Vitrification for reclaiming spent alkaline batteries

The object of this study is to stabilize spent alkaline batteries and to recover useful metals. A blend of dolomite, limestone, and cullet was added to act as a reductant and a glass matrix former in vitrification. Specimens were vitrified using an electrical heating furnace at 1400 °C and the output products included slag, ingot, flue gas, and fly ash. The major constituents of the slag were Ca, Mn, and Si, and the results of the toxicity leaching characteristics met the standards in Taiwan. The ingot was a good material for use in production of stainless steel, due to being mainly composed of Fe and Mn. For the fly ash, the high level of Zn makes it economical to recover. The distribution of metals indicated that most of Co, Cr, Cu, Fe, Mn, and Ni moved to the ingot, while Al, Ca, Mg, and Si stayed in the slag; Hg vaporized as gas phase into the flue gas; and Cd, Pb, and Zn were predominately in the fly ash. Recovery efficiency for Fe and Zn was >90% and the results show that vitrification is a promising technology for reclaiming spent alkaline batteries.     

TSP,PM<Subscript>10</Subscript> and health risk assessment for heavy metals (Cr,Ni, Cu,Zn, Cd,Pb) in the ambience of the production line for waste cathode ray tube recycling

Recently, a typical semi-automatic recycling line is proved to be a feasible method for resource recovery of raw material of waste CRTs. However, there are no relevant studies about health risk assessment of the particles and heavy metals diffused from this physical recycling process for CRTs. In this study, TSP, PM₁₀ and heavy metals (Cr, Ni, Cu, Zn, Cd and Pb) in the ambience of the workshop have been evaluated. The mean concentrations of TSP and PM₁₀ in the workshop were 481.5 and 316.9 μg/m³, respectively. Meanwhile, it can be seen that Zn (8.1 and 7.9 μg/m³, respectively) was the most enriched metal in TSP and PM₁₀, followed by Pb (3.2 and 3.0 μg/m³, respectively). Health risk assessment showed that the total hazard index was 3.29, exceeding the danger threshold. The health risk of different metals was Cr > Cd > Ni. In short, the research results show that mechanical–physical process for e-waste recycling do exist the pollutant mission. So the effective measures should be taken to reduce the harm of pollutants on the workers’ health.     

Mercury flows in a zinc smelting facility in South Korea

To prepare for the international mercury convention, the characteristics of mercury emissions from a zinc smelting facility in South Korea have been reviewed and a material flow analysis (MFA) has been conducted in this research. As inputs into the mercury MFA study, zinc ores and sulfuric acid were examined, whereas wastewater sludge, effluence water, spent catalyst, and emissions from the casting and roasting processes were examined as outputs. Mercury concentrations extracted from end products like zinc ingots, cadmium ingots, and sulfuric acid were then analyzed. Our results showed that the wastewater sludge discharged from the zinc smelting process had a relatively higher concentration of mercury, indicating that the concentration of mercury was further enriched in the wastewater sludge. The wastes discharged through the zinc smelting process should be thoroughly controlled, as results of the MFA showed that approximately 89 % of the mercury contained in the original input was later found in the waste. According to this study, the higher the concentration of mercury within zinc ores at the input stage, the higher is the mercury concentration found in the wastewater sludge at the output stage.     

Semi-technical demonstration of the 3R process

The 3R Process: (1) recovers fly ash and HCl from the flue gases; (2) removes heavy metals from the fly ash by extraction with HCl; (3) and returns a pelletized fly ash to the incinerator. Recoveries of about 90% of the Cd, 65% of the Zn and 20% of the Pb and Cu have been achieved in pilot tests. Full scale experiments proved the thermal decomposition of PCDD/PCDF. The 3R products meet the Swiss elution requirements.     

Mercury Capture on Fly Ash and Sorbents: The Effects of Coal Properties and Combustion Conditions

The US fleet of coal-fired power plants, with generating capacity of just over 300 GW, is known to be a major source of domestic mercury (Hg) emissions. To address this, in March 2005, the Environmental Protection Agency (EPA) promulgated the Clean Air Mercury Rule (CAMR) to reduce emissions of mercury from these plants. It is generally believed that most of the initial (Phase I) mercury reductions will come as a co-benefit of existing controls used to remove particulate matter (PM), SO₂, and NO _X . Deeper reductions in emissions (as required in Phase II of CAMR) may require the installation of mercury-specific control technology. Duct injection of activated carbon sorbents is the mercury-specific control technology that has been most widely studied and has been demonstrated over a wide range of coal types and combustion conditions. The effectiveness of the mercury control options (both “co-benefit control” and “mercury-specific control”) is significantly impacted by site-specific characteristics such as the combustion conditions, the configuration of existing air pollution controls, and the type of coal burned. This paper identifies the role of coal properties and combustion conditions in the capture of mercury by fly ash and injected sorbents.     

Removal of mercury from flue gas using sewage sludge-based adsorbents

Mercury from coal-fired utility boilers, as the largest atmospheric mercury emission source, imposes serious environmental risks and health concerns. In order to explore the possibility of reducing costs of activated carbon injection, we investigated the most promising mercury control technology, Hg⁰ removal using ZnCl₂-impregnated adsorbents derived from sewage sludge. The results demonstrated that sludge-based adsorbents (SBAs) had fairly high mercury adsorption capacity over a wide range of temperatures (80–170 °C). Oxidizing atmosphere could improve the adsorption of Hg⁰ and weaken the inhibition of SO₂ on mercury adsorption to some extent. NO exhibited no obvious impact on mercury removal performance. In addition, to clarify whether oxygen- or chlorine-containing functional groups attributed to good mercury adsorption capacity of SBAs, the oxygen-containing functional groups were removed using Boehm’s method, and a temperature-programmed decomposition desorption experiment was conducted. The results suggest that chlorine-containing functional groups played a significant role in the removal process of mercury from flue gas using SBAs.     

Heavy metals in domestic refuse and their distribution in incinerator residues

The principal heavy metal loads to municipal solid waste incinerators are determined from analyses of bottom ash, fly ash and gaseous effluents. Upper values in g per Mg refuse are: Cl, 8000; F, 200; S, 5000; Zn, 2000; Pb, 1200; Cu, 600; Cr, 250; Ni, 80; Cd, 15; Hg, 5; As, 4. More than half of the Cl, Cd, Hg and As pass into the flue gas and are either captured in the fly ash or emitted in the stack gas.     

The effect of the addition of fly ash to municipal digested sludge on its electroosmotic dewatering

Effective handling of municipal digested sludge requires that the product cake have low water content. To this end, we investigated the change in sludge dewaterability after the addition of fly ash to municipal digested sludge, dewatering of which is difficult because of its high organic content. The performance of the dewatering is compared with that of electroosmotic dewatering (EDW) and conventional mechanical dewatering (CMD). Fly ash classified by sieving to the size of 25–75 μm and >75 μm is added to the municipal digested sludge by 10, 20, and 50 wt% by wet base. When adding fly ash particles to municipal digested sludge, dewatering efficiency improved with smaller fly ash particle size and with increase in the amount. When sludge was dewatered using an electroosmotic dewatering method, the dewatering efficiency is improved about 40% by adding fly ash of 25–75 μm particle size with 20 wt% when compared with conventional mechanical dewatering method without adding the fly ash. It is concluded that fly ash particles rich in inorganic material are helpful in the dewatering process when added to municipal digested sludge and EDW is more effective than CDW.     

The potential of SO2 for reducing corrosion in WtE plants

Due to the high-temperature boiler corrosion induced by chloride-rich fly ash deposits, steam generation in today’s Waste-to-Energy (WtE) plants is typically designed only for 40 bar/400 °C as an economic compromise between acceptable corrosion rate and maximum power generation. The high-corrosive metal chlorides in the fly ash can react with SO₂ forming low-corrosive sulfates. The sulfation efficiency is enhanced by high SO₂ levels and sufficient residence time of the flue gas at high-temperatures (700–900 °C). The fly ash sulfation was tested in full scale in a Swedish WtE plant by applying the economic sulfur recirculation method. Probes of several alloys (16Mo3, Inconel 625, Sanicro 28) were exposed for 1000 h at controlled material temperatures in the superheater position, at normal and during sulfating operation respectively. Analyses of the fly ash showed that the molar Cl/S was decreased to values well below 1 and the corresponding corrosion rates of the individual material samples were less than half when sulfur recirculation was in operation. These positive findings demonstrate that the sulfur recirculation process has high potential for low-corrosive high-temperature steam generation (T ≈ 500 °C) and improved electricity production. Further steam superheating can be realized by staged superheating using small amounts of secondary fuel.     

Heavy metal speciation in various types of fly ash from municipal solid waste incinerator

Fly ash (FA) from municipal solid waste incinerators has been known as hazardous waste, which is mostly because of the high content of heavy metal and dioxins. Besides the content, the form of the heavy metals in fly ash is also very important, because it is tightly related with the leaching behavior of fly ash in diverse circumstances. To evaluate the environment potential risk of fly ash, the Tessier chemical extraction method was adopted. In this study, four kinds of fly ash were examined, one sample from China (CFA) and the other three from Japan (RFA, CaFA and NaFA). Five metal elements were detected and they were Ni, Cr, Cd, Pb, and Cu. The result of total heavy metals’ concentration showed CFA has the lowest content. As to the Tessier chemical extraction experiments, the results show that Cd, Pb, and Cu have higher leaching risk in the environment than other heavy metals. The result of leaching test experiment showed that the more exchangeable speciation of Cd, Cr and Pb in FA, the more it could leach out in natural environment.     

Behaviour of Cd,Cr, Mn,Ni, Pb,and Zn in sewage sludge incineration by fluidised bed furnace

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.     

Mercury leaching characteristics of waste treatment residues generated from various sources in Korea

In this study, mercury (Hg) leaching characteristics of the waste treatment residues (fly ash, bottom ash, sludge, and phosphor powder) generated from various sources (municipal, industrial, medical waste incinerators, sewage sludge incinerator, oil refinery, coal-fired power plant, steel manufacturing plant, fluorescent lamp recycler, and cement kiln) in Korea were investigated. First, both Hg content analysis and toxicity characteristic leaching procedure (TCLP) testing was conducted for 31 collected residue samples. The Hg content analysis showed that fly ash from waste incinerators contained more Hg than the other residue samples. However, the TCLP values of fly ash samples with similar Hg content varied widely based on the residue type. Fly ash samples with low and high Hg leaching ratios (R_L) were further analyzed to identify the major factors that influence the Hg leaching potential. Buffering capacity of the low-R_L fly ash was higher than that of the high-R_L fly ash. The Hg speciation results suggest that the low-R_L fly ashes consisted primarily of low-solubility Hg compounds (Hg₂Cl₂, Hg⁰ or HgS), whereas the high-R_L fly ashes contain more than 20% high-solubility Hg compounds (HgCl₂ or HgSO₄).     

Feasibility of a monitoring system for detecting changes in dioxin concentrations of both in flue gas and fly ash in incineration plants

Surrogate measurements should be low in cost and quick to perform. To examine its feasibility, continuous surrogate monitoring was performed using an organic halogen compound (OHC) analyzer. Surrogates for dioxins (DXNs) from waste incinerators were examined by changing the operating conditions such as the atomized volume of activated carbon added and the temperature at the inlet of the dust collector. OHCs were measured along with DXNs in flue gas at the inlet and the outlet of the dust collector of two waste incinerators over five runs; the fly ash was sampled at the same time. Although the final flue gas concentration of DXNs at the incineration plants was below the regulation criteria, this does not mean complete reduction of DXNs. In addition, the de novo synthesis of DXNs inside the dust collectors was studied by analyzing the mass balance for DXNs concentrations in flue gas and fly ash. Semivolatile chlorinated organic compound concentrations at the outlet of the bag filter were basically well correlated with DXNs levels at the inlet of the bag filter in the test runs. When advanced flue gas treatment is applied by using a bag filter and lime/activated carbon adsorbent, DXNs that may be generated during flue gas cooling processes move to the fly ash, and this amount determines the mass balance of the entire system. It may be useful to monitor surrogate organic halogens for detecting changes in DXN concentrations of both flue gas and fly ash in incineration plants.     

Sludge as dioxins suppressant in hospital waste incineration

Nitrogen containing compounds such as ammonia, urea and amines can effectively inhibit the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Sewage sludge accumulates both sulfur and nitrogen during wastewater treatment so it could be used to reduce PCDD/Fs formation. Indeed, it is observed in this study that the gas evolving from the sludge drying process can significantly suppress chlorobenzene (CBz) and PCDD/Fs formation from fly ash collected from a hospital waste incinerator. For instance, the reduction of hexachlorobenzene (HxCBz) and PCDD/Fs amount was 92.1% and 78.7%, respectively, when the drying gas evolving from 2g sludge flew through 2g fly ash. These tests were conducted in the frame of projects devoted to hospital waste incineration. The disposal technology for hospital waste (HW), developed in this institute, features rotary kiln pyrolysis combined with post-combustion followed by flue gas cleaning. Hence, some preliminary tests were devoted to investigate dioxins suppression by co-pyrolysis and co-combustion of polyvinyl chloride (PVC) and sludge in lab scale. More experimental research will be conducted to appropriately assess these effects of sludge on PCDD/Fs emissions during co-pyrolysis/combustion of HW and sludge.     

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.     

Sludge earthworm composting technology by Eisenia fetida

Prior to vermicompost application to the soils, there is a need to determine the heavy metal concentrations in the final vermicomposts. Acute toxicity on Eisenia fetida for copper (Cu) and cadmium (Cd) were conducted by artificial soils tests. The dosage of interest is typically the median lethal concentration (LC₅₀) that will kill 50 % of the population of organisms within the test period. The dry artificial soil is pre-moistened 1 or 2 days before the test by adding deionized water to obtain approximately half of the required final water content of 40–60 % of the maximum water holding capacity. The 14-day LC₅₀ values (95 % confidence interval) for Cu and Cd were 530 (450–624) and 1118 (988–1265) mg kg^?1, respectively. The vermicomposting was designed to evaluate the effects of earthworm activity on heavy metals in sewage sludge. Compared with the sludge before vermicomposting by Eisenia fetida, the results are as follows: (1) water content, the pH value and organic matter content decreased, (2) total nitrogen content increased, total phosphorus content and total potassium content decreased, (3) available nitrogen concentration, available phosphorus content increased, and (4) the total content of five metals (Cu, Ni, Cd, Pb and Zn) decreased, and the bioaccumulation factor shows that vermicomposting can efficiently remove heavy metals. Therefore, it can be concluded that the soil use of sludge of the Wastewater Treatment Plant in Huaibei is feasible.     

Effect of unburned carbon on lead, zinc, and copper recovery from molten fly ash by chloride-induced volatilization

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%.     

Accumulation and fate of selected heavy metals in a biological wastewater treatment system

The aim of this research was to study the accumulation and removal of heavy metals (Cd, Cu, Pb, Zn) by a biological wastewater treatment system. Heavy metal contents in the influent and effluent wastewater were compared. Also, the heavy metal contents in the sludge before and after anaerobic digestion were compared. The results showed: (1) more pronounced variations in the contents of Cu and Zn than that of Cd and Pb, which showed that at 0.02 for Cd and 0.05 mg/l for Pb, the reduction in their contents was insignificant; (2) that removal of heavy metals was directly proportional to their initial contents in the influent wastewater. Corresponding to the influent contents, in increasing order, the reduction in heavy metal contents was: Cd相似文献   

Influence of calcium chloride on the thermal behavior of heavy and alkali metals in sewage sludge incineration

In order to separate and reuse heavy and alkali metals from flue gas during sewage sludge incineration, experiments were carried out in a pilot incinerator. The experimental results show that most of the heavy and alkali metals form condensed phase at temperature above 600 degrees C. With the addition of 5% calcium chloride into sewage sludge, the gas/solid transformation temperature of part of the metals (As, Cu, Mg and Na) is evidently decreased due to the formation of chloride, while calcium chloride seems to have no significant influence on Zn and P. Moreover, the mass fractions of some heavy and alkali metals in the collected fly ash are relatively high. For example, the mass fractions for Pb and Cu in the fly ash collected by the filter are 1.19% and 19.7%, respectively, which are well above those in lead and copper ores. In the case of adding 5% calcium chloride, the heavy and alkali metals can be divided into three groups based on their conversion temperature: Group A that includes Na, Zn, K, Mg and P, which are converted into condensed phase above 600 degrees C; Group B that includes Pb and Cu which solidify when the temperature is above 400 degrees C; and Group C that includes As, whose condensation temperature is as low as 300 degrees C.     

Flue gas desulfurization gypsum and coal fly ash as basic components of prefabricated building materials

The manufacture of prefabricated building materials containing binding products such as ettringite (6CaO·Al₂O₃·3SO₃·32H₂O) and calcium silicate hydrate (CSH) can give, in addition to other well-defined industrial activities, the opportunity of using wastes and by-products as raw materials, thus contributing to further saving of natural resources and protection of the environment.Two ternary mixtures, composed by 40% flue gas desulfurization (FGD) gypsum or natural gypsum (as a reference material), 35% calcium hydroxide and 25% coal fly ash, were submitted to laboratory hydrothermal treatments carried out within time and temperature ranges of 2 h–7 days and 55–85 °C, respectively. The formation of (i) ettringite, by hydration of calcium sulfate given by FGD or natural gypsum, alumina of fly ash and part of calcium hydroxide, and (ii) CSH, by hydration of silica contained in fly ash and residual lime, was observed within both the reacting systems. For the FGD gypsum-based mixture, the conversion toward ettringite and CSH was highest at 70 °C and increased with curing time. Some discrepancies in the hydration behavior between the mixtures were ascribed to differences in mineralogical composition between natural and FGD gypsum.