Evaluation of metals in the residue of paper sludge after recovery of pulp components using an ionic liquid

The quantity of sludge produced by the paper industry in Japan in 2011 was estimated to be 27.91 million tons wet weight. This amount is the third largest among all industrial wastes. To explore ways of reusing recovered paper pulp and safely disposing of the residue, we investigated the distribution of metals in the process of recovery of pulp from two types of paper sludge using an ionic liquid. 32 and 46 % of pulp from paper sludge A and B was recovered using ionic liquid, respectively; the resultant weight reduction of the solid mass was comparable to that of incineration. There were virtually no heavy metals but aluminum in the recovered pulp, which makes its reuse viable at present. The characteristics of the metals in the residues differed according to the treatment used and properties of the paper sludge. Copper accounted for ~10 % in the ionic liquid used for recovery of pulp from the paper sludges. This suggests that [bmIm]Cl has the potential to dissolve a specific amount of copper compared to other metals.     

The adsorption characteristics of heavy metals by various particle sizes of MSWI bottom ash

The incineration rate of municipal solid waste (MSW) has been increased because of difficulty in securing a proper disposal site for MSW in Korea. The advantage of incineration is reduction of the volume of waste; however, significant amounts of bottom ash and fly ash were generated in the incineration process. Their treatment has attracted growing interest because of the potential toxicity of hazardous heavy metals. Generally, heavy metals are less released from bottom ash than from fly ash. In this study the adsorption characteristics of heavy metals were investigated using various particle sizes of MSWI bottom ash. Since bottom ash has a broad particle size distribution, it was sieved to size classes of +20, -20, -48, -80, -100 mesh. Cation exchange capacity (CEC) was analyzed by the ammonium acetate method to evaluate the potential as an adsorbent. The CEC values and surface areas increase as the range of particle size becomes finer. The adsorption experiment was conducted using synthetic (Cu and Ni) and plating rinse water as a function of reaction time (10-180 min), liquid/solid ratio (2-100) and particle size (+20 to -100 mesh), respectively. The adsorption rate increased with decreasing particle size and with increasing liquid/solid ratio; however, the removal efficiency of Cu was higher than that of Ni. In the case of plating rinse water, the adsorption rate decreased sharply at high liquid/solid ratio, and it showed over 80% of adsorption rates for Cu and Ni at an initial pH of 3.     

Impacts of ultrasound on selective leaching recovery of heavy metals from metal-containing waste sludge

Lab synthesized metal-bearing sludge (LSMS) was used in series of designed lab tests to evaluate impacts of ultrasound on selective separation of heavy metals through acid leaching. The tests eliminated the potential of induced bias generated by utilizing field sludge that were produced from different location sources. The results showed that metal pairs of Cu and Fe, Cu and Cr, and Cr and Fe inside LSMS could be practically separated with one metal being contained in a liquid phase and another in a solid phase through acid leaching processes enhanced by ultrasound. With assistance of ultrasound, the acid leaching demonstrated a more efficient segregation between metals within LSMS than a conventional leaching that doesn’t have ultrasonic enhancement, and the tests provided in a generic means that ultrasonically enhanced acid leaching could cost-efficiently recover heavy metals from metal-containing waste sludge.     

Alteration of municipal solid waste incineration bottom ash focusing on the evolution of iron-rich constituents

Municipal solid waste incineration (MSWI) bottom ash contains a considerable amount of Fe-rich constituents. The behaviors of these constituents, such as dissolution and precipitation, are quite important as they regulate the distribution of a series of ions between the liquid (percolated fluid) and solid (ash deposit) phases. This paper studied both fresh and weathered MSWI bottom ash from the mineralogical and geochemical viewpoint by utilizing optical microscopy, scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX), and powder X-ray diffraction. The analysis results revealed that for the fresh bottom ash, iron preferentially existed in the chemical forms of spinel group (mainly Fe(3)O(4), and a series of Al- or Ti- substituted varieties), metallic inclusions (including Fe-P, Fe-S, Fe-Cu-Pb), hematite (Fe(2)O(3)) and unburned iron pieces. In the 1-20 years weathered bottom ash collected from a landfill site, interconversions among these Fe-rich constituents were identified. Consequently, numerous secondary products were developed, including goethite (α-FeOOH), lepidocrocite (γ-FeOOH), hematite, magnetite, wustite (FeO), Fe-Si-rich gel phase. Of all these transformation products, hydrous iron oxides were the most common secondary minerals. Quantitative chemical analysis of these secondary products by SEM/EDX disclosed a strong association between the newly formed hydrous iron oxides and heavy metals (e.g. Pb, Zn, Ni, and Cu). The results of this study suggest that the processes of natural weathering and secondary mineralization contribute to reduction of the potential risks of heavy metals to the surrounding environments.     

Heavy metal release from different ashes during serial batch tests using water and acid

Most ashes contain a significant amount of heavy metals and when released from disposed or used ash materials, they can form a major environmental concern for underground waters. The use of water extracts to assess the easily mobilisable content of heavy metals may not provide an appropriate measure. This study describes the patterns of heavy metal release from ash materials in context with results from the German standard extraction method DIN-S4 (DIN 38 414 S4). Samples of four different ashes (municipal solid waste incineration ash, wood ash, brown coal ash and hard coal ash) were subjected to a number of serial batch tests with liquid renewal, some of which involved the addition of acid to neutralize carbonates and oxides. Release of heavy metals showed different patterns depending on the element, the type of material, the method of extraction and the type of the extractant used. Only a small fraction of the total heavy metal contents occurred as water soluble salts; of special significance was the amount of Cr released from the wood ash. The reaction time (1, 24 or 72 h between each extraction step with water) had only a small effect on the release of heavy metals. However, the release of most of the heavy metals was governed by the dissolution processes following proton inputs, indicating that pH-dependent tests such as CEN TC 292 or others are required to estimate long-term effects of heavy metal releases from ashes. Based on the chemical characteristics of ash materials in terms of their form and solubility of heavy metals, recommendations were made on the disposal or use of the four ash materials.     

Thermochemical treatment of sewage sludge ashes for phosphorus recovery

Phosphorus (P) is an essential element for all living organisms and cannot be replaced. Municipal sewage sludge is a carrier of phosphorus, but also contains organic pollutants and heavy metals. A two-step thermal treatment is suggested, including mono-incineration of sewage sludge and subsequent thermochemical treatment of the ashes. Organic pollutants are completely destroyed by mono-incineration. The resulting sewage sludge ashes contain P, but also heavy metals. P in the ashes exhibits low bioavailability, a disadvantage in farming. Therefore, in a second thermochemical step, P is transferred into mineral phases available for plants, and heavy metals are removed as well. The thermochemical treatment was investigated in a laboratory-scale rotary furnace by treating seven different sewage sludge ashes under systematic variation of operational parameters. Heavy metal removal and the increase of the P-bioavailability were the focus of the investigation. The present experimental study shows that these objectives have been achieved with the proposed process. The P-bioavailability was significantly increased due to the formation of new mineral phases such as chlorapatite, farringtonite and stanfieldite during thermochemical treatment.     

Kinetic vaporization of heavy metals during fluidized bed thermal treatment of municipal solid waste

Heavy metals volatilization during thermal treatment of model solid waste was theoretically and experimentally investigated in a fluidized bed reactor. Lead, cadmium, zinc and copper, the most four conventional heavy metals were investigated. Particle temperature model and metal diffusion model were established to simulate the volatilization of CdCl₂ evaporation and investigate the possible influencing factors. The diffusion coefficient, porosity and particle size had significant effects on metal volatilization. The higher diffusion coefficient and porosity resulted in the higher metal evaporation. The influence of redox conditions, HCl, water and mineral matrice were also investigated experimentally. The metal volatilization can be promoted by the injection of HCl, while oxygen played a negative role. The diffusion process of heavy metals within particles also had a significant influence on kinetics of their vaporization. The interaction between heavy metals and mineral matter can decrease metal evaporation amount by forming stable metallic species.     

The BATINTREC process for reclaiming used batteries

The Integrated Battery Recycling (BATINTREC) process is an innovative technology for the recycling of used batteries and electronic waste, which combines vacuum metallurgical reprocessing and a ferrite synthesis process. Vacuum metallurgical reprocessing can be used to reclaim the mercury (Hg) in the dry batteries and the cadmium (Cd) in the Ni-Cd batteries. The ferrite synthesis process reclaims the other heavy metals by synthesizing ferrite in a liquid phase. Mixtures of manganese oxide and carbon black are also produced in the ferrite synthesis process. The effluent from the process is recycled, thus significantly minimizing its discharge. The heavy metal contents of the effluent could meet the Integrated Wastewater Discharge Standard of China if the ratio of the crushed battery scrap and powder to FeSO4.7H2O is set at 1:6. This process could not only stabilize the heavy metals, but also recover useful resource from the waste.     

Carbonization of johkasou sludge using batch-type equipment

The carbonization of dehydrated johkasou sludge was examined using batch-type equipment. Based on the temperature changes in the carbonization room and the gas combustion room, the carbonization process was divided into three phases: phase I, drying the sludge; phase II, thermal decomposition of the dried sludge; phase III, after phase II. The times required for phases I and II were strongly correlated with the amounts of water and solid matter, respectively, in dehydrated sludge. The reduction rate of the sludge on completion of phase I was about 90% on average, and the decomposition rate of solid matter increased with time during phase II or phase II plus phase III until it reached about 50%. TOC concentration of the eluate from the carbonized sludge was used as an index to evaluate the progress of the carbonization process, and the highest temperature in the carbonization room was recognized as an important operational factor. The specific surface area and pore volume of carbonized sludge were smaller than those of charcoals and activated carbons by 1–3 orders of magnitude and 1–2 orders of magnitude, respectively. No elution of heavy metals was observed from any of the carbonized sludges examined. The reduced amount of carbon in dehydrated johkasou sludge was estimated to be about 25% of the decomposed organic matter.     

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.     

Cement clinker: An environmental sink for residues from hazardous waste treatment in cement kilns

About 70% of all of the liquid and solid hazardous wastes commercially incinerated in the United States is being burned in cement kilns. The process inevitably results in residues, primarily heavy metals, entering the clinker and waste dusts (cement kiln dust, CKD) produced by these kilns. The effects of this trend on the nature and chemical composition of cement, actual and future, are discussed. The wastes burned by cement kilns are expected to increasingly have higher levels of heavy metals per Btu. In general, the effects are very simple to describe but have as yet unknown consequences. The present American Society for Testing and Materials (ASTM) standard does not effectively control hazardous waste burning residues in Portland Cement.The regulatory and economic pressures on CKD disposal suggest that much of it, and its heavy metal residues, will, in time, end up in the clinker and the resultant cement. The end point to the trend is the ability to make cement that passes the performance specifications while containing high levels of heavy metals. The only other alternative is to maximize the levels of heavy metals in the CKD, minimize the amount of CKD, and dispose of its as a hazardous waste.It is recommended that an effort to correlate heavy metal levels in clinker with adverse effects be undertaken, a new standard for cement containing hazardous and other waste residuals be developed, and labeling be required.     

Assessment of biotechnological strategies for the valorization of metal bearing wastes

The present work deals with the application of biotechnology for the mobilization of metals from different solid wastes: end of life industrial catalysts, heavy metal contaminated marine sediments and fluorescent powders coming from a cathode ray tube glass recycling process. Performed experiments were aimed at assessing the performance of acidophilic chemoautotrophic Fe/S-oxidizing bacteria for such different solid matrices, also focusing on the effect of solid concentration and of different substrata. The achieved results have evidenced that metal solubilization seems to be strongly influenced by the metal speciation and partitioning in the solid matrix. No biological effect was observed for Ni, Zn, As, Cr mobilization from marine sediments (34%, 44%, 15%, 10% yields, respectively) due to metal partitioning. On the other hand, for spent refinery catalysts (Ni, V, Mo extractions of 83%, 90% and 40%, respectively) and fluorescent powders (Zn and Y extraction of 55% and 70%, respectively), the improvement in metal extraction observed in the presence of a microbial activity confirms the key role of Fe/S oxidizing bacteria and ferrous iron. A negative effect of solid concentration was in general observed on bioleaching performances, due to the toxicity of dissolved metals and/or to the solid organic component.     

Thermal and hydrometallurgical recovery methods of heavy metals from municipal solid waste fly ash

Heavy metals in fly ash from municipal solid waste incinerators are present in high concentrations. Therefore fly ash must be treated as a hazardous material. On the other hand, it may be a potential source of heavy metals. Zinc, lead, cadmium, and copper can be relatively easily removed during the thermal treatment of fly ash, e.g. in the form of chlorides. In return, wet extraction methods could provide promising results for these elements including chromium and nickel. The aim of this study was to investigate and compare thermal and hydrometallurgical treatment of municipal solid waste fly ash. Thermal treatment of fly ash was performed in a rotary reactor at temperatures between 950 and 1050 °C and in a muffle oven at temperatures from 500 to 1200 °C. The removal more than 90% was reached by easy volatile heavy metals such as cadmium and lead and also by copper, however at higher temperature in the muffle oven. The alkaline (sodium hydroxide) and acid (sulphuric acid) leaching of the fly ash was carried out while the influence of temperature, time, concentration, and liquid/solid ratio were investigated. The combination of alkaline-acidic leaching enhanced the removal of, namely, zinc, chromium and nickel.     

Leaching of heavy metals by citric acid from fly ash generated in municipal waste incineration plants

The leaching behavior of heavy metals from municipal waste incineration (MWI) fly ash was investigated in this study. The leaching process includes two steps, i.e., fly ash was firstly washed with water, and then subjected to citric acid leaching. The main parameters of the washing process such as liquid/solid ratio, washing time, and number of washing were tested. The optimum conditions for water washing were found as follows: washing time 5–10 min, liquid/solid ratio 10:1 (ml:g), and number of washing was twice; under these conditions, 86% Na, 70% K, 12% Ca, 1.2% Al, and 0.5% Pb were removed from the fly ash in the prewashing. From the results of screening tests of leaching lixiviants, citric acid was found to be the most effective leaching agent, taking account of its environmentally benign characteristics. Optimum metal extraction can be achieved with citric acid under the following conditions: pH 3.0, liquid/solid ratio 40 (ml:g), citric acid concentration 0.10 mol/dm³, contact time 20 min at room temperature.     

Impact of moisture on volatility of heavy metals in municipal solid waste incinerated in a laboratory scale simulated incinerator

In this work, the impact of moisture on the volatility of heavy metals present in municipal solid wastes (MSW) in a laboratory scale simulated incinerator was studied, using synthetic waste consisting of 5.4 g of wood powder, 2.6 g lava, 1.9 polythene, 0.19 g polyvinyl chloride, and a given quantity of water and heavy metals represented by lead, zinc and copper in forms of metallic, chlorides and oxides. It is found that the presence of high moisture in MSW will greatly reduce the volatilization of heavy metals in MSW in the incineration process. The volatilization behavior of chlorides, oxides and the metallic species with respect to the effect of moistures is quite different. For copper, the presence of moisture in MSW depresses the volatilization of oxides, and increases that of chloride and the metallic species, while in contrast, the volatilization of both lead and zinc is always depressed by the presence of moisture in MSW, regardless of the chemical forms used. The chemical mechanisms, which govern the volatilization behaviors of different chemical forms in the incineration process, are proposed. Hydrolysis, dewatering of hydrolyzed species, sublimation, chemical transformation of less volatiles to more volatiles or reverse, may participate in and affect the volatilization of heavy metals in MSW.     

Treatment of mixed contamination in water using cyclodextrin‐based materials

This study investigated the effectiveness of a cyclodextrin‐based solid material for the removal of mixed dissolved contaminants. The solid material was prepared by condensation of α‐cyclodextrin. The removal efficiency was found to be 70 percent for total heavy metals (cadmium, lead, chromium, iron, nickel, cobalt, and mercury) to 98 percent for polychlorinated biphenyls (PCBs). The optimum pH for heavy metal removal was approximately 5 and for PCBs it was in the range of 5–7. All of these heavy metals were successfully recovered from the spent cyclodextrin‐based material using nitric acid, allowing the material to be reused for further passes. The results also showed that the presence of alkaline and alkaline earth metals did not have a significant effect on the removal efficiency, indicating that the cyclodextrin‐based material could selectively remove the heavy metals of concern without being consumed by alkaline and alkaline‐earth metals. © 2006 Government of Canada.     

Immobilisation of heavy metal in cement-based solidification/stabilisation: a review

Heavy metal-bearing waste usually needs solidification/stabilization (s/s) prior to landfill to lower the leaching rate. Cement is the most adaptable binder currently available for the immobilisation of heavy metals. The selection of cements and operating parameters depends upon an understanding of chemistry of the system. This paper discusses interactions of heavy metals and cement phases in the solidification/stabilisation process. It provides a clarification of heavy metal effects on cement hydration. According to the decomposition rate of minerals, heavy metals accelerate the hydration of tricalcium silicate (C3S) and Portland cement, although they retard the precipitation of portlandite due to the reduction of pH resulted from hydrolyses of heavy metal ions. The chemical mechanism relevant to the accelerating effect of heavy metals is considered to be H+ attacks on cement phases and the precipitation of calcium heavy metal double hydroxides, which consumes calcium ions and then promotes the decomposition of C3S. In this work, molecular models of calcium silicate hydrate gel are presented based on the examination of 29Si solid-state magic angle spinning/nuclear magnetic resonance (MAS/NMR). This paper also reviews immobilisation mechanisms of heavy metals in hydrated cement matrices, focusing on the sorption, precipitation and chemical incorporation of cement hydration products. It is concluded that further research on the phase development during cement hydration in the presence of heavy metals and thermodynamic modelling is needed to improve effectiveness of cement-based s/s and extend this waste management technique.     

Monitoring the stabilization of municipal solid waste incineration fly ash by phosphation: mineralogical and balance approach

The application of a micro-characterization protocol coupled with a balance approach has allowed the relevant monitoring of a phosphation process for fly ash produced by municipal solid waste incineration. The three main steps of this process consist in removing the salts (chlorides, sulfates) by dissolution at basic pH, phosphation of the residue to trap metals, and its calcination to destroy dioxin-like compounds. The chemical and mineralogical balances compiled on the samples after each step of the process validate these main objectives and highlight the wide phosphorus distribution throughout the sample during the phosphation process, as well as the formation of apatite-type crystallized phosphates. During calcination, the increase in the proportion of crystallized phosphates apatite and whitlockite is largely attributable to the presence of an available calcium source, corresponding to the calcite formed during washing. The metals Pb and Zn, initially distributed in the silicate and carbonate phases, are broadly redistributed in the phosphate neoformations after carbonate dissolution, thus guaranteeing a more permanent stabilization.     

气化炉渣的重金属浸出特性及化学形态分析

分别采用硫酸硝酸法、水平振荡法和醋酸缓冲溶液法制取气化炉渣的浸出液,考察了不同提取方式对浸出液中重金属质量浓度的影响。采用改进BCR连续提取法对气化炉渣中的重金属Cr,Zn,Cu,Pb,Ni,As,Cd的化学形态进行了分析。实验结果表明：煤气化工艺中的气化炉渣属第Ⅰ类一般工业固体废物;在3种提取方式中,醋酸缓冲溶液法的重金属浸出种类最多,且浸出量最大;Cd和Cr对环境具有较高的潜在危害性,Cu次之,Zn,Pb,Ni,As主要以残渣态形式存在,对环境的直接危害性较低。     

A lysimeter experimental study and numerical characterisation of the leaching of incinerator bottom ash waste

Incinerator bottom ash (IBA) is a residual produced from incinerating municipal solid waste. In the past, IBA presented a big waste disposal problem; however, various recycling approaches have been adopted in recent years to mitigate this problem, as well as to provide a useful alternative to using primary aggregate resources. The use of IBA as an alternative to conventional aggregates in different civil engineering construction applications helps to conserve premium grade aggregate supplies; however, when IBA is in contact with water in the field, as a consequence of precipitation events or changes in water table, elements, such as salts and heavy metals, may be released to the soil and ground water. In this work, IBA waste was mixed with limestone aggregate to produce a blend with acceptable mechanical properties and minimum environmental risks for use as road foundation. The study focused on evaluating potential environmental impacts of some constituents, including sulphate, chloride, sodium, copper, zinc and lead in IBA blends using a lysimeter as a large scale leaching tool. Moreover, a specific scenario simulating field conditions was adopted in the lysimeter to assess the potential impact of changing conditions, such as IBA content in the blend, liquid to solid ratio (L/S) and pH value, on long-term release of heavy metals and salts. Then, numerical modelling was used to predict the release of the aforementioned constituents from IBA based on initial measurement of intrinsic material properties and the kinetic desorption process concept. Experimental results showed that zinc and lead were released in very low concentrations but sodium and sulphate were in high concentrations. The control limestone only blend also demonstrated low release concentrations of constituents in comparison to IBA blends, where constituent concentrations increased with increase in IBA content. Experimental results were compared with numerical results obtained using a non-equilibrium desorption model. Good agreement was found between the two sets of data.