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1.
To study the volatilization and condensation behaviors of low-boiling-point elements in the waste melting process, experiments were conducted to collect the dust from a coke-type incineration residue melting furnace. Then, a comparison was made between the experimental results and the calculated values obtained from a thermodynamic equilibrium model in terms of the chemical composition of the dust. The composition of the dust collected from a cylindrical filter in the exhaust gas duct was determined by chemical methods, scanning electron microscopy/energy-dispersive X-ray spectroscopy, and X-ray analysis. As a result, the sampled dust was classified into two different types: fine particles mainly containing Na, K, Pb, and Zn collected from the side face of the cylindrical filter, and large particles containing Ca, Si, and Al collected from the bottom face of the cylindrical filter. From X-ray analysis of the sampled dust, NaCl, KCl, PbS, and ZnS were identified in the fine-particle dust, while CaO, SiO2, Al2O3 were detected in the large-particle dust. From the results of the thermodynamic equilibrium calculation in the gas cooling process from 2000 to 600 K, it was found that Na, K, Pb, and Zn volatilized as metals in the melting furnace were condensed as alkali chlorides such as NaCl and KCl and heavy metal sulfides such as PbS and ZnS. These computational results were in good agreement with the X-ray diffraction results of the sampled dust at a gas temperature of 823 K for the formation of NaCl, KCl, PbS, and ZnS.  相似文献   

2.
In the process of metal separation by ash-melting, Fe and Cu in the incineration residue remain in the melting furnace as molten metal, whereas Pb and Zn in the residue are volatilized. This study investigated the effects of the chemical composition of incineration fly ash on the metal-separation efficiency of the ash-melting process. Incineration fly ash with different chemical compositions was melted with bottom ash in a lab-scale reactor, and the efficiency with which Pb and Zn were volatilized preventing the volatilization of Fe and Cu was evaluated. In addition, the behavior of these metals was simulated by thermodynamic equilibrium calculations. Depending on the exhaust gas treatment system used in the incinerator, the relationships among Na, K, and Cl concentrations in the incineration fly ash differed, which affected the efficiency of the metal separation. The amounts of Fe and Cu volatilized decreased by the decrease in the molar ratio of Cl to Na and K in the ash, promoting metal separation. The thermodynamic simulation predicted that the chlorination volatilization of Fe and Cu was prevented by the decrease in the molar ratio, as mentioned before. By melting incineration fly ash with the low molar ratio in a non-oxidative atmosphere, most of the Pb and Zn in the ash were volatilized leaving behind Fe and Cu.  相似文献   

3.
Antimony volatilization in municipal waste incineration was studied. Two municipal waste samples and antimony(III) oxide (Sb4O6) were heated to 500°C and 700°C in an air stream in a quartz furnace. The volatilization of Sb4O6 occurred more at 700°C that at 500°C. Conversely, antimony volatilization form municipal waste was stronger at 500°C than at 700°C. This implies that antimony from municipal waste is volatilized as chloride instead of oxide. The chlorine sources for antimony chlorination, a gas-phase reaction involving hydrochloric acid and a solid-phase reaction of inorganic chlorine, e.g., CaCl2, were compared. Only the solid-phase reaction could offer enough active chlorine to induce chlorination of antimony oxide. Received: July 2, 1998 / Accepted: January 28, 1999  相似文献   

4.
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.  相似文献   

5.
The present work focuses on investigation of the effective recovery of heavy metals from molten fly ash by applying chloride-induced volatilization. In particular, the effect of unburned carbon on the chloride-induced volatilization of lead, zinc, and copper from model and real molten fly ashes was investigated in the temperature range 873–1173 K under a N2 atmosphere. As a result, almost 100% of lead and a significant proportion of zinc were volatilized from the real molten fly ash samples at 1173 K. In contrast, for the model fly ash, volatilization ratios of lead and zinc at 1173 K were only 85% and 25%, respectively. Further, the results of X-ray diffraction analysis suggested that PbO in molten fly ash was converted either to Pb2OCl2 or Pb by respective chlorination and reduction reactions. Meanwhile ZnO and CuO in the molten fly ash were reduced to Zn and Cu by reaction with unburned carbon. Subsequently, Pb, Zn, and Pb2OCl2 were volatilized, but Cu remained in the solid residue. Finally, the volatilization ratio of zinc increased with the addition of carbon, and more than 98% of zinc was volatilized at 1173 K from a fly ash with a carbon content of 20%.  相似文献   

6.
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.  相似文献   

7.
This study aimed to identify distribution of metals and the influential factors on metal concentrations in incineration residues. Bottom ash and fly ash were sampled from 19 stoker and seven fluidized bed incinerators, which were selected to have a variety of furnace capacity, furnace temperature, and input waste. In the results, shredded bulky waste in input waste increased the concentration of some metals, such as Cd and Pb, and the effect was confirmed by analysis of shredded bulky waste. During MSW incineration, lithophilic metals such as Fe, Cu, Cr, and Al remained mainly in the bottom ash while Cd volatilized from the furnace and condensed to the fly ash. About two thirds of Pb and Zn was found in the bottom ash despite their high volatility. Finally, based on the results obtained in this study, the amount of metal in incineration residues of MSW was calculated and the loss of metal was estimated in terms of mass and money. A considerable amount of metal was found to be lost as waste material by landfilling of incineration residues.  相似文献   

8.
A thermodynamic calculation was carried out to predict the behavior and speciation of heavy metals (HMs), Pb, Zn, Cu, and Cd, during municipal solid waste (MSW) incineration with the different moisture levels. The calculation was based on the minimization of the total Gibbs free energy of the multi-components and multi-phases closed system reaching chemical equilibrium. The calculation also indicated the reaction directions and tendencies of HMs components. The impacts of chlorine additives (No PVC, 1%PVC, and 5%PVC) and moisture on the behavior of HMs were investigated at different temperature levels in the system (750 °C, 950 °C, and 1150 °C). Furthermore, because the incineration temperature falls down with the increase in moisture in waste, the co-influence of moisture and temperature in combusting MSW on the HMs was also studied with the given chlorine (as 1%PVC + 0.5%NaCl). The results showed that in the non-chlorine system, the impact of the moisture on Pb, Zn, and Cu was not significant, and the ratio of compound transformation was less than 10%, except the Cd compounds at 950 °C and 1150 °C. In the system with low chlorine (as 1%PVC) at constant temperature, the chlorides of HMs (Cd, Pb, Zn, and Cu) transferred to oxides, and when the content of chlorine rose up (as 5%PVC), the ratio of the chlorides of HMs (Cd, Pb, Zn, and Cu) transferring to oxides fell down noticeably. When the moisture varied together with the temperature, the Zn and Cu compounds transferred from chlorides to oxides with increase in moisture as well as decrease in temperature. At the temperature of 700–1000 °C, the impact of temperature on Pb and Cd was little and the moisture was the main factor; while at the temperature of 1000–1200 °C, the impact of increase in moisture and decrease in temperature on Pb and Cd was almost equal and reversed.  相似文献   

9.
This study investigated that water washing effects on the metals emission reduction in melting of municipal solid waste incinerator (MSWI) fly ash. Experimental conditions were conducted at liquid-to-solid (L/S) ratio 10, 20, and 100 for water-washing process and its subsequent melting treatment at 1450 °C for 2 h. The simple water-washing process as a pre-treatment for MSWI fly ash can remove most of the chlorides, leachable salts, and amphoteric heavy metals from the MSWI fly ash, resulting in the washed ash having lowered chlorine content. MSWI fly ashes washed by L/S ratio 10 and above that were melted at 1450 °C produced slag containing relatively high vitrificaton ratio of Cu and Pb. Besides, the vitrification ratios of Na, K, Ca, and Mg in washed MSWI fly ash were also higher than that of MSWI fly ash. The results indicated that washed MSWI fly ash can reduce the emission of metallic chlorides during its subsequent melting treatment.  相似文献   

10.
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.  相似文献   

11.
The End-of-life Vehicles Recycling Act went into effect on January 1, 2005, in Japan and requires the proper treatment of airbags, chlorofluorocarbons (CFCs), and automobile shredder residue (ASR). The need for optimal treatment and recycling of ASR, in particular, has been increasing year after year because ASR is regarded as being difficult to treat. Dioxin-related compounds, brominated flame retardants (BFRs), heavy metals, chlorine and organotin compounds are all present in high concentrations in ASR. The authors conducted ASR melting treatment tests using a 10-tons/day-scale direct melting system (DMS), which employs shaft-type gasification and melting technology. The results obtained showed that dioxin-related compounds and BFRs were decomposed by this melting treatment. The high-temperature reducing atmosphere in the melting furnace moved volatile heavy metals such as lead and zinc into the fly ash where they were distributed at a rate of more than 90% of the input amount. This treatment was also found to be effective in the decomposition of organotin, with a rate of decomposition higher than 99.996% of the input amount. Via the recovery of heavy metals concentrated in the fly ash, all the products discharged from this treatment system were utilized effectively for the complete realization of an ASR recycling system that requires no final disposal sites.  相似文献   

12.
In Japan, melting-furnace fly ash (MFA) generated from ash melting and gasification/melting plants is considered an “urban mine” due to its high metal content. This study aimed to develop a novel approach to pretreating MFA for metal recovery. Water extraction with CO2 bubbling was investigated because MFA mainly consists of water-soluble salts containing elements such as Cl, Ca, Na, and K. Instead of acid addition, CO2 bubbling was applied to maintain the optimal pH for minimizing the release of target metal elements and maximizing the removal of undesirable elements during water extraction. The results revealed that CO2 bubbling effectively decreased the release of Pb, Zn, and Cd into the treatment water. This was mainly due to coprecipitation with CaCO3, which was primarily formed by the reaction of Ca2+ from the MFA with CO3 2− from the CO2 gas. The bubbling process also helped accelerate the removal of Cl from MFA. Furthermore, the study showed that it is possible to lower the water-to-solid ratio to 5 with only a slight reduction in water extraction effect. Finally, approximately four times the concentration of target metals (rare metals and Cu, Pb, and Zn) was achieved by removing 90% of Cl, 70%–90% of Na and K, and 30%–40% of Ca through water extraction with CO2 bubbling, resulting in a concentration of target metals that was nearly equal to that of ore.  相似文献   

13.
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.  相似文献   

14.
The Japanese Government introduced the Law on Recycling of End-of-Life Vehicles (ELV Recycling Law) in 2002. This law requires manufacturers to retrieve chlorofluorocarbons (CFCs), airbags, and automobile shredder residue (ASR) from ELVs and to properly recycle the remaining materials. This framework is compared with European ELV directives. Pilot-scale incineration plant testing has revealed a greater formation of by-product persistent organic pollutants (POPs) during the primary combustion of ASR compared to normal municipal solid waste. This may be attributed to the abundance of chlorine, Cu, and Fe in ASR, as Cu and Fe have been found to catalyze the formation of POPs under certain conditions. However, most by-product POPs were destroyed by the secondary combustion, and almost all were removed after flue gas treatment. The direct melting system is a shaft-type gasification and melting technology that has proved effective in many municipal solid waste applications. This system can be applied to ASR recycling for effective decomposition of brominated flame retardants and polybrominated dioxins.  相似文献   

15.
This study evaluates the effects of co-gasification of municipal solid waste with and without the municipal solid waste bottom ash using two large-scale commercial operation plants. From the viewpoint of operation data, there is no significant difference between municipal solid waste treatment with and without the bottom ash. The carbon conversion ratios are as high as 91.7% and 95.3%, respectively and this leads to significantly low PCDD/DFs yields via complete syngas combustion. The gross power generation efficiencies are 18.9% with the bottom ash and 23.0% without municipal solid waste bottom ash, respectively. The effects of the equivalence ratio are also evaluated. With the equivalence ratio increasing, carbon monoxide concentration is decreased, and carbon dioxide and the syngas temperature (top gas temperature) are increased. The carbon conversion ratio is also increased. These tendencies are seen in both modes.Co-gasification using the gasification and melting system (Direct Melting System) has a possibility to recover materials effectively. More than 90% of chlorine is distributed in fly ash. Low-boiling-point heavy metals, such as lead and zinc, are distributed in fly ash at rates of 95.2% and 92.0%, respectively. Most of high-boiling-point heavy metals, such as iron and copper, are distributed in metal. It is also clarified that slag is stable and contains few harmful heavy metals such as lead. Compared with the conventional waste management framework, 85% of the final landfill amount reduction is achieved by co-gasification of municipal solid waste with bottom ash and incombustible residues. These results indicate that the combined production of slag with co-gasification of municipal solid waste with the bottom ash constitutes an ideal approach to environmental conservation and resource recycling.  相似文献   

16.
 A method of determining the chlorine (Cl) and sulfur (S) in municipal solid waste (MSW) was studied. The quartz furnace method was improved in two ways: recovery from ash by hot extraction with dilute nitric acid, and avoidance of the volatilization of alkali (earth) metal chlorides by setting the sample combustion temperature at 600°C. In a comparison with the bomb method, using nine sets of kitchen garbage and waste plastics, the bomb method yielded a 15%–25% lower value than the improved quartz furnace method. Combustion in the bomb was frequently incomplete, resulting in recovery losses of Cl and S. The average kitchen garbage involved 5.2 mg Cl/g, of which at least 24.1% would be converted to HCl. Plastics contained 23 mg Cl/g generating 88.1% HCl on average. In the same way, kitchen garbage contained 3.0 mg S/g, generating 52.3% SO x , whereas plastics contained 1.1 mg S/g with 55.1% SO x formation. Received: March 20, 2002 / Accepted: October 13, 2002  相似文献   

17.
Cd, Cr, Mn, Ni, Pb, and Zn behaviour during sewage sludge incineration was investigated in seven pilot tests using a circulating fluidised bed furnace. Dewatered sludge at a solids concentration of 15-18% was fed to the furnace either alone (two tests) or spiked with chlorinated organic compounds (five tests). The behaviour of metals in the fluidised bed furnace was studied by comparing metal concentrations in the two main ash streams: ash separated from the cyclone immediately following the fluidised bed furnace, and fly ash recovered in the final bag filter. A metal enrichment factor was defined as the ratio of metal concentration between filter ash and cyclone ash. Only Cd and Pb showed any significant enrichment. Their enrichment factors were mainly affected by chlorine concentration in the feed sludge. To check whether simple equilibrium models may explain and predict metal behaviour, experimental data were compared with percentage of the metal vaporisation in the combustion chamber predicted using a thermodynamic model. Discrepancies between model predictions and experimental results are accounted for by considering that kinetics may be a limiting factor in the formation of metal chloride gaseous species. Due to the very short sludge residence time in the fluidised bed furnace, the gaseous compounds have little chance to evolve completely.  相似文献   

18.
The quantitative evaluation of emissions from incineration is essential when Life Cycle Assessment (LCA) studies consider this process as an end-of-life solution for some wastes. Thus, the objective of this work is to quantify the main gaseous emissions produced when spent AA alkaline batteries are incinerated. With this aim, batteries were kept for 1h at 1273K in a refractory steel tube hold in a horizontal electric furnace with temperature control. At one end of the refractory steel tube, a constant air flow input assures the presence of oxygen in the atmosphere and guides the gaseous emissions to a filter system followed by a set of two bubbler flasks having an aqueous solution of 10% (v/v) nitric acid. After each set of experiments, sulphur, chlorides and metals (As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Tl and Zn) were analyzed in both the solutions obtained from the steel tube washing and from the bubblers. Sulphur, chlorides and metals were quantified, respectively, using barium sulfate gravimetry, the Volhard method and atomic absorption spectrometry (AAS). The emissions of zinc, the most emitted metal, represent about 6.5% of the zinc content in the batteries. Emissions of manganese (whose oxide is the main component of the cathode) and iron (from the cathode collector) are negligible when compared with their amount in AA alkaline batteries. Mercury is the metal with higher volatility in the composition of the batteries and was collected even in the second bubbler flask. The amount of chlorides collected corresponds to about 36% of the chlorine in the battery sleeve that is made from PVC. A considerable part of the HCl formed in PVC plastic sleeve incineration is neutralized with KOH, zinc and manganese oxides and, thus, it is not totally released in the gas. Some of the emissions are predictable through a thermodynamic data analysis at temperatures in the range of 1200-1300K taking into account the composition of the batteries. This analysis was done for most of potential reactions between components in the batteries as well as between them and the surrounding atmosphere and it reasonably agrees the experimental results. The results obtained show the role of alkaline batteries at the acid gases cleaning process, through the neutralization reactions of some of their components. Therefore, LCA of spent AA alkaline batteries at the municipal solid waste (MSW) incineration process must consider this contribution.  相似文献   

19.
Vitrification of electric arc furnace dusts   总被引:6,自引:0,他引:6  
Electric arc furnace baghouse dust (EAFD), a waste by-product of the steelmaking process, contains the elements that are volatilized from the charge during the melting (Cr, Pb, Zn, Cu and Cd). The results of leaching tests show that the concentration of these elements exceeds the regulatory limits. Consequently, EAFD cannot be disposed of in ordinary landfill sites without stabilization of the heavy metals. In this work, the vitrification of EAFD, from both carbon and stainless steel productions, were studied. The vitrification process was selected as the inertizing process because it permits the immobilization of the hazardous elements in the glass network and represents an environmentally acceptable method for the stabilization of this waste. Classes of various compositions were obtained by mixing EAFD with glass cullet and sand. The EAFD and the glass products were characterized by DTA, TG, X-ray analysis and by the TCLP test. The results show that the stability of the product is influenced by the glass structure, which mainly depends on the Si/O ratio. Secondary crystallization heat-treatment were carried out on some samples. The results highlighted the formation of spinel phases, which reduced the chemical durability in acid media. The possibility to recover Zn from carbon steel production EAFD was investigated and about 60-70% of metal recovery was obtained. The resulting glass show higher chemical stability than glasses obtained without metal recovery.  相似文献   

20.
Trace element partitioning in solid waste (household waste, industrial waste, waste wood chips and waste mixtures) incineration residues was investigated. Samples of fly ash and bottom ash were collected from six incineration facilities across Sweden including two grate fired and four fluidized bed incinerators, to have a variation in the input fuel composition (from pure biofuel to mixture of waste) and different temperature boiler conditions. As trace element concentrations in the input waste at the same facilities have already been analyzed, the present study focuses on the concentration of trace elements in the waste fuel, their distribution in the incineration residues with respect to chlorine content of waste and combustion temperature.Results indicate that Zn, Cu and Pb are dominating trace elements in the waste fuel. Highly volatile elements mercury and cadmium are mainly found in fly ash in all cases; 2/3 of lead also end up in fly ash while Zn, As and Sb show a large variation in distribution with most of them residing in the fly ash. Lithophilic elements such as copper and chromium are mainly found in bottom ash from grate fired facilities while partition mostly into fly ash from fluidized bed incinerators, especially for plants fuelled by waste wood or ordinary wood chips. There is no specific correlation between input concentration of an element in the waste fuel and fraction partitioned to fly ash. Temperature and chlorine content have significant effects on partitioning characteristics by increasing the formation and vaporization of highly volatile metal chlorides. Zinc and cadmium concentrations in fly ash increase with the incineration temperature.  相似文献   

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