Volatilization behavior of lead from molten slag under conditions simulating municipal solid waste melting

To reutilize molten slag derived from an ash melting process, the lead volatilization mechanism under reducing conditions was investigated. Reducing conditions were established by introducing a CO-CO₂-N₂ gas mixture to the reactor or by adding graphite to the molten slag prior to the experiments. As samples, two types of simulated molten slag composed of CaO-SiO₂-Al₂O₃ mixed with PbO were used and the lead volatilization behavior was studied at 1773 K. It was found that the lead volatilization rate increased on increasing the amount of reducing agent for both graphite and the CO-CO₂ gas mixture. For the CO-CO₂ reducing gas mixture, this increase was mainly attributed to PbO conversion to Pb. For the addition of graphite, the increase in lead volatilization ratio was considered to partially result from PbO conversion to Pb and partially from a reaction of graphite with SiO₂ yielding volatile SiO. The volatile SiO gas was then emitted from the furnace, which brought about a reduction in the SiO₂ content of the slag. As a result, the slag viscosity decreased, which led to an enhancement of the lead volatilization ratio.     

Characteristics of element distributions in an MSW ash melting treatment system

Thermal treatment of municipal solid waste (MSW) has become a common practice in waste volume reduction and resource recovery. For the utilization of molten slag for construction materials and metal recovery, it is important to understand the behavior of heavy metals in the melting process. In this study, the correlation between the contents of elements in feed materials and MSW molten slag and their distributions in the ash melting process, including metal residues, are investigated. The hazardous metal contents in the molten slag were significantly related to the contents of metals in the feed materials. Therefore, the separation of products containing these metals in waste materials could be an effective means of producing environmentally safe molten slag with a low hazardous metals content. The distribution ratios of elements in the ash melting process were also determined. The elements Zn and Pb were found to have a distribution ratio of over 60% in fly ash from the melting furnace and the contents of these metals were also high; therefore, Zn and Pb could be potential target metals for recycling from fly ash from the melting furnace. Meanwhile, Cu, Ni, Mo, Sn, and Sb were found to have distribution ratios of over 60% in the metal residue. Therefore, metal residue could be a good resource for these metals, as the contents of Cu, Ni, Mo, Sn, and Sb in metal residue are higher than those in other output materials.     

Morphological characteristics of waste polyethylene/polypropylene plastics during pyrolysis and representative morphological signal characterizing pyrolysis stages

In this work, the morphological characteristics of waste polyethylene (PE)/polypropylene (PP) plastics during their pyrolysis process were investigated, and based on their basic image changing patterns representative morphological signals describing the pyrolysis stages were obtained. PE and PP granules and films were used as typical plastics for testing, and influence of impurities was also investigated. During pyrolysis experiments, photographs of the testing samples were taken sequentially with a high-speed infrared camera, and the quantitative parameters that describe the morphological characteristics of these photographs were explored using the “Image Pro Plus (v6.3)” digital image processing software. The experimental results showed that plastics pyrolysis involved four stages: melting, two stages of decomposition which are characterized with bubble formation caused by volatile evaporating, and ash deposition; and each stage was characterized with its own phase changing behaviors and morphological features. Two stages of decomposition are the key step of pyrolysis since they took up half or more of the reaction time; melting step consumed another half of reaction time in experiments when raw materials were heated up from ambient temperatures; and coke-like deposition appeared as a result of decomposition completion. Two morphological signals defined from digital image processing, namely, pixel area of the interested reaction region and bubble ratio (BR) caused by volatile evaporating were found to change regularly with pyrolysis stages. In particular, for all experimental scenarios with plastics films and granules, the BR curves always exhibited a slowly drop as melting started and then a sharp increase followed by a deep decrease corresponding to the first stage of intense decomposition, afterwards a second increase – drop section corresponding to the second stage of decomposition appeared. As ash deposition happened, the BR dropped to zero or very low values. When impurities were involved, the shape of BR curves showed that intense decomposition started earlier but morphological characteristics remained the same. In addition, compared to parameters such as pressure, the BR reflects reaction stages better and its change with pyrolysis process of PE/PP plastics with or without impurities was more intrinsically process correlated; therefore it can be adopted as a signal for pyrolysis process characterization, as well as offering guide to process improvement and reactor design.     

Gasification characteristics of MSW and an ANN prediction model

Gasification characteristics make up the important parts of municipal solid waste (MSW) gasification and melting technology. These characteristics are closely related to the composition of MSW, which alters with climates and seasons. It is important to find a practical way to predict gasification characteristics. In this paper, five typical kinds of organic components (wood, paper, kitchen garbage, plastic, and textile) and three representative types of simulated MSW are gasified in a fluidized-bed at 400-800 degrees C with the equivalence ratio (ER) in the range of 0.2-0.6. The lower heating value (LHV) of gas, gasification products, and gas yield are reported. The results indicate that gasification characteristics are different from sample to sample. Based on the experimental data, an artificial neural networks (ANN) model is developed to predict gasification characteristics. The training and validating relative errors are within +/-15% and +/-20%, respectively, and predicting relative errors of an industrial sample are below +/-25%. This indicates that it is acceptable to predict gasification characteristics via ANN model.     

Numerical study of heat transfer characteristics of char from waste tire pyrolysis

To investigate heat transfer of char from waste tire pyrolysis, the cooling of char was simulated by the computational fluid dynamics. To scrutinize the heat transfer characteristics, bed height, temperature of cooling wall, and mixing time were selected as calculation parameters. From the results, increasing the char bed height from 0.005 to 0.02 m, the total heat transfer is decreased as from 45.5 to 26.5 J. As the char bed height is further increased from 0.02 to 0.06 m, the total heat transfer is decreased from 26.5 to 9.1 J. The char bed height affects the total heat transfer significantly. The total heat transfer decreases from 15.9 to 14.0 J as the temperature of cooling wall increases from 273.15 to 323.15 K. The total heat transfer mildly depends on the temperature of cooling wall. The particle mixing time increases from 10 to 120 s and the total heat transfer decreases from 28.6 to 22.6 J. It is noted that the particle contact is enhanced between char particles as well as the particles and cooling wall as the particle mixing time decreases. Consequently, heat transfer is augmented.     

Studies on the pyrolysis behavior of gasification and melting systems for municipal solid waste

 It is important to investigate the pyrolysis processes of municipal solid waste (MSW) in the same way as for any mixture comprised of multiple substances. In this article, a two-reaction model for a variety of MSW mixtures is proposed to predict mass changes due to pyrolysis. In order to formulate the model based on pyrolysis kinetics, we conducted experiments to determine the kinetic model parameters. By thermal analysis of the typical components of MSW, mass changes attributable to the pyrolysis reaction were found at about 350°C for paper, 400°–500°C for plastics, and 200°–400°C for garbage (dry condition). Activation energies were obtained by the Ozawa method based on the mass changes in pyrolysis. Thus, the pyrolysis behavior is formulated as a function of temperature. Then the pyrolysis mass change of the mixture can be predicted by using a weighted sum of the individual components. The model proved useful in experiments with real waste (refuse-derived fuels). Furthermore, the weight yields (pyrolysis gas, tars, solid residues) of the mixture can be calculated by their additive property after measuring the mass balance of each component. Received: May 11, 2001 / Accepted: November 16, 2001     

Behavior of metals in ash melting and gasification-melting of municipal solid waste (MSW)

In this study, metal behavior in ash-melting and municipal solid waste (MSW) gasification-melting facilities were investigated. Eight ash-melting and three MSW gasification-melting facilities with a variety of melting processes and feedstocks were selected. From each facility, melting furnace fly ash (MFA) and molten slag were sampled, and feedstock of the ash-melting processes was also taken. For the ash melting process, the generation rate of MFA was well correlated with the ratio of incineration fly ash (IFA) in feedstock, and this was because MFA was formed mostly by mass transfer from IFA and a limited amount from bottom ash (BA). Distribution ratios of metal elements to MFA were generally determined by volatility of the metal element, but chlorine content in feedstock had a significant effect on Cu and a marginal effect on Pb. Distribution ratio of Zn to MFA was influenced by the oxidizing atmosphere in the furnace. High MFA generation and distribution ratio of non-volatile metals to MFA in gasification-melting facilities was probably caused by carry-over of fine particles to the air pollution control system due to large gas volume. Finally, dilution effect was shown to have a significant effect on metal concentration in MFA.     

Physico-chemical and biological treatment of MSW landfill leachate

This paper analyses the evolution of the physico-chemical characteristics of the leachate from the Central Landfill of Asturias (Spain), which has been operating since 1986, as well as different treatment options. The organic pollutant load of the leachate, expressed as chemical oxygen demand (COD), reached maximum values during the first year of operation of the landfill (around 80,000 mg/L), gradually decreasing over subsequent years to less than 5000 mg/L. The concentration of ammonium, however, has not decreased, presenting values of up to 2000 mg/L. When feasible, recirculation can greatly decrease the organic matter content of the leachate to values of 1500–1600 mg COD/L. Applying anaerobic treatment to leachates with a COD between 11,000 and 16,000 mg/L, removal efficiencies of 80–88% were obtained for organic loading rates of 7 kg COD/m³ d. For leachates with lower COD (4000–6000 mg/L), the efficiency decreased to around 60% for organic loading rates of 1 kg COD/m³ d.Applying coagulation–flocculation with iron trichloride or with aluminium polychloride, it was possible to reduce the non-biodegradable organic matter by 73–62% when treating old landfill leachate (COD: 4800 mg/L, BOD₅: 670 mg/L), also reducing turbidity and colour by more than 97%. It is likewise possible to reduce the non-biodegradable organic matter that remains after biological treatment by adsorption with activated carbon, although adsorption capacities are usually low (from 15 to 150 mg COD/g adsorbent). As regards ammonium nitrogen, this can be reduced to final effluent values of 5 mg/L by means of nitrification/denitrification and to values of 126 mg/L by stripping at pH 12 and 48 h of stirring.     

Greenhouse gas emissions from MSW incineration in China: Impacts of waste characteristics and energy recovery

Determination of the amount of greenhouse gas (GHG) emitted during municipal solid waste incineration (MSWI) is complex because both contributions and savings of GHGs exist in the process. To identify the critical factors influencing GHG emissions from MSWI in China, a GHG accounting model was established and applied to six Chinese cities located in different regions. The results showed that MSWI in most of the cities was the source of GHGs, with emissions of 25–207 kg CO₂-eq t^?1 rw. Within all process stages, the emission of fossil CO₂ from the combustion of MSW was the main contributor (111–254 kg CO₂-eq t^?1 rw), while the substitution of electricity reduced the GHG emissions by 150–247 kg CO₂-eq t^?1 rw. By affecting the fossil carbon content and the lower heating value of the waste, the contents of plastic and food waste in the MSW were the critical factors influencing GHG emissions of MSWI. Decreasing food waste content in MSW by half will significantly reduce the GHG emissions from MSWI, and such a reduction will convert MSWI in Urumqi and Tianjin from GHG sources to GHG sinks. Comparison of the GHG emissions in the six Chinese cities with those in European countries revealed that higher energy recovery efficiency in Europe induced much greater reductions in GHG emissions. Recovering the excess heat after generation of electricity would be a good measure to convert MSWI in all the six cities evaluated herein into sinks of GHGs.     

Characterization of PCDD/Fs and heavy metals from MSW incineration plant in Harbin

The characterization of PCDD/Fs and heavy metals in the flue gas and fly ash of Harbin municipal solid waste (MSW) incineration plant, located in the northeast of China, was investigated in this study. The MSW was treated in a twin internal fluidized (TIF) bed incinerator. The results indicate that the emission of PCDD/Fs into the environment is 0.02 ng I-TEQ/m3 and the level of PCDD/Fs in the fabric filter fly ash is 0.7982 ng I-TEQ/g. The leachability levels of Pb, Cd and Hg in the fly ash are below the limits of environmental protection standard in China. However, the contents of Cu, Zn, and Hg are high in the fly ash. This suggests that the fly ash is a hazardous waste that requires special treatment and disposal. The practice of more than four years of operation shows that the TIF bed incinerator is very suitable and practical for China.     

Characterization of a mineral waste resulting from the melting treatment of air pollution control residues

Air pollution control (APC) residues which are generated by municipal solid waste (MSW) incineration show a high-level of pollution potential. In order to stabilize such APC residues, the French power supply company (EDF) is developing a thermal treatment process which leads to the production of a vitrified material. A structural characterization of the vitrified product was carried out by applying complementary investigation methods: XRD, SEM, Raman spectroscopy, EPMA, and data interpretation methods such as mineralogical analysis and principal component analysis (PCA). The major phase of the material was a solid solution of melilite type composed of five end-members: gehlenite (44%), åkermanite (25%), ferri-gehlenite (5%), sodamelilite (14%) and hardystonite (11%). The minor phases identified were spinels and pyroxenes.An ANC leaching test was performed in order to observe the treatment effect on pollutant release. The natural pH was close to 10, and the major element release was less than in the case of untreated APC. This was a consequence of melilite formation. The effect of pH was fundamental for heavy metals release: lower solubilization occurs at pH 10 than at APC’s natural pH (11–12).     

Nylon recovery from carpet waste through pyrolysis under the presence of zinc oxide and the roll-milling treatment

Recycling of carpet waste is not extensively carried out because of its complex combination of materials. A representative type of carpet consists of three layers: nylon fibers, adhesives, and backing materials made of poly(vinyl chloride), PVC. Thermal treatment of carpet waste, thus, leads to the emission of hazardous chlorinated compounds. In the present work, we have employed the one-directional thermal treatment of the backing materials under the presence of zinc oxide, which promotes the thermal degradation of PVC. Nylon fibers could be effectively recovered by the consequent milling treatment from the brittle backing materials. The influence of process parameters, such as pyrolysis temperature and reaction time, on the separation efficiency is discussed.     

Characterization and phosphate stabilization of dusts from the vitrification of MSW combustion residues

The use of soluble PO₄³⁻ as a heavy metal chemical stabilization agent was evaluated for a dust generated from melting or vitrification of municipal solid waste combustion residues. Vitrification dusts contain high concentrations of volatile elements such as Cl, Na, K, S, Pb, and Zn. These elements are present in the dusts largely as simple salts (e.g. PbCl₂, ZnSO₄) which are highly leachable. At an experimental dose of 0.4 moles of soluble PO₄³⁻ per kg of residue, the pH-dependent leaching (pH 5,7,9) showed that the treatment was able to reduce equilibrium concentrations by factors of 3 to 100 for many metals; particularly Cd, Cu, Pb and Zn. Bulk and surface spectroscopies showed that the insoluble reaction products are tertiary metal phosphate [e.g. Zn₃(PO₄)₂] and apatite [e.g. Pb₅(PO₄)₃Cl] family minerals. Geochemical thermodynamic equilibrium modeling showed that apatite family and tertiary metal phosphate phases act as controlling solids for the equilibrium concentrations of Ca²⁺, Zn²⁺, Pb²⁺, Cu²⁺, and Cd²⁺ in the leachates during pH-dependent leaching. Both end members and ideal solid solutions were seen to be controlling solids. Soluble phosphate effectively converted soluble metal salts into insoluble metal phosphate phases despite the relatively low doses and dry mixing conditions that were used. Soluble phosphate is an effective stabilization agent for divalent heavy metals in melting dusts where leachable metals are present in high concentrations.     

Characteristics of products and PCDD/DF emissions from a pyrolysis process of urethane/styrofoam waste from electrical home appliances

A plastic fraction consisting mainly of polyurethane/styrofoam waste is generated after separating valuable spare parts and metals from used electrical home appliances. In Korea, such waste is currently incinerated in cement kilns or is landfilled. However, owing to its high volatile matter content, conversion into gaseous or liquid pyrolysis products is a preferable alternative. A pyrolysis process of polyurethane and styrofoam waste from electrical home appliances was evaluated by characterizing the products generated at 500°–800°C. The para meters determined were the yields of gas, oil, and char; the characteristics of the remaining char; and the con centration of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzo-furans in the product gas. As expected, the char yield decreased at higher temperatures, whereas gas and oil yields showed increasing tendency. The oil products could be used as storable fuels with a calorific value of 6000–8000 kcal/kg. Fine pores were observed in the char. The adsorption and decolorizing ability of the char were almost the same as those of activated carbon, so that pyrolysis char has potential for use as a sorbent. Further feasibility studies will be needed before utilizing pyrolysis technology to recover either fuels or usable products from polyurethane/styrofoam waste.     

垃圾焚烧烟气中二(噁)英零排放技术实践

介绍了绍兴新民热电有限公司用煤和垃圾混烧循环流化床技术处理城市生活垃圾，焚烧烟气经活性炭吸附、半干法和布袋除尘器净化工艺处理后，烟气中二噁英接近零排放。     

Pyrolysis characteristics of bean dregs and in situ visualization of pyrolysis transformation

Biomass is an important renewable and sustainable source of energy. Waste products from biomass are considered as attractive feedstocks for the production of fuel. This work deals with the pyrolysis of bean dregs, a biomass waste from soybean processing industry. A technique has been developed to study bean dregs pyrolysis by in situ visualization of bean dregs transformation in a quartz capillary under a microscope using a charge-coupled device (CCD) camera monitoring system. The technique enables us to observe directly the processes and temperatures of bean dregs transformation during pyrolysis. In situ visualization of reaction revealed that how oily liquids are generated and expulsed concurrently from bean dregs during pyrolysis. Pyrolysis characteristics were investigated under a highly purified N₂ atmosphere using a thermogravimetric analyzer from room temperature to 800 °C at different heating rates of 10, 30 and 50 °C/min. The results showed that three stages appeared in this thermal degradation process. The initial decomposition temperature and the peak shifted towards higher temperature with an increase in heating rate. Kinetic parameters in terms of apparent activation energy and pre-exponential factor were determined.     

Characterisation of the physico-mechanical parameters of MSW

Following the basics of soil mechanics, the physico-mechanical behaviour of municipal solid waste (MSW) can be defined through constitutive relationships which are expressed with respect to three physical parameters: the dry density, the porosity and the gravimetric liquid content. In order to take into account the complexity of MSW (grain size distribution and heterogeneity larger than for conventional soils), a special oedometer was designed to carry out laboratory experiments. This apparatus allowed a coupled measurement of physical parameters for MSW settlement under stress. The studied material was a typical sample of fresh MSW from a French landfill. The relevant physical parameters were measured using a gas pycnometer. Moreover, the compressibility of MSW was studied with respect to the initial gravimetric liquid content. Proposed methods to assess the set of three physical parameters allow a relevant understanding of the physico-mechanical behaviour of MSW under compression, specifically, the evolution of the limit liquid content. The present method can be extended to any type of MSW.     

Leaching characteristics of rare metal elements and chlorine in fly ash from ash melting plants for metal recovery

In terms of resource recovery and environmental impact, melting furnace fly ash (MFA) is attracting much attention in Japan due to its high metal content. The study aims to obtain fundamental information on using a water extraction method not only to concentrate valuable rare metals but also to remove undesirable substances such as chlorine for their recovery from MFA. The composition and leaching characteristics of MFA was investigated. The results revealed that the metal content in MFA is nearly equal to raw ore quality. The content of Ag, In, Pd, Pb, and Zn is, in fact, higher than the content of raw ore. As for leaching behavior, Ag, Bi, In, Ga, Ge, Sb, Sn, and Te showed the lowest release at a neutral pH range. Pd was leached constantly regardless of pH, but its concentration was quite low. On the other hand, most of the Tl was easily leached, revealing that water extraction is not appropriate for Tl recovery from MFA. Major elements Cl, Ca, Na, and K, occupying about 70% of MFA, were mostly leached regardless of pH. Base metal elements Cu, Pb, and Zn showed minimum solubility at a neutral pH. The leaching ratio of target rare metal elements and base metal elements suggests that the optimal pH for water extraction is 8-10, at which the leaching concentration is minimized. The water extraction process removed most of the Cl, Ca, Na, and K, and the concentration of rare metals and base metals increased by four or five times.     

Characteristics of bricks made from waste steel slag

The characteristics of bricks made from steel slag were investigated in this research. Slag addition was shown to reduce the required firing temperature. When the firing temperature was greater than 1050 degrees C and the slag addition less than 10%, the bricks met ROC national standard CNS 3319 third-class brick for builders. The percentage of slag increased as the quartz and kaolin decreased in the sintered samples while the magnesium aluminum silicate and calcium silicate increased. There were no new crystal phases observed in these samples.     

Characterization of syngas produced from MSW gasification at commercial-scale ENERGOS Plants

Characterization of the syngas produced in the gasification process has been performed at commercial-scale Energy-from-Waste plants under various conditions of lambda value and syngas temperature. The lambda value from the gasification process is here defined as the ratio of the gasification air to the total stoichiometric air for complete combustion of the fuel input. Evaluation of the syngas calorific value has been performed by three different methods, i.e., estimation of the syngas calorific value from continuous in-line process measurements by mass and energy conservation equations, measurement of the syngas composition based on gas chromatography and calculation of the Gross Calorific Value from the measured composition, and direct continuous measurement of the calorific value using based on gas calorimeter.