue gas. Next, the techniques used in flue gas cleaning in China are reviewed and the acidification potential by cleaned flue gas is estimated. Still, acidification induced by municipal solid waste incinerators remains marginal compared with the effects of coal-fired power plants.

Influence of temperature and atmosphere on polychlorinated dibenzo-p-dioxins and dibenzofurans desorption from waste incineration fly ash.

A fly ash sample was heated for 1 h to 200°C, 300°C and 400°C, in order to study the influence of temperature and gas phase composition on the removal of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from fly ash derived from municipal solid waste incineration. The tests were conducted by treating a fixed bed of fly ash both in an inert (nitrogen) and in a reducing (nitrogen+hydrogen) gas flow in a horizontal bench-scale quartz tubular reactor, heated by a surrounding tubular furnace. The results indicate that most of the PCDD/Fs in fly ash were removed by thermal treatment, especially when the temperature was higher than 300°C: the PCDD/Fs' removal efficiency attained up to 96%. PCDD/Fs dechlorination and destruction were much more important than PCDD/Fs desorption, under either inert or reducing atmosphere. At 200°C and 300°C, the experiments with reducing atmosphere yielded slightly better results than those in nitrogen; yet, this tendency was reversed at 400°C. In general, both treatment modes can fully meet the requirements regarding the concentration of dioxins in fly ash to be sent for landfill in China.

Dioxins and polyvinylchloride in combustion and fires.

This review on polyvinylchloride (PVC) and dioxins collects, collates, and compares data from selected sources on the formation of polychlorinated dibenzofurans (PCDFs) and dibenzo-p-dioxins (PCDDs), or in brief dioxins, in combustion and fires. In professional spheres, the incineration of PVC as part of municipal solid waste is seldom seen as a problem, since deep flue gas cleaning is required anyhow. Conversely, with its high content of chlorine, PVC is frequently branded as a major chlorine donor and spitefully leads to substantial formation of dioxins during poorly controlled or uncontrolled combustion and open fires. Numerous still ill-documented and diverse factors of influence may affect the formation of dioxins during combustion: on the one hand PVC-compounds represent an array of materials with widely different formulations; on the other hand these may all be exposed to fires of different nature and consequences. Hence, attention should be paid to PVC with respect to the ignition and development of fires, as well as attenuating the emission of objectionable compounds, such as carbon monoxide, hydrogen chloride, polycyclic aromatic hydrocarbons, and dioxins. This review summarises available dioxin emissions data, gathers experimental and simulation studies of fires and combustion tests involving PVC, and identifies and analyses the effects of several local factors of influence, affecting the formation of dioxins during PVC combustion.

Dioxins from medical waste incineration: Normal operation and transient conditions.

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are key pollutants in waste incineration. At present, incinerator managers and official supervisors focus only on emissions evolving during steady-state operation. Yet, these emissions may considerably be raised during periods of poor combustion, plant shutdown, and especially when starting-up from cold. Until now there were no data on transient emissions from medical (or hospital) waste incineration (MWI). However, MWI is reputed to engender higher emissions than those from municipal solid waste incineration (MSWI). The emission levels in this study recorded for shutdown and start-up, however, were significantly higher: 483 ± 184 ng Nm(-3) (1.47 ± 0.17 ng I-TEQ Nm(-3)) for shutdown and 735 ng Nm(-3) (7.73 ng I-TEQ Nm(-3)) for start-up conditions, respectively. Thus, the average (I-TEQ) concentration during shutdown is 2.6 (3.8) times higher than the average concentration during normal operation, and the average (I-TEQ) concentration during start-up is 4.0 (almost 20) times higher. So monitoring should cover the entire incineration cycle, including start-up, operation and shutdown, rather than optimised operation only. This suggestion is important for medical waste incinerators, as these facilities frequently start up and shut down, because of their small size, or of lacking waste supply. Forthcoming operation should shift towards much longer operating cycles, i.e., a single weekly start-up and shutdown.

Pilot tests on the catalytic filtration of dioxins.

Tests were conducted to study the removal efficiencies (REs) of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from flue gas during a test program involving a pilot-scale catalytic filter (CF) module and a full-scale municipal solid waste incinerator (MSWI). The REs attained with the CF on a side stream and a conventional activated carbon (AC) injection and baghouse filtration system in the full-scale MSWI are evaluated via simultaneous sampling and analysis of both gas- and particle-phase PCDD/Fs. Flue gas without AC is supplied to the pilot-scale CF module for evaluating its RE capabilities. The REs achieved with the CF at 180 °C are 96.80 and 99.50%, respectively, for the gas phase and the particulate contained. The gas-phase PCDD/F RE rises significantly at 200 and 220 °C. The air/cloth (A/C) ratio defined as is the gas flow rate (m(3)/min) divided by the filtration area (m(2)) also affects the PCDD/F RE, especially in the gas phase. At 180 °C, a RE of gas-phase PCDD/Fs of 95.94% is attained with the CF at 0.8 m/min, yet it decreases at higher A/C ratios (1 and 1.2 m/min). A significantly lower toxic equivalency (TEQ) concentration (0.71 ng I-TEQ/g) was measured in the filter dust of the CF module compared to that collected by the AC adsorption system (4.18 ng I-TEQ/g), apparently because of the destruction of gas-phase PCDD/Fs by the catalyst.

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, f (s), 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.

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. A series of de novo tests, conducted over a wide range of temperature (from 250 to 550 °C) and for four different oxygen contents (0, 5, 10, 20 %), confirmed the promoting effect of CrCl3 on the PCDD/F formation. In situ X-ray Absorption Fine Structure (XAFS) spectroscopy was applied to investigate the behavior of CrCl3 during heating, describing the entire picture of CrCl3-promoted formation pathways of dioxins. The effect of oxygen was studied by measuring XAFS spectra on samples heated at different oxygen concentrations. According to these spectra, chromium compounds play two key roles during dioxins formation: (a) chlorinating carbon, using chlorine derived from conversion of CrCl3 into Cr2O3, and further oxidation to Cr(VI), and (b) facilitating oxidative destruction of the carbon matrix, while reducing Cr(VI) to Cr2O3.

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 SiO2-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 6.75 to 0.64 ng I-TEQ/g, after 14 h of milling with 10 wt % SiO2-Al, and dechlorination is identified as the major degradation pathway. Then, this additive is applied in a horizontal ball mill, and the results indicate that the degradation of PCDD/Fs follows the kinetic model established in planetary ball mills. However, longer milling time is required for the same supplied-energy because of the lower energy density of horizontal ball mills, resulting in partial loss of Al reactivity and a lower degradation efficiency of PCDD/Fs. During MCD, the evolution of PCDD/F-signatures is analogous, indicating a similar acting mechanism of all additives in both the two milling systems. Finally, a major dechlorination pathway of PCDD-congeners is proposed based on the signature analysis of congeners synthesized from chlorophenols.

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. Compared to simple water washing, MA treatment of CFB FA further reduces the residual amount of chlorine in fly ash from 0.72 to 0.33 wt%, giving the possibility of doubling the capacity of cement kiln for fly ash disposal. The improvement in chlorine removal relates to the conversion of FA compounds from a crystalline to an amorphous state, increasing the solubility of sparingly soluble chlorides. During the curing of mortars, traces of aluminum or other nonferrous metals in CFB FA are oxidized, liberating lots of hydrogen gas; this would cause expansion problems and significantly reduce the flexural and compressive strength. MA treatment of CFB FA solves such expansion problems by exhausting these reactions in advance, respectively enhancing flexural and compressive strength from 5.7 and 35.3 MPa to 9.1 and 56.9 MPa, which is comparable to the performance of Ordinary Portland Cement. Finally, an innovative pre-treatment technique for CFB FA, combining wet ball milling and counter-current two-stage water washing, is proposed for facilitating its recycling.

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. Furthermore, highly chlorinated PCDD/Fs homologues were abundant in that sample, while the profiles were contrary to those of other materials. More importantly, the entire isomer signatures of all 61 samples were analysed, involving various materials, temperatures, oxygen levels, particle size and inhibitors, with special emphasis on those congeners associated with chlorophenol precursor routes, as well as seventeen 2,3,7,8-substituted PCDD/Fs. Strong correlation was found among seven PCDD-congeners of CP-route. The analysis of the molecular structure of these congeners revealed that 2,4,6/2,3,5-trichlorophenol may act as a precursor to form all those PCDD-congeners by condensation. In addition, the influence of various factors (temperature, oxygen level, particle size, inhibitors addition etc.) on the relative importance of CP-route congeners and 2,3,7,8-substituted congeners was discussed, with the goal of shedding more light on the mechanism of PCDD/Fs-formation.

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. The speciation of carbon and chlorine on ash surfaces was established, showing a positive correlation between organic chlorine and oxygen-containing carbon functional groups. The load of PCDD/F and PCB (especially dioxin-like PCB) tends to rise rapidly with falling temperature of flue gas, reaching their highest value in economiser ashes. The formation of PCDD/F congeners through the chlorophenol precursor route apparently was enhanced downstream the boiler. Principal component analysis (PCA) was applied to study the links between the ash characteristics and distribution of chloro-aromatics. The primary purpose of this study is improving the understanding of any links between the characteristics of ash from waste heat systems and its potential to form PCDD/F and PCB. The question is raised whether further characterisation of fly ash may assist to establish a diagnosis of poor plant operation, inclusive the generation, destruction and eventual emission of persistent organic pollutants (POPs).

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. Both PCDD/F-output and its signature are extensively characterised, including homologue and congener profiles. For the first time, a complete isomer-specific analysis is systematically established, for all samples. Special attention is paid to the chlorophenols route PCDD/F, to the 2,3,7,8-substituted congeners, and to their relationship and antagonism.

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. The residual content of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) was monitored, as well as polycyclic aromatic hydrocarbons (PAH), a potential precursor of PCDD/F and amorphous carbon or graphite. Finally, de novo formation experiments were performed to test the chemical reactivity of the treated fly ash. The PCDD/F in milled samples was compared to those resulting from de novo tests on these same samples. The results suggest that both milling as well as de novo tests significantly alter the PCDD/F signature, suggesting substantial differences in the mechanisms of formation and destruction.

Hot rolling sludge incineration: Suppression of PCDD/Fs by spent anion exchange resins.

Steel industry is the main industrial source of 'dioxins', i.e. polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF). These arise mainly in the off-gas from sintering plant, yet also other operations, such as continuous casting, and hot and cold rolling could generate albeit minor amounts of dioxins. In this contribution it is verified in how far the incineration of hot rolling sludge (HRS) could contribute to such emissions and, if so, how these could be suppressed at low cost. Spent anion exchange resin (SAER) appeared as a dioxins suppressant during combustion tests of hot rolling sludge in a bench-scale tubular furnace. The reduction efficiency (RE) of PCDD/F and I-TEQ-generation attained 91.1% and 90.2%, respectively, with the addition of 2.5wt.% resin, and the highest dioxins RE reached 97.8% with 10wt.% resin addition. The PCDD/PCDF ratio raised markedly when adding resin, indicating stronger suppression for PCDF- than for PCDD-formation. However, further research is still needed to establish the effect of resin on PCDD/F formation and inhibition during full-scale experiments. The off-gas released by sludge and resin co-combustion was also monitored and the residue analysed by Energy Dispersive Spectrometer (EDS); the results revealed that the SO2 concentration in the off-gas was higher during co-combustion than when burning HRS only. Likewise, the sulphur content in the combustion residue rises with resin addition. Still, the suggestion that suppression of PCDD/F formation should be ascribed to the poisoning of catalytic metal by S-containing compounds seems to be invalidated by the high initial S/Cl-ratio of HRS, even before SAER addition. These surprising findings were further analysed by a scrutiny of fingerprints obtained at the five distinct dosages tested. The relative amount of 2,3,7,8-PCDD/F was remarkably depressed by inhibitor addition and the relative importance of the chlorophenols route strongly expanded. Several reaction schemes, showing the results of further signature analysis are presented and are expected to throw more light on the mechanism of formation and its suppression.

Catalytic oxidation of PCDD/F on a V2O5-WO3/TiO2 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-1), 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. Also, the occurrence of carbon deposition negatively influenced catalytic oxidation activity. Regeneration with oxygen or air allowed to remove the deposited carbon and the original catalytic activity was largely restored after calcination. In a second part of this study, the PCDD/F-formation from DCBz, hexachlorobenzene (HCBz), o-monochlorophenol (o-MCP) and pentachlorophenol (PeCP) was demonstrated and tentatively explored. To prepare for further elucidation of the reaction mechanism, a complete isomer-specific analysis was prepared.

Low temperature degradation of polychlorinated dibenzo-p-dioxins and dibenzofurans over a VOx-CeOx/TiO2 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 VOx-CeOx/TiO2 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. Ozone (500 ppm) was also introduced into the system to increase the activity of catalyst, and removal efficiency of PCDD/Fs increased further to 97.4% and 98.8% at 200 and 240 °C, respectively. In addition, a lab-scale reaction system was installed to study the degradation mechanism of PCDD/Fs. Octa-chlorinated dibenzo-p-dioxin (OCDD) was selected as the study object due to the most stable structure and maximum chlorine atom number. The intermediate products resulting from the conversion of OCDD were monitored using gas chromatography/mass spectrometry and Fourier transform infrared spectroscopy and a possible reaction pathway was proposed. Dechlorination persists until the complete conversion of OCDD. Oxidation decomposes OCDD-molecules mainly into organic substances having one, two or more benzene rings, yet also alkanes, cycloalkanes and heterocompounds of sulphur, nitrogen, and halogens appear. However, more work is still needed to fit those trace products into mechanistic schemes.

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. Each metal catalyst generates a significantly different signature, also affected by the presence or absence of oxygen in the reaction atmosphere. Oxide and chloride catalysts supply distinctive signatures, suggesting singly weighted pathways. Quite a large number of data was handled, so that throughout this analysis special attention was given to testing and developing an appropriate methodology, allowing appropriate correlation analysis and statistical data treatment. The large tables resulting relate to the 11 catalytic systems, studied at 3 levels of oxygen concentration, with 94 PCDD/F-congeners considered individually. They constitute an extensive reference data bank for confronting novel experimental data with this vast data set.

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. Most output reports to the gas phase and the PCDD/F signature is significantly different for residue and gas phase. Also PCB are formed, at a scale of 224 ng/g (300 °C). Compared with 1,2-DiCBz, HCBz converts into PCDD/F even more actively at 350 and 400 °C: the total PCDD/F output created attains 967 pg/g PCDD and 465 pg/g PCDF at 350 °C. As a precursor, 1,2-DiCBz favours formation of PCDF, while PCDD predominates, when the HCBz contaminated soil is treated.