Total recycling of CCA treated wood waste by low-temperature pyrolysis

A system to turn a potentially harmful stream of solid waste into a set of substreams with either commercial value or highly concentrated residual streams is presented. The waste which is considered is metal impregnated (in particular Chromated Copper Arsenate (CCA) treated) wood waste and timber, such as telephone poles, railway sleepers, timber from landscape and cooling towers, wooden silos, hop-poles, cable drums and wooden playground equipment. These waste streams sum up to several 100,000 tons of material per year currently to be dumped in every major country of the European Community (EC). Technologies need to be developed to reduce this CCA treated wood waste, such that all of the metals are contained in a marketable product stream, and the pyrolysis gases and/or pyrolysis liquid are used to their maximum potential with respect to energy recuperation. Pyrolysing the CCA treated wood waste may be a good solution to the growing disposal problem since low temperatures and no oxidising agents are used, which result in lower loss of metals compared to combustion. An experimental labscale pyrolysis system has been developed to study the influence of the pyrolysis temperature and the duration of the pyrolysis process on the release of metals and the mass reduction. The macrodistribution and microdistribution of the metals in the solid pyrolysis residue is studied using Inductively Coupled Plasma Mass Spectrometry (ICP–MS) and Scanning Electron Microscopy coupled with Energy Dispersive X-ray Analysis (SEM–EDXA). Furthermore, a complete mass balance is calculated over the pyrolysis system. Based on these results a semi-industrial pyrolysis system (pilot plant scale) has been developed consisting of three stages: grinding, packed bed pyrolysis and metal separation. Special types of equipment have been developed to carry out the three stages. A new grinding system has been developed, based on a crushing mechanism rather than a cutting mechanism. The crushed wood is introduced by means of a screw feeding system into a reaction column. In this pyrolysis reactor the wood is heated by subjecting it to a flow of hot gases. This causes an adiabatic pyrolysis, which results in volatilisation of the volatile compounds whereas the mineral compounds (containing the metals) remain entrapped in a coal-type residue which is very rich in carbon. The condensable compounds in the pyrolysis gas condense while leaving the reaction zone due to the inverse temperature gradient. The pyrolysis gas leaving the reactor is used as fuel for the hot gas generator. The charcoal which is extracted at the bottom of the reactor, is cooled, compressed, removed and stored, ready to feed the subsequent stage. A specially developed grinder is used to remove the metal particles from the charcoal and the separation between metal and charcoal particles is accomplished in a pneumatic centrifuge as a result of the difference in density. Using this system the ultimate waste is less than 3% of the initial wood mass. Results obtained with a semi-industrial scale prototype confirm the effectiveness of the process.     

Assessment of the use of spent copper slag for land reclamation.

The shortage of waste landfill space for waste disposal and the high demand for fill materials for land reclamation projects in Singapore have prompted a study on the feasibility of using spent copper slag as fill material in land reclamation. The physical and geotechnical properties of the spent copper slag were first assessed by laboratory tests, including hydraulic conductivity and shear strength tests. The physical and geotechnical properties were compared with those of conventional fill materials such as sands. The potential environmental impacts associated with the use of the spent copper slag for land reclamation were also evaluated by conducting laboratory tests including pH and Eh measurements, batch-leaching tests, acid neutralization capacity determination, and monitoring of long-term dissolution of the material. The spent copper slag was slightly alkaline, with pH 8.4 at a solid : water ratio of 1 : 1. The batch-leaching test results show that the concentrations of the regulated heavy metals leached from the material at pH 5.0 were significantly lower than the maximum concentrations for their toxicity limits referred by US EPA's Toxicity Characteristic Leaching Procedure (TCLP). It was also found that the material is unlikely to cause significant change in the redox condition of the subsurface environment over a long-term period. In terms of physical and geotechnical properties, the spent copper slag is a good fill material. In general, the spent copper slag is suitable to be used as a fill material for land reclamation.     

Immobilization of copper flotation waste using red mud and clinoptilolite

The flash smelting process has been used in the copper industry for a number of years and has replaced most of the reverberatory applications, known as conventional copper smelting processes. Copper smelters produce large amounts of copper slag or copper flotation waste and the dumping of these quantities of copper slag causes economic, environmental and space problems. The aim of this study was to perform a laboratory investigation to assess the feasibility of immobilizing the heavy metals contained in copper flotation waste. For this purpose, samples of copper flotation waste were immobilized with relatively small proportions of red mud and large proportions of clinoptilolite. The results of laboratory leaching demonstrate that addition of red mud and clinoptilolite to the copper flotation waste drastically reduced the heavy metal content in the effluent and the red mud performed better than clinoptilolite. This study also compared the leaching behaviour of metals in copper flotation waste by short-time extraction tests such as the toxicity characteristic leaching procedure (TCLP), deionized water (DI) and field leach test (FLT). The results of leach tests showed that the results of the FLT and DI methods were close and generally lower than those of the TCLP methods.     

An investigation of the presence of methane and other gases at the Uzundere-Izmir solid waste disposal site, Izmir, Turkey

Izmir is a large metropolitan city with a population of 3,114,860. The city consists of 27 townships, each township has a population of not less than 10,000 inhabitants. The two major solid waste disposal sites are in the townships of Uzundere and Harmandali. The amount of solid waste that is disposed at each of these sites is about 800 and 1800 t/day, respectively. In Uzundere, compost is produced from the organic fraction of urban solid wastes while the residual material is deposited at a disposal site with a remaining capacity of 700,000 m(3) as of 2001. Gas monitoring and measurements were carried out at the disposal site in Uzundere. For this purpose, nine sampling wells were drilled on selected locations. Each well was furnished with perforated metal pipes suitable for gas monitoring and measurements. The following gases were monitored: O(2), CH(4), CO, CO(2), and H(2)S. The most important finding was that the concentrations of CH(4) in the wells ranged from 7 to 57%. Dilution of the CH(4) by O(2) down to the LEL levels (5-15%) is always possible and poses a continuing risk at the site. Furthermore, the levels of O(2) require that access to the site be limited to only authorized personnel.     

Heavy metal content of combustible municipal solid waste in Denmark.

Data on the heavy metal composition of outlets from Danish incinerators was used to estimate the concentration of Zn, Cu, Pb, Cr, Ni, Cd, As and Hg in combustible waste (wet as received) at 14 Danish incinerators, representing about 80% of the waste incinerated in Denmark. Zn (1020 mg kg(-1)), Cu (620 mg kg(-1)) and Pb (370 mg kg(-1)) showed the highest concentration, whereas Hg (0.6 mg kg(-1)) showed the lowest concentration. The variation among the incinerators was in most cases within a factor of two to three, except for Cr that in two cases showed unexplained high concentrations. The fact that the data represent many incinerators and, in several cases, observations from a period of 4 to 5 years provides a good statistical basis for evaluating the content of heavy metals in combustible Danish waste. Such data may be used for identifying incinerators receiving waste with high concentrations of heavy metals suggesting the introduction of source control, or, if repeated in time, the data must also be used for monitoring the impacts of national regulation controlling heavy metals. It is recommended that future investigations consider the use of sample digestion methods that ensure complete digestion in order to use the data for determining the total heavy metal content of waste.     

Metal leachability, heavy metals, polycyclic aromatic hydrocarbons and polychlorinated biphenyls in fly and bottom ashes of a medical waste incineration facility

Medical waste from hospitals and other healthcare institutions has become an imperative environmental and public safety problem. Medical waste in Greece has become one of the most urgent environmental problems, because there are 14,000 tons produced annually, of which only a small proportion is incinerated. In the prefecture of Attica there is only one modern municipal medical waste incinerator (started 2004) burning selected infectious hospital waste (5-6 tons day(-1)). Fly and bottom residues (ashes) are collected and stored temporarily in barrels. High values of metal leachability prohibit the landfilling of these ashes, as imposed by EU directives. In the present study we determined quantitatively the heavy metals and other elements in the fly and bottom ashes of the medical waste incinerator, by inductively coupled plasma emission spectrometry (ICP) and by energy dispersive X-ray analysis (EDAX). Heavy metals, which are very toxic, such as Pb, Cd, Ni, Cr, Cu and Zn were found in high concentrations in both fly and bottom ashes. Metal leachability of fly and bottom ashes by water and kerosene was measured by ICP and the results showed that toxic metals in both ashes, such as Pb, Cr, Cd, Cu and Zn, have high leaching values. These values indicate that metals can become soluble and mobile if ash is deposited in landfills, thus restricting their burial according to EU regulations. Analysis of polychlorinated biphenyls and polycyclic aromatic hydrocarbons in fly and bottom ashes showed that their concentrations were very low. This is the first known study in Greece and the results showed that incineration of medical waste can be very effective in minimizing the most hazardous and infectious health-care waste. The presence of toxic metals with high leachability values remains an important draw back of incineration of medical waste and various methods of treating these residues to diminish leaching are been considered at present to overcome this serious technical problem.     

Co-gasification of municipal solid waste and material recovery in a large-scale gasification and melting system

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

Leachability testing of metallic wastes.

The performance of two tests, a batch test and a percolation test for the characterization of waste as suggested in the EU council decision 2003/33/EC was investigated. The tests were carried out on two solid waste streams from a metal recycling industry. The concentrations of heavy metals such as Cu, Zn and Pb were more than one order of magnitude lower than the proposed limit values. Generally, batch test values were equal or higher than percolation test values. With the proposed test procedures both materials could be considered as non-dangerous wastes. The test performance was also investigated using a leachant with higher ionic strength instead of demineralized water as prescribed. The results clearly show a significant increase in the concentration of some heavy metals. Total concentrations of phenolic compounds and polychlorinated biphenyls were less than 1 p.p.m. and 2 p.p.b., respectively. The precision of the batch and the percolation tests were on average 48 and 35%, respectively.     

Urban Metal Flows – A Case Study of Stockholm. Review and Conclusions

Metals have rapidly accumulated in the anthroposphere, especiallyin urban areas, indicating possible environmental and resource problems. Here, Stockholm City was chosen for a case study of urban metal flows, i.e. metal inflow to, metals in the stock of,and metal outflow from the anthroposphere to the biosphere. Themetal stock of Stockholm is large and still growing. The large amounts of metals in the solid waste fraction totally dominatethe outflow from the city. For major parts of the stock, the emissions from goods in use are negligible. There are, however,goods applications corresponding to significant emissions: e.g. the traffic sector (Cu, Zn, Cr, Ni, Pb), the tapwater system (Cu), roofs/fronts or other metal surfaces (Cu, Zn). Today's known metal flows from the anthroposphere of Stockholm to the biosphere and sewage sludge are quantitatively dominated by Zn(34 ton y^-1) and Cu (14 ton y^-1). Historical and present emissions have resulted in high metal concentrations insediments (especially Cd, Hg and Pb, but also Cu and Zn), groundwater (Cu, Hg) and in soils (Hg, Cu, Pb). At present theannual median concentrations are below the Swedish limits for metals in sewage sludge, even if the safety margins aresmall for Cd, Hg and to some extent Cu. The flows of Cu and Zn to Stockholm soils are high with a significant accumulationindicating an environmental impact in a longer time perspective.High levels of metals in surface sediments in the waterenvironments reflects an ongoing input where these metals aretransported from known (Cu, Zn) and or partly unknown (Cd, Hg, Pb) sources. In future urban areas, monitoring of metal flows must be performed both in the anthroposphere and the biospherein order to have a pro active approach to urban environmentalproblems and to get prompt answers to measures taken.     

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.     

Evolution of heavy metals in municipal solid waste during bio-drying and implications of their subsequent transfer during combustion

Bio-drying has been applied to improve the heating value of municipal solid waste (MSW) prior to combustion. In the present study, evolution of heavy metals in MSW during bio-drying and subsequent combustion was studied using one aerobic and two combined hydrolytic-aerobic scenarios. Heavy metals were concentrated during bio-drying and transformed between different metal fractions, namely the exchangeable, carbonate-bound, iron- and manganese-oxides-bound, organic-matter-bound and residual fractions. The amounts of heavy metals per kg of bio-dried MSW transferred into combustion flue gas increased with bio-drying time, primarily due to metals enrichment from organics degradation. Because of their volatility, the partitioning ratios of As and Hg in flue gas remained stable so that bio-drying and heavy metal speciation had little effect on their transfer and partitioning during combustion. In contrast, the partitioning ratios of Pb, Zn and Cu tended to increase after bio-drying, which likely enhanced their release potential during combustion.     

Report: transboundary hazardous waste management. part II: performance auditing of treatment facilities in importing countries.

Before implementing the self-monitoring model programme of the Basel Convention in the Asia, Taiwan has conducted a comprehensive 4-year follow-up project to visit the governmental authorities and waste-disposal facilities in the countries that import waste from Taiwan. A total of nine treatment facilities, six of which are reported in this paper, and the five countries where the plants are located were visited in 2001-2002. France, Belgium and Finland primarily handled polychlorinated biphenyl capacitors, steel mill dust and metal waste. The United States accepted metal sludge, mainly electroplating sludge, from Taiwan. Waste printed circuit boards, waste wires and cables, and a mixture of waste metals and electronics were the major items exported to China. Relatively speaking, most treatment plants for hazardous waste paid close attention to environmental management, such as pollution control and monitoring, site zoning, system management regarding occupational safety and hygiene, data management, permits application, and image promotion. Under the tight restrictions formulated by the central environment agency, waste treatment plants in China managed the environmental issues seriously. For example, one of the treatment plants had ISO 14001 certification. It is believed that with continuous implementation of regulations, more improvement is foreseeable. Meanwhile, Taiwan and China should also continuously enhance their collaboration regarding the transboundary management of hazardous waste.     

Relocation of net-acid-generating waste to improve post-mining water chemistry

Acidic drainage and metal leaching are long-term environmental liabilities that can persist for many decades to millennia. One technique to improve the water chemistry and ecology of post-mining landscapes is to relocate and submerge net-acid-generating mine materials in a lake or water-retaining impoundment. One example of a carefully executed relocation of waste rock took place at the Eskay Creek Mine in Canada. Pre-relocation studies included an empirical relationship that related (1) the amount of acidity retained by the waste rock during past oxidation to (2) the amount of lime needed in each truckload for neutralization of the acidity and for suppression of metal release. During relocation, thousands of rinse pH measurements indicated net acidity varied significantly over short distances within the waste rock and that acidic rock could not be reliably segregated from near-netural rock. After relocation, water from the watershed continued to be acidic for a few years, then returned to near-neutral pH and near-background concentrations of metals. The chemistry of the lake where the waste rock was submerged remains near background conditions. Therefore, with careful planning and implementation, the relocation and submergence of net-acid-generating materials can greatly improve post-mining water chemistry.     

Evaluation of heavy metal leaching from spent household batteries disposed in municipal solid waste

Batch leaching tests and simulated landfill lysimeter tests were performed to evaluate the contents of heavy metals leached from spent batteries in the municipal solid waste. The toxicity characteristic leaching procedure was utilized to perform the batch leaching tests of 36 spent batteries. Four lysimeters were prepared with battery contents ranging from 0% to 100% by weight for column tests, and the experiments were performed at ambient temperature. The age of all the batteries used in the study ranged from freshly disposed up to approximately 3 years old. The results from the batch tests showed that the type of battery influenced the heavy metal concentrations in the leached solutions. The lysimeter experiment results illustrated that at lower pH levels more metals are leached than at higher pH levels. The increasing amount of batteries disposed in landfills can contribute to the leaching of more metals, especially Mn and Zn, into the environment. These results indicate that the direct disposal of spent household batteries into a MSW landfill can increase the heavy metal contents in the landfill leachate.     

Fate of metals contained in waste electrical and electronic equipment in a municipal waste treatment process

In Japan, waste electrical and electronic equipment (WEEE) that is not covered by the recycling laws are treated as municipal solid waste. A part of common metals are recovered during the treatment; however, other metals are rarely recovered and their destinations are not clear. This study investigated the distribution ratios and substance flows of 55 metals contained in WEEE during municipal waste treatment using shredding and separation techniques at a Japanese municipal waste treatment plant. The results revealed that more than half of Cu and most of Al contained in WEEE end up in landfills or dissipate under the current municipal waste treatment system. Among the other metals contained in WEEE, at least 70% of the mass was distributed to the small-grain fraction through the shredding and separation and is to be landfilled. Most kinds of metals were concentrated several fold in the small-grain fraction through the process and therefore the small-grain fraction may be a next target for recovery of metals in terms of both metal content and amount. Separate collection and pre-sorting of small digital products can work as effective way for reducing precious metals and less common metals to be landfilled to some extent; however, much of the total masses of those metals would still end up in landfills and it is also important to consider how to recover and utilize metals contained in other WEEE such as audio/video equipment.     

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.     

Recovery of high purity zinc from filter ash produced during the thermal treatment of waste and inerting of residual materials.

The method described below recovers zinc, a valuable metal that is present in high concentrations in filter ash from the thermal treatment of waste, and returns the filter ash stripped of heavy metals to the combustion process in order to destroy organic substances. On an industrial scale, the heavy metals in the filter ash were mobilized by means of hydrochloric acid in the acidic fluids produced in the flue-gas scrubbing process without the addition of further chemicals. A pilot plant for implementing the selective reactive extraction (SRE) method on the ash extracts, using a highly selective complexant, was operated over a period of several months in order to obtain a concentrated, high-purity zinc salt solution (mono metal solution). A zinc depletion rate of 99.8% in the aqueous extract was achieved using mixer-settler units. The residual zinc concentration in the waste water was then < 2 mg L(-1). By stripping the loaded organic phase, a concentrated, high-purity mono metal solution with 190 g L(-1) zinc was obtained. Zinc metal with a purity > 99.99% is then separated by means of electrolysis. To destroy organic substances present in the filter ash, particularly dioxins and furans, the extracted filter ash cake was returned to the combustion process together with household waste. Plant operation, raw and pure gas parameters, and quality of the bottom ash produced were not impacted by such recirculation. The profitability of the overall process is attributable both to the recovery of valuable zinc metal and to the cost savings made in waste water treatment and in the disposal of the waste combustion residues because the remaining mixture of filter ash and bottom ash can be reused in a combined form. This method therefore supports the sustainable and economically viable reuse of filter ash.     

Flow analysis of metals in a municipal solid waste management system

This study aimed to identify the metal flow in a municipal solid waste (MSW) management system. Outputs of a resource recovery facility, refuse derived fuel (RDF) production facility, carbonization facility, plastics liquefaction facility, composting facility, and bio-gasification facility were analyzed for metal content and leaching concentration. In terms of metal content, bulky and incombustible waste had the highest values. Char from a carbonization facility, which treats household waste, had a higher metal content than MSW incinerator bottom ash. A leaching test revealed that Cd and Pb in char and Pb in RDF production residue exceeded the Japanese regulatory criteria for landfilling, so special attention should be paid to final disposal of these substances. By multiplying metal content and the generation rate of outputs, the metal content of input waste to each facility was estimated. For most metals except Cr, the total contribution ratio of paper/textile/plastics, bulky waste, and incombustible waste was over 80%. Approximately 30% of Cr originated from plastic packaging. Finally, several MSW management scenarios showed that most metals are transferred to landfills and the leaching potential of metals to the environment is quite small.     

Controlled combustion tests and bottom ash analysis using household waste with varying composition

The influence of the co-combustion of household waste with either sewage sludge, shredder fluff, electronic and electrical waste (WEEE) or PVC on the bottom ash quality and content was investigated under controlled laboratory conditions using a pot furnace. This laboratory approach avoids the interpretation problems related to large variations in input waste composition and combustion conditions that are observed in large scale MSW incinerators. The data for metals content, transfer coefficients and leaching values are presented relative to data for a base household waste composition that did not contain any of the added special wastes. The small WEEE invited direct measurement of precious metals content in the ashes, where measurement accuracy is facilitated by using only mobile phone scrap for small WEEE. The analyses were carried out for different particle size ranges that are of relevance to the recyclability of metals and minerals in the ashes. Positive correlations were found between elements content of the input waste and the bottom ashes, and also between increased levels of Cl, Mo and Cu in the input waste and their leaching in the bottom ashes. These correlations indicate that addition of PVC, small WEEE and shredder fluff in input waste can have a negative influence on the quality of the bottom ashes. Enrichment of Au and Ag occurred in the fractions between 0.15 and 6 mm. The precious metals content represents an economically interesting intrinsic value, even when the observed peak values are properly averaged over a larger volume of ashes. Overall, it has been shown that changes in quality and content of bottom ashes may be traced back to the varied input waste composition.