Rapid-extraction oxidation process to recover and reuse copper chromium and arsenic from industrial wood preservative sludge

Chromated copper arsenate (CCA) wood preservative can form insoluble sludges when the hexavalent chromium component is reduced by wood extractives, wood particles and preservative additives in the solution. This sludge accumulates in treating solution work tanks, sumps and in-line filters and must be disposed of as hazardous wastes by waste disposal companies at high costs. A number of commercial sludges were investigated and found to contain 18-94% copper, chromium and arsenic as oxides combined with sand, oil, wood particles, additives and wood extractives. We have developed a multi-stage recycling process whereby approximately 97% of the CCA components are recovered from the sludge. It involves extraction with sodium hypochlorite to remove and oxidize chromium (more than 90%) and extract most of the arsenic (approx. 80%) followed by extraction of the copper and remaining arsenic and chromium with phosphoric acid. The phosphoric acid extract contains some trivalent chromium, which is subsequently oxidized by sodium hypochlorite. The combined oxidized extract containing CrVI, CuII and AsV was compatible with CCA treating solutions and could be re-used commercially for treating wood without having a significant effect on the preservative fixation rate or the leach resistance of the treated wood. A cost analysis showed that the economic savings from recovery of CCA chemicals and reduced landfill costs exceeded the variable costs for materials and energy for the process by as much as Can $966 per tonne of sludge if sodium sulfite can be acquired in bulk quantities for the process.     

Exergy analysis of the Chartherm process for energy valorization and material recuperation of chromated copper arsenate (CCA) treated wood waste

The Chartherm process (Thermya, Bordeaux, France) is a thermochemical conversion process to treat chromated copper arsenate (CCA) impregnated wood waste. The process aims at maximum energy valorization and material recuperation by combining the principles of low-temperature slow pyrolysis and distillation in a smart way. The main objective of the exergy analysis presented in this paper is to find the critical points in the Chartherm process where it is necessary to apply some measures in order to reduce exergy consumption and to make energy use more economic and efficient. It is found that the process efficiency can be increased with 2.3-4.2% by using the heat lost by the reactor, implementing a combined heat and power (CHP) system, or recuperating the waste heat from the exhaust gases to preheat the product gas. Furthermore, a comparison between the exergetic performances of a ‘chartherisation’ reactor and an idealized gasification reactor shows that both reactors destroy about the same amount of exergy (i.e. 3500 kW kg_wood⁻¹) during thermochemical conversion of CCA-treated wood. However, the Chartherm process possesses additional capabilities with respect to arsenic and tar treatment, as well as the extra benefit of recuperating materials.     

Fungicidal value of wood tar from pyrolysis of treated wood

The objective of the paper was to estimate the fungicidal value of wood tar extracted as a product of pyrolysis of wood previously treated with either creosote oil or CCB-type salt preservative. The effectiveness of wood treated with one of these two wood tar residuals was compared to the effectiveness of wood treated with virgin creosote oil (type WEI-B) and an untreated control. Wood was impregnated with alcohol solutions of the two extracted preservatives or virgin creosote oil and then subjected to the Coniophora puteana, Poria placenta and Coriolus versicolor fungi. The fungicidal values of the investigated preservatives were determined with the use of the short agar-block method and the aging test according to the standard EN 84. It was found that wood tar extracted by pyrolysis of old creosote-treated wood and then used to treat wood may have potential as a preservative for wood protection or as a component of preservatives.     

Conversion of CCA-treated wood to ethanol: a method to reduce leaching of metals from disposed treated wood prior to disposal

The objective of this paper is to evaluate the feasibility of producing ethanol from CCA-treated wood that is highly leachable. Following the initial tests, CCA-treated wood was hydrolysed and fermented and the results showed not only that ethanol was produced during the fermentation process but that metals were taken up by the yeast. Toxicity characteristic leaching procedure tests of the hydrolysed wood leached less than 4 mg/L of As while minimal amounts of Cr and Cu remained in the hydrolysed wood which makes landfilling of hydrolysed wood acceptable and less hazardous. A slightly lower amount of ethanol from CCA-treated than untreated wood was produced (6 and 7 g/L, respectively). In general, it suggests that production of ethanol as a source of energy from a hazardous waste (CCA-treated wood) is feasible.     

失效动力锂离子电池再利用和有用金属回收技术研究

动力锂离子电池以其贮电能力大、充放电速度快等优点被广泛应用在电动汽车上,近年来失效电动汽车动力锂离子电池报废量不断增加,但未得到有效处理回收,造成了巨大的资源浪费和环境污染.失效电池还有80％左右的容量可以使用,可以在场地车或者储能电站进行再利用,以达到材料和电池的最大利用率;同时电池中含有多种有用金属（如Co,Al,Ni,Li等）且相对含量较高,极具回收价值.针对失效动力锂离子电池的再利用和有用金属的各种回收方法进行了评述.     

Application of ameliorated wood pulp to recover Cd(II), Pb(II), and Ni(II) from e-waste

In this study, dl-malic acid and hydrogen peroxide were used as leaching agents to remove metals from e-waste (printed-circuit boards) and itaconic acid-grafted poly(vinyl alcohol)-encapsulated wood pulp (IA-g-PVA-en-WP) to uptake metals from leachate with high proficiency [11.63 mg g^?1; 93.03 % for Cd(II), 11.90 mg g^?1; 95.18 % for Pb(II), and 12.14 mg g^?1; 97.08 % for Ni(II)]. Metals were recovered from the loaded biosorbent by desorption studies. The standard analytical techniques, such as elemental analysis, Fourier-transform-infrared spectroscopy, scanning electron microscopy, atomic force microscopy, and thermogravimetric analysis, were used to characterize the recovering agent (biosorbent). At equilibrium, the metal uptake data were fitted to Langmuir and D–R isotherms (R ² > 0.99) significantly, revealing, the homogeneous distribution of active sites on biosorbent’s backbone. The possible mechanism appeared to be ion exchanges of metal ions with H⁺ together with binding over functionalities (COO^?). Dimensionless equilibrium parameter (R _L) showed the favourability of metal uptake at lower concentration, while mean adsorption energy (E) certified the physical binding of metal on functionalities which was further confirmed by sticking probability and activation energy parameters. Reusability studies were also conducted to state the performance of biosorbent.     

Factors affecting sodium hypochlorite extraction of CCA from treated wood

Significant amounts of chromated copper arsenate (CCA) treated wood products, such as utility poles and residential construction wood, remain in service. There is increasing public concern about environmental contamination from CCA-treated wood when it is removed from service for reuse or recycling, placed in landfills or burned in commercial incinerators. In this paper, we investigated the effects of time, temperature and sodium hypochlorite concentration on chromium oxidation and extraction of chromated copper arsenate from CCA-treated wood (Type C) removed from service. Of the conditions evaluated, reaction of milled wood with sodium hypochlorite for one hour at room temperature followed by heating at 75 °C for two hours gave the highest extraction efficiency. An average of 95% Cr, 99% Cu and 96% As could be removed from CCA-treated, milled wood by this process. Most of the extracted chromium was oxidized to the hexavalent state and could therefore be recycled in a CCA treating solution. Sodium hypochlorite extracting solutions could be reused several times to extract CCA components from additional treated wood samples.     

Removal of copper,chromium and arsenic from preservative-treated wood by chemical extraction-fungal bioleaching

Large volumes of preservative-treated wood containing toxic Cr, Cu and As salts are decommissioned worldwide. This study investigated the effectiveness of solid-state fermentation with copper-tolerant brown-rot fungi for the remediation of wood treated with chromated copper arsenate (CCA) and acid copper chromate (ACC) formulations. Treatment of CCA- and ACC-wood with the most effective strain, Antrodia vaillantii FRLP-14G, attained extensive leaching of As and/or Cr, but Cu elimination was poor (<18%). Additional research showed that a variety of organic acids, including citrate, are effective Cu extractants. Based on these findings, a process combining chemical extraction and subsequent fungal treatment was developed that proved highly effective in removing inorganic pollutants from CCA-wood. Extraction of CCA-wood with citric acid (30 mM, pH 3.10) followed by a 28-day solid-state fermentation period removed 87% Cu, 80% Cr, and 100% As. These results indicate the potential of the two-stage process for the remediation of preservative-treated wood.     

Characterization and recovery of mercury from spent fluorescent lamps

Fluorescent lamps rely on mercury as the source of ultraviolet radiation for the production of visible light. Partitioning of mercury among vapor phase, loose phosphor powders produced during breaking and washing steps, glass matrices, phosphor powders attached on the glass and aluminum end caps was examined from simulated laboratory lamp recycling tests for different types of spent and new fluorescent lamps. Mercury concentrations in lamp glasses taken from commercial lamp recyclers were also analyzed for comparison with the simulated results of spent and new lamps of different types. The mercury content of the glass from spent lamps was highly variable depending on the lamp type and manufacturer; the median values of the mercury concentration in glasses for spent 26- (T8) and 38-mm (T12) diameter fluorescent lamps were approximately 30 and 45 microg/g, respectively. The average mercury concentration of samples taken from recycler A was 29.6 microg/g, which was about 64% of median value measured from the spent T12 lamps. Over 94% of total mercury in lamps remained either as a component of phosphor powders attached inside the lamp or in glass matrices. New T12 lamps had a higher partitioning percentage of elemental mercury in the vapor phase (0.17%) than spent T12 lamps (0.04%), while spent lamps had higher partitioning percentages of mercury resided on end-caps and phosphor powders detached from the breaking and washing steps. The TCLP values of simulated all lamp-glasses and samples obtained from recyclers were higher than the limit of LDR standard (0.025 mg/L). After investigating acid treatment and high temperature treatment as mercury reclamation techniques, it was found that heating provided the most effective mercury capture. Although the initial mercury concentrations of individual sample were different, the mercury concentrations after 1 h exposure at 100 degrees C were below 4 mug/g for all samples (i.e., <1% remaining). Therefore, it is recommended that heating be used for recovering mercury from spent fluorescent lamps.     

Preparation and performance of arsenate (V) adsorbents derived from concrete wastes

Solid adsorbent materials, prepared from waste cement powder and concrete sludge were assessed for removal of arsenic in the form of arsenic (As(V)) from water. All the materials exhibited arsenic removal capacity when added to distilled water containing 10–700 mg/L arsenic. The arsenic removal isotherms were expressed by the Langmuir type equations, and the highest removal capacity was observed for the adsorbent prepared from concrete sludge with heat treatment at 105 °C, the maximum removal capacity being 175 mg-As(V)/g. Based on changes in arsenic and calcium ion concentrations, and solution pH, the removal mechanism for arsenic was considered to involve the precipitation of calcium arsenate, Ca₃(AsO₄)₂. The enhanced removal of arsenic for the adsorbent prepared from concrete sludge with heat treatment was thought to reflect ion exchange by ettringite. The prepared adsorbents, derived from waste cement and concrete using simple procedures, may offer a cost effective approach for arsenic removal and clean-up of contaminated waters, especially in developing countries.     

Treatment of exhaust fluorescent lamps to recover yttrium: experimental and process analyses

The paper deals with recovery of yttrium from fluorescent powder coming from dismantling of spent fluorescent tubes. Metals are leached by using different acids (nitric, hydrochloric and sulphuric) and ammonia in different leaching tests. These tests show that ammonia is not suitable to recover yttrium, whereas HNO(3) produces toxic vapours. A full factorial design is carried out with HCl and H(2)SO(4) to evaluate the influence of operating factors. HCl and H(2)SO(4) leaching systems give similar results in terms of yttrium extraction yield, but the last one allows to reduce calcium extraction with subsequent advantage during recovery of yttrium compounds in the downstream. The greatest extraction of yttrium is obtained by 20% w/v S/L ratio, 4N H(2)SO(4) concentration and 90°C. Yttrium and calcium yields are nearly 85% and 5%, respectively. The analysis of variance shows that acid concentration alone and interaction between acid and pulp density have a significant positive effect on yttrium solubilization for both HCl and H(2)SO(4) medium. Two models are empirically developed to estimate yttrium and calcium concentration during leaching. Precipitation tests demonstrate that at least the stoichiometric amount of oxalic acid is necessary to recover yttrium efficiently and a pure yttrium oxalate n-hydrate can be produced (99% grade). The process is economically feasible if other components of the fluorescent lamps (glass, ferrous and non-ferrous scraps) are recovered after the equipment dismantling and valorized, besides the cost that is usually paid to recycling companies for collection, treatment or final disposal of such fluorescent powders.     

Recovery of aluminium, nickel-copper alloys and salts from spent fluorescent lamps

This study explores a combined pyro-hydrometallurgical method to recover pure aluminium, nickel-copper alloy(s), and some valuable salts from spent fluorescent lamps (SFLs). It also examines the safe recycling of clean glass tubes for the fluorescent lamp industry. Spent lamps were decapped under water containing 35% acetone to achieve safe capture of mercury vapour. Cleaned glass tubes, if broken, were cut using a rotating diamond disc to a standard shorter length. Aluminium and copper-nickel alloys in the separated metallic parts were recovered using suitable flux to decrease metal losses going to slag. Operation variables affecting the quality of the products and the extent of recovery with the suggested method were investigated. Results revealed that total loss in the glass tube recycling operation was 2% of the SFLs. Pure aluminium meeting standard specification DIN 1712 was recovered by melting at 800 degrees C under sodium chloride/carbon flux for 20 min. Standard nickel-copper alloys with less than 0.1% tin were prepared by melting at 1250 degrees C using a sodium borate/carbon flux. De-tinning of the molten nickel-copper alloy was carried out using oxygen gas. Tin in the slag as oxide was recovered by reduction using carbon or hydrogen gas at 650-700 degrees C. Different valuable chloride salts were also obtained in good quality. Further research is recommended on the thermodynamics of nickel-copper recovery, yttrium and europium recovery, and process economics.     

Thermal treatment for recovery of manganese and zinc from zinc-carbon and alkaline spent batteries

The aim of this paper is the recovery of manganese and zinc from a mixture of zinc-carbon and alkaline spent batteries, containing 40.9% of Mn and 30.1% of Zn, after preliminary physical treatment followed by removal of mercury. Separation of the metals has been carried out on the basis of their different boiling points, being 357°C and 906°C the boiling point of mercury and zinc and 1564°C the melting point of Mn(2)O(3). Characterization by chemical analysis, TGA/DTA and X-ray powder diffraction of the mixture has been carried out after comminution sieving and shaking table treatment to remove the anodic collectors and most of chlorides contained in the mixture. The mixture has been roasted at various temperatures and resident times in a flow of air to set the best conditions to remove mercury that were 400°C and 10min. After that, the flow of air has been turned into a nitrogen one (inert atmosphere) and the temperatures raised, thus permitting the zinc oxide to be reduced to metallic zinc by the carbon present in the original mixture and recovered after volatilization as a high grade concentrate, while manganese was left in the residue. The recovery and the grade of the two metals, at 1000°C and 30min residence time, were 84% and 100% for zinc and 85% and 63% for manganese, respectively. The recovery of zinc increased to 99% with a grade of 97% at 1200°C and 30min residence time, while the recovery and grade of manganese were 86% and 87%, respectively, at that temperature. Moreover, the chlorinated compounds that could form by the combustion of the plastics contained in the spent batteries, are destroyed at the temperature required by the process.     

Leachate migration from spent mushroom substrate through intact and repacked subsurface soil columns

Field weathering of spent mushroom substrate (SMS) produces soluble compost leachate that percolates into underlying soils and may adversely impact groundwater. Laboratory experiments were conducted to investigate movement and retention of SMS leachate solutes in subsurface soil columns. Spent mushroom substrate leachate with high concentrations of dissolved organic matter (DOM) and inorganic salts was passively loaded to intact and repacked columns of Bt1 soil (fine-loamy, mixed, semiactive, mesic Typic Hapludults) and effluents were monitored for changes in chemical composition. Transport of SMS leachate in undisturbed soil cores was mainly via preferential flow, whereas matrix flow was predominant in repacked soil columns. Leachate DOM and phosphate were sorbed by soil minerals while Cl-, SO4(2-), Na+ and NH4+ were eluted. Leachate K+ displaced exchangeable native cations and was retained. Biodegradation of leachate DOM resulted in reduction and elution of soil Mn and Fe, especially in repacked columns. Persistent anoxia also inhibited nitrification. Precipitation of gypsum and CaCO3 blocked preferential flow channels, and movement of SMS leachate was subsequently reduced. The results demonstrate that SMS leachate migrates via rapid preferential flow initially, followed by matrix flow at a lower rate. Leachate solutes may transport to depth in soil profiles through preferential channels. To protect water resources, weathering of deep SMS piles should be conducted on compact surfaces or in fields with a condensed soil layer (no structural cracks) above the groundwater table, and measures controlling leachate runoff be imposed.     

An ecologically oriented database to guide remediation and reuse of contaminated sites

This article presents a database developed to determine the potential reuse of contaminated sites for primarily ecologically and culturally based activities. The database consists of 172 quantitative and qualitative measures of on‐site land suitability, ecological, cultural, and recreational value, and off‐site suitability, economic, and demographic information. Using sites owned by the U.S. Department of Energy (DOE) as a case study, the article evaluates the quality of available data and suggests ways of using it for planning ecologically sensitive remediation activities and future land use. This type of database can be developed and used by anyone who needs to select, review, or evaluate site remediation and future land use options. Also discussed are the challenges associated with compiling and using data that has been generated by many sources over several years. © 2003 Wiley Periodicals, Inc.     

Geopolymer synthesized from spent fluid catalytic cracking catalyst and its heavy metal immobilization behavior

Journal of Material Cycles and Waste Management - Porous geopolymers (GP) are energy saving, environment-friendly and simple in preparation, which has attracted increasing attention from both...     

Solid waste from aluminum recycling process: characterization and reuse of its economically valuable constituents

Due to economic advantages, many companies in Brazil recover Al from the process of crushing and water-leaching of secondary aluminum dross. Wastes from this process (non-metallic products and salts) are usually landfilled or disposed without treatment, causing many environmental damages. The purpose of this work is to investigate, in a recycling company sited in Sao Paulo metropolitan area (Brazil), the potential use of the non-metallic product (NMP) in the production of concrete blocks and to evaluate the presence of important chemical compounds that may be useful for other applications. Chemical and mineralogical analyses revealed that NMP is composed of refractory and abrasive oxides (alpha-Al2O3, MgAl2O4, SiO2) and an important source of transition alumina: alpha-Al(OH)3. Concrete blocks were made by adding two parts of NMP to one part of cement and four parts of sand. The blocks were tested according to the Brazilian standard (NBR7173/1982) and they passed dimension, humidity and absorption tests but not compressive strength tests. However, particular NMP constituents have accelerated the strength rate development of the blocks, thus decreasing working time. The commercial use of NMP can reduce the amount of discarded wastes contributing to environmental preservation.     

Recycling and reuse of waste from electricity distribution networks as reinforcement agents in polymeric composites

Of the waste generated from electricity distribution networks, wooden posts treated with chromated copper arsenate (CCA) and ceramic insulators make up the majority of the materials for which no effective recycling scheme has been developed. This study aims to recycle and reuse this waste as reinforcement elements in polymer composites and hybrid composites, promoting an ecologically and economically viable alternative for the disposal of this waste. The CCA wooden posts were cut, crushed and recycled via acid leaching using 0.2 and 0.4 N H₂SO₄ in triplicate at 70 °C and then washed and dried. The ceramic insulators were fragmented in a hydraulic press and separated by particle size using a vibrating sieve. The composites were mixed in a twin-screw extruder and injected into the test specimens, which were subjected to physical, mechanical, thermal and morphological characterization. The results indicate that the acid treatment most effective for removing heavy metals in the wood utilizes 0.4 N H₂SO₄. However, the composites made from wood treated with 0.2 N H₂SO₄ exhibited the highest mechanical properties of the composites, whereas the use of a ceramic insulator produces composites with better thermal stability and impact strength. This study is part of the research and development project of ANEEL (Agência Nacional de Energia Elétrica) and funded by CPFL (Companhia Paulista de Força e Luz).