污泥灰中磷的湿化学法回收技术研究进展

从污泥灰中磷的提取、磷与重金属的分离和磷产品的制备3方面综述了国内外湿化学法回收污泥灰中磷的研究进展,重点分析了磷提取过程中的各种影响因素,并对今后污泥灰中磷的湿化学法回收技术的研究方向进行了展望。指出:利用萃取的方法将提取液中的无机强酸萃取出来并回收重复利用,可大幅降低酸的消耗量;在回收磷的同时可研究回收不同种类金属的方法,尤其是价值较大的重金属,以进一步提高污泥灰资源的回收价值。     

Simultaneous recovery of vanadium and nickel from power plant fly-ash: Optimization of parameters using response surface methodology

Simultaneous recovery of vanadium (V) and nickel (Ni), which are classified as two of the most hazardous metal species from power plant heavy fuel fly-ash, was studied using a hydrometallurgical process consisting of acid leaching using sulfuric acid. Leaching parameters were investigated and optimized in order to maximize the recovery of both vanadium and nickel. The independent leaching parameters investigated were liquid to solid ratio (S/L) (5–12.5 wt.%), temperature (45–80 °C), sulfuric acid concentration (5–25 v/v%) and leaching time (1–5 h). Response surface methodology (RSM) was used to optimize the process parameters. The most effective parameter on the recovery of both elements was found to be temperature and the least effective was time for V and acid concentration for Ni. Based on the results, optimum condition for metals recovery (actual recovery of ca.94% for V and 81% for Ni) was determined to be solid to liquid ratio of 9.15 wt.%, temperature of 80 °C, sulfuric acid concentration of 19.47 v/v% and leaching time of 2 h. The maximum V and Ni predicted recovery of 91.34% and 80.26% was achieved.     

Feasibility study of the separation of chlorinated films from plastic packaging wastes

This study describes the possible separation of chlorinated plastic films (PVC and PVDC) from other heavy plastic packaging waste (PPW) by selective twist formation and gravity separation. Twists formation was mechanically induced in chlorinated plastic films, whereas twist formation did not occur in PS and PET films. After twist formation, all the films had the apparent density of less than 1.0 g/cm³ and floated in water even though the true density was more than 1.0 g/cm³. However, the apparent density of the PS and the PET films increased with agitation to more than 1.0 g/cm³, whereas that of chlorinated plastic films was kept less than 1.0 g/cm³. The main reason would be the air being held inside the chlorinated plastic films which was difficult to be removed by agitation. Simple gravity separation after twist formation was applied for artificial film with 10 wt.% of the chlorinated films and real PPW films with 9 wt.% of the chlorinated films. About 76 wt.% of the artificial PPW films and 75 wt.% of real PPW films after the removal of PP and PE were recovered as settling fraction with 4.7 wt.% and 3.0 wt.% of chlorinated plastic films, respectively. These results indicate that simple gravity separation process after twist formation can be used to reduce the chlorinated plastic concentration from mixed heavy PPW films.     

Stabilization of heavy metals in MSWI fly ash using silica fume

The objective of this work was to investigate the feasibility and effectiveness of silica fume on stabilizing heavy metals in municipal solid waste incineration (MSWI) fly ash. In addition to compressive strength measurements, hydrated pastes were characterized by X-ray diffraction (XRD), thermal-analyses (DTA/TG), and MAS NMR (²⁷Al and ²⁹Si) techniques. It was found that silica fume additions could effectively reduce the leaching of toxic heavy metals. At the addition of 20% silica fume, leaching concentrations for Cu, Pb and Zn of the hydrated paste cured for 7 days decreased from 0.32 mg/L to 0.05 mg/L, 40.99 mg/L to 4.40 mg/L, and 6.96 mg/L to 0.21 mg/L compared with the MSWI fly ash. After curing for 135 days, Cd and Pb in the leachates were not detected, while Cu and Zn concentrations decreased to 0.02 mg/L and 0.03 mg/L. The speciation of Pb and Cd by the modified version of the European Community Bureau of Reference (BCR) extractions showed that these metals converted into more stable state in hydrated pastes of MSWI fly ash in the presence of silica fume. Although exchangeable and weak-acid soluble fractions of Cu and Zn increased with hydration time, silica fume addition of 10% can satisfy the requirement of detoxification for heavy metals investigated in terms of the identification standard of hazardous waste of China.     

Phosphate recovery from phosphorus-rich solution obtained from chicken manure incineration ash

The recovery of phosphorus from waste is very important for Japan because Japan has no natural phosphorus resources. In order to recover phosphorus from incineration ash of chicken manure, an acid dissolution–alkali precipitation method was investigated. Phosphorus content in the ash was 8%. The ash was treated with hydrochloric acid to obtain phosphorus-rich solution. Phosphorus could then be recovered as a precipitant by adding sodium hydroxide solution into the phosphorus-rich solution and gradually changing the pH in the solution to 3, 4, and 8. At pH 3, a small amount of phosphorus was precipitated to remove iron, which would cause coloring of subsequent precipitants. At pH 4, 84% of the phosphorus in the original solution could be recovered as CaHPO₄ · 2H₂O with a purity of 92%. At pH 8, 8% of the phosphorus in the phosphorus-rich solution could be recovered as identified hydroxyapatite. A recovery rate of 92% phosphorus as CaHPO₄ · 2H₂O and identified as hydroxyapatite was achieved.     

Chemical stabilization of medical waste fly ash using chelating agent and phosphates: Heavy metals and ecotoxicity evaluation

Chemical stabilization of heavy metals in medical waste fly ash has been carried out using the following compounds: a chelating agent (Ashnite S803), a commercial acidic phosphoric acid solution (Ashnite R303) as well as basic one (Ashnite R201). In order to predict the leachability of heavy metals, Japanese Leaching Test (JLT-13) procedure was applied to the stabilized fly ash products. An ecotoxicity assessment of the stabilized fly ash products leachate and the unstabilized fly ash leachate was conducted using a battery of bioassays based on lettuce root elongation inhibition, Daphnia magna mortality and Vibrio fischeri photoinhibition. The results showed that the three stabilizing agents were able to significantly decrease (ANOVA, P < 0.05) the concentration of heavy metals in the leachates. Although the leachate from both stabilized and unstabilized fly ash were very toxic to lettuce and daphnids, the incorporation of these stabilizing agents diminished significantly (ANOVA, P < 0.05) the toxicity of the leachates towards the three tested organisms. Pearson correlation analysis was used to analyze the strength of the relationship between chemical elements concentration in the leachate and bioassays results. Most of the heavy metals in the leachate were significantly correlated (ANOVA, P < 0.05) with the toxicity values of the bioassays. However, the correlation was not found between the concentration of dissolved organic carbon (DOC) and the toxicity effect of the leachate to the tested organisms.     

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.     

Full-scale blending treatment of fresh MSWI leachate with municipal wastewater in a wastewater treatment plant

Fresh leachate, generated in municipal solid waste incineration (MSWI) plants, contains various pollutants with extremely high strength organics, which usually requires expensive and complex treatment processes. This study investigated the feasibility of blending treatment of MSWI leachate with municipal wastewater. Fresh MSWI leachate was pretreated by coagulation–flocculation with FeCl₃ 2 g/L and CaO 25 g/L, plate-and-frame filter press, followed by ammonia stripping at pH above 12. After that, blending treatment was carried out in a full-scale municipal wastewater treatment plant (WWTP) for approximately 3 months. Different operational modes consisting of different pretreated leachate and methanol addition levels were tested, and their performances were evaluated. Results showed that throughout the experimental period, monitored parameters in the WWTP effluent, including COD (<60 mg/L), BOD₅ (<20 mg/L), ammonium (<8 mg/L), phosphorus (<1.5 mg/L) and heavy metals, generally complied with the Chinese sewage discharged standard. Under the experimental conditions, a certain amount of methanol was needed to fulfill TN removal. An estimation of the operation cost revealed that the expenditure of blending treatment was much lower than the total costs of respective treatment of MSWI leachate and municipal wastewater. The outcomes indicated that blending treatment could not only improve the treatability of the MSWI leachate, but also reduce the treatment cost of the two different wastewaters.     

Characterization of Shredder Residues generated and deposited in Denmark

This study presents a detailed characterization of Shredder residues (SR) generated and deposited in Denmark from 1990 to 2010. It represents approximately 85% of total Danish SR. A comprehensive sampling, size fractionation and chemical analysis was carried out on entire samples as well as on each individual size fraction. All significant elemental contents except oxygen were analyzed. The unexplained “balance” was subsequently explained by oxygen content in metal oxides, carbonates, sulphates and in organics, mainly cellulose. Using mass and calorific balance approaches, it was possible to balance the composition and, thereby, estimate the degree of oxidation of elements including metals. This revealed that larger fractions (>10 mm, 10–4 mm, 4–1 mm) contain significant amount of valuable free metals for recovery. The fractionation revealed that the >10 mm coarse fraction was the largest amount of SR being 35–40% (w/w) with a metal content constituting about 4–9% of the total SR by weight and the <1 mm fine fraction constituted 27–37% (w/w) of the total weight. The lower heat value (LHV) of SR samples over different time periods (1990–2010) was between 7 and 17 MJ/kg, declining with decreasing particle size. The SR composition is greatly dependent on the applied shredding and post shredding processes at the shredding plants causing some variations. There are uncertainties related to sampling and preparation of samples for analyses due to its heterogeneous nature and uncertainties in the chemical analyses results (≈15–25%). This exhaustive characterization is believed to constitute hitherto the best data platform for assessing potential value and feasibility of further resource recovery from SR.     

Heavy metal and nutrient changes during vermicomposting animal manure spiked with mushroom residues

A pilot-scale trial of four months was conducted to investigate the responses of heavy metal and nutrient to composting animal manure spiked with mushroom residues with and without earthworms. Results showed that earthworm activities accelerated organic matter mineralization (e.g. reduction in C/N ratio, increase in total concentrations of N, P, K) and humification (e.g. increase in humic acid concentration, humification ratio and humification index). Despite composting increased total heavy metal (i.e. As, Pb, Cu, Zn) concentrations irrespective of earthworm, the availability of heavy metals extracted by DTPA significantly (P < 0.05) decreased particularly in treatments with earthworms introduced. The shift from available to unavailable fractions of heavy metals was either due to earthworm bioaccumulation, as indicated by total heavy metal concentrations being higher in earthworm tissues, or due to the formation of stable metal-humus complexes as indicated by the promotion of humification. Our results suggest that vermicomposting process could magnify the nutrient quality but relieve the heavy metals risk of agricultural organic wastes.     

Recovery of valuable materials from waste liquid crystal display panel

Associated with the rapid development of the information and electronic industry, liquid crystal displays (LCDs) have been increasingly sold as displays. However, during the discarding at their end-of-life stage, significant environmental hazards, impacts on health and a loss of resources may occur, if the scraps are not managed in an appropriate way. In order to improve the efficiency of the recovery of valuable materials from waste LCDs panel in an environmentally sound manner, this study presents a combined recycling technology process on the basis of manual dismantling and chemical treatment of LCDs. Three key processes of this technology have been studied, including the separation of LCD polarizing film by thermal shock method the removal of liquid crystals between the glass substrates by the ultrasonic cleaning, and the recovery of indium metal from glass by dissolution. The results show that valuable materials (e.g. indium) and harmful substances (e.g. liquid crystals) could be efficiently recovered or separated through above-mentioned combined technology. The optimal conditions are: (1) the peak temperature of thermal shock to separate polarizing film, ranges from 230 to 240 °C, where pyrolysis could be avoided; (2) the ultrasonic-assisted cleaning was most efficient at a frequency of 40 KHz (P = 40 W) and the exposure of the substrate to industrial detergents for 10 min; and (3) indium separation from glass in a mix of concentrated hydrochloric acid at 38% and nitric acid at 69% (HCl:HNO₃:H₂O = 45:5:50, volume ratio). The indium separation process was conducted with an exposure time of 30 min at a constant temperature of 60 °C.     

Urban Mining: Quality and quantity of recyclable and recoverable material mechanically and physically extractable from residual waste

The mechanically sorted dry fraction (MSDF) and Fines (<20 mm) arising from the mechanical biological treatment of residual municipal solid waste (RMSW) contains respectively about 11% w/w each of recyclable and recoverable materials. Processing a large sample of MSDF in an existing full-scale mechanical sorting facility equipped with near infrared and 2-3 dimensional selectors led to the extraction of about 6% w/w of recyclables with respect to the RMSW weight. Maximum selection efficiency was achieved for metals, about 98% w/w, whereas it was lower for Waste Electrical and Electronic Equipment (WEEE), about 2% w/w. After a simulated lab scale soil washing treatment it was possible to extract about 2% w/w of inert exploitable substances recoverable as construction materials, with respect to the amount of RMSW. The passing curve showed that inert materials were mainly sand with a particle size ranging from 0.063 to 2 mm. Leaching tests showed quite low heavy metal concentrations with the exception of the particles retained by the 0.5 mm sieve. A minimum pollutant concentration was in the leachate from the 10 and 20 mm particle size fractions.     

Size fractionation of organic matter and heavy metals in raw and treated leachate

This study characterized the organic matter and heavy metals in the leachate from two typical municipal solid waste (MSW) sanitary landfills in China, the recently established (3-year-old) Liulitun landfill and the mature (11-year-old) Beishenshu landfill, using a size fractionation procedure. The organic matter of all raw and treated leachate samples primarily existed in a truly-dissolved fraction with an apparent molecular weight (AMW) of <1 kDa, and its percentage decreased with an increase in overall AMW. The leachate from the newer landfill had a higher percentage of truly-dissolved organic matter. After anaerobic treatment, this leachate had a similar size fraction of organic matter to that seen for the raw leachate of the mature landfill. Biochemical processes had different removal efficiencies for various types of AMW organic matter, and the concentration of moderate AMW organic matter appeared to increase throughout these processes. Most of the heavy metals existed in a colloidal fraction (AMW >1 kDa and particle size <0.45 μm). The behaviors of different species of heavy metals had large variations. The size fractions of heavy metal species were significantly affected by treatment processes and landfill age, except for Zn. The concentration ratio of heavy metals to organic matter was maximal in the colloidal fraction and showed an inverse change to that seen for organic matter concentration changes caused by biochemical processes. Consequently, the pollution levels of heavy metals were substantially increased by treatment processes, although their concentrations decreased.     

Recovery of metals from waste printed circuit boards by supercritical water pre-treatment combined with acid leaching process

Waste printed circuit boards (PCBs) contain a large number of metals such as Cu, Sn, Pb, Cd, Cr, Zn, and Mn. In this work, an efficient and environmentally friendly process for metals recovery from waste PCBs by supercritical water (SCW) pre-treatment combined with acid leaching was developed. In the proposed process, waste PCBs were pre-treated by SCW, then the separated solid phase product with concentrated metals was subjected to an acid leaching process for metals recovery. The effect of SCW pre-treatment on the recovery of different metals from waste PCBs was investigated. Two methods of SCW pre-treatment were studied: supercritical water oxidation (SCWO) and supercritical water depolymerization (SCWD). Experimental results indicated that SCWO and SCWD pre-treatment had significant effect on the recovery of different metals. SCWO pre-treatment was highly efficient for enhancing the recovery of Cu and Pb, and the recovery efficiency increased significantly with increasing pre-treatment temperature. The recovery efficiency of Cu and Pb for SCWO pre-treatment at 420 °C was 99.8% and 80%, respectively, whereas most of the Sn and Cr were immobilized in the residue. The recovery of all studied metals was enhanced by SCWD pre-treatment and increased along with pre-treatment temperature. Up to 90% of Sn, Zn, Cr, Cd, and Mn could be recovered for SCWD pre-treatment at 440 °C.     

Washing treatment of automotive shredder residue (ASR)

Worldwide, the amount of end-of-life vehicles (ELVs) reaches 50 million units per year. Once the ELV has been processed, it may then be shredded and sorted to recover valuable metals that are recycled in iron and steelmaking processes. The residual fraction, called automotive shredder residue (ASR), represents 25% of the ELV and is usually landfilled. In order to deal with the leachable fraction of ASR that poses a potential threat to the environment, a washing treatment before landfilling was applied. To assess the potential for full-scale application of washing treatment, tests were carried out in different conditions (L/S = 3 and 5 L/kg_TS; t = 3 and 6 h). Moreover, to understand whether the grain size of waste could affect the washing efficiency, the treatment was applied to ground (<4 mm) and not-ground samples. The findings obtained revealed that, on average, washing treatment achieved removal rates of more than 60% for dissolved organic carbon (DOC), chemical oxygen demand (COD) and total Kjeldahl nitrogen (TKN). With regard to metals and chlorides, sulphates and fluoride leachable fraction, a removal efficiency of approximately 60% was obtained, as confirmed also by EC values. The comparison between the results for ground and not-ground samples did not highlight significant differences.     

Strategies for the enhancement of automobile shredder residues (ASRs) recycling: Results and cost assessment

With reference to the European regulation about the management of End-of-Life Vehicles (ELVs), Directive 2000/53/EC imposes the achievement of a recycling target of 85%, and 95% of total recovery by 2015. Over the last few years many efforts have been made to find solutions to properly manage the waste coming from ELVs with the aim of complying with the targets fixed by the Directive.This paper focuses on the economical evaluation of a treatment process, that includes physical (size and density), magnetic and electrical separations, performed on the light fraction of the automobile shredder residue (ASR) with the aim of reducing the amount of waste to dispose of in a landfill and enhancing the recovery of valuable fractions as stated by the EU Directive. The afore mentioned process is able to enhance the recovery of ferrous and non-ferrous metals of an amount equal to about 1% b.w. (by weight) of the ELV weight, and to separate a high energetic-content product suitable for thermal valorization for an amount close to (but not higher than) 10% b.w. of the ELV weight.The results of the economical assessment led to annual operating costs of the treatment ranging from 300,000 €/y to 350,000 €/y. Since the considered plant treats about 13,500 metric tons of ASR per year, this would correspond to an operating cost of approximately 20–25 €/t. Taking into account the amount and the selling price of the scrap iron and of the non magnetic metal recovered by the process, thus leading to a gain of about 30 €/t per ton of light ASR treated, the cost of the recovery process is balanced by the profit from the selling of the recovered metals. On the other hand, the proposed treatment is able to achieve the fulfillment of the targets stated by Directive 2000/53/EC concerning thermal valorization and reduce the amount of waste generated from ELV shredding to landfill.     

Hydrothermal solidification behavior of municipal solid waste incineration bottom ash without any additives

Municipal solid waste incineration (MSWI) bottom ash could be solidified with and without slaked lime (calcium hydroxide) addition by a hydrothermal method under steam pressure of 1.56 MPa at 200 °C for up to 72 h. Experimental results showed that CSH gel or tobermorite exerted a main influence on strength development, and without any additives CSH gel was easy to form, while slaked lime addition favored to form tobermorite. Tobermorite seemed to exert a larger effect on the strength development than CSH gel. Leaching results showed that the concentrations of heavy metals dissolved from the solidified specimens were effectively reduced after hydrothermal processing. The immobilization was mainly due to the tobermorite or CSH gel formation, and Pb²⁺ and Zn²⁺ seemed to be fixed more readily than Cr⁶⁺, which might be the reason that the structural Ca²⁺ within tobermorite or CSH gel was exchanged by Pb²⁺ and Zn²⁺ more easily than Cr⁶⁺. In addition, there existed a close relationship between leaching concentration and strength enhancement, and a higher strength seemed to exert a larger effect on immobilization of heavy metals.     

Generation of copper rich metallic phases from waste printed circuit boards

The rapid consumption and obsolescence of electronics have resulted in e-waste being one of the fastest growing waste streams worldwide. Printed circuit boards (PCBs) are among the most complex e-waste, containing significant quantities of hazardous and toxic materials leading to high levels of pollution if landfilled or processed inappropriately. However, PCBs are also an important resource of metals including copper, tin, lead and precious metals; their recycling is appealing especially as the concentration of these metals in PCBs is considerably higher than in their ores. This article is focused on a novel approach to recover copper rich phases from waste PCBs. Crushed PCBs were heat treated at 1150 °C under argon gas flowing at 1 L/min into a horizontal tube furnace. Samples were placed into an alumina crucible and positioned in the cold zone of the furnace for 5 min to avoid thermal shock, and then pushed into the hot zone, with specimens exposed to high temperatures for 10 and 20 min. After treatment, residues were pulled back to the cold zone and kept there for 5 min to avoid thermal cracking and re-oxidation. This process resulted in the generation of a metallic phase in the form of droplets and a carbonaceous residue. The metallic phase was formed of copper-rich red droplets and tin-rich white droplets along with the presence of several precious metals. The carbonaceous residue was found to consist of slag and ～30% carbon. The process conditions led to the segregation of hazardous lead and tin clusters in the metallic phase. The heat treatment temperature was chosen to be above the melting point of copper; molten copper helped to concentrate metallic constituents and their separation from the carbonaceous residue and the slag. Inert atmosphere prevented the re-oxidation of metals and the loss of carbon in the gaseous fraction. Recycling e-waste is expected to lead to enhanced metal recovery, conserving natural resources and providing an environmentally sustainable solution to the management of waste products.     

Recovery of materials from waste printed circuit boards by vacuum pyrolysis and vacuum centrifugal separation

In this research, a two-step process consisting of vacuum pyrolysis and vacuum centrifugal separation was employed to treat waste printed circuit boards (WPCBs). Firstly, WPCBs were pyrolysed under vacuum condition at 600 °C for 30 min in a lab-scale reactor. Then, the obtained pyrolysis residue was heated under vacuum until the solder was melted, and then the molten solder was separated from the pyrolysis residue by the centrifugal force. The results of vacuum pyrolysis showed that the type-A of WPCBs (the base plates of which was made from cellulose paper reinforced phenolic resin) pyrolysed to form an average of 67.97 wt.% residue, 27.73 wt.% oil, and 4.30 wt.% gas; and pyrolysis of the type-B of WPCBs (the base plates of which was made from glass fiber reinforced epoxy resin) led to an average mass balance of 72.20 wt.% residue, 21.45 wt.% oil, and 6.35 wt.% gas. The results of vacuum centrifugal separation showed that the separation of solder was complete when the pyrolysis residue was heated at 400 °C, and the rotating drum was rotated at 1200 rpm for 10 min. The pyrolysis oil and gas can be used as fuel or chemical feedstock after treatment. The pyrolysis residue after solder separation contained various metals, glass fibers and other inorganic materials, which could be recycled for further processing. The recovered solder can be reused directly and it can also be a good resource of lead and tin for refining.     

Solidification/stabilization of ash from medical waste incineration into geopolymers

In the present work, bottom and fly ash, generated from incinerated medical waste, was used as a raw material for the production of geopolymers. The stabilization (S/S) process studied in this paper has been evaluated by means of the leaching and mechanical properties of the S/S solids obtained. Hospital waste ash, sodium hydroxide, sodium silicate solution and metakaolin were mixed. Geopolymers were cured at 50 °C for 24 h. After a certain aging time of 7 and 28 days, the strength of the geopolymer specimens, the leachability of heavy metals and the mineralogical phase of the produced geopolymers were studied. The effects of the additions of fly ash and calcium compounds were also investigated. The results showed that hospital waste ash can be utilized as source material for the production of geopolymers. The addition of fly ash and calcium compounds considerably improves the strength of the geopolymer specimens (2–8 MPa). Finally, the solidified matrices indicated that geopolymerization process is able to reduce the amount of the heavy metals found in the leachate of the hospital waste ash.