Paper fibers as a carbon source for the de novo formation of polychlorinated dioxins and furans

The formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) from carbon that was produced by the pyrolysis of paper fibers and from wood charcoal was investigated experimentally. Fibers obtained from filter paper were pyrolyzed at 300° and 800°C to produce low- and high-temperature carbon samples. The two types of carbon and wood charcoal were mixed with silica (SiO₂) and trace copper oxide to produce three synthetic fly ash samples. Experiments to measure the formation of PCCDs/Fs from the three ash samples were conducted using a bench-scale reactor. The two carbon samples derived from paper fibers generated more PCDDs/Fs than was generated by the wood charcoal. The PCDDs/Fs generated by the low-temperature carbon and by the wood charcoal were dominated by the lower-chlorinated PCDFs. Such unique homologue distribution patterns are very similar to those generated by the open burning of household waste. The high-temperature carbon generated more highly chlorinated PCDDs/Fs. The effect of pyrolysis temperature on the de novo formation of PCDDs/Fs from residual carbon is discussed. Paper and paper products contained in household waste are likely to be the source of unburned carbon that contributes to high PCDD/F emissions in the open burning of household waste.     

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.     

Removal of copper,chromium, and arsenic from CCA-C treated wood by EDTA extraction

Ethylenediaminetetracetic acid (EDTA) is one of the most common chelators used to bind the metal ions in extremely stable complexes in heavy metal contaminated soils and thus to remediate such substrates. EDTA forms water soluble complexes with many metal ions and it is used to release the various metals. In this study, EDTA extraction of copper, chromium, and arsenic from chromated copper arsenate (CCA-C) treated wood was evaluated using batch leaching experiments. CCA-treated wood samples were extracted with eight different concentrations of EDTA for 4, 8, 18, and 24 h at room temperature. Exposing CCA-treated chips and sawdust to EDTA extraction enhanced removal of CCA components compared with extraction by deionized water. Grinding CCA-treated wood chips into 40-mesh sawdust provided greater access to and removal of CCA components. Extraction with 1% EDTA solution for 24 h removed 60% copper, 13% chromium, and 25% arsenic from treated chips. EDTA extraction of treated sawdust samples resulted in 93% copper, 36% chromium, and 38% arsenic removal. CCA leaching from treated wood blocks was also evaluated according to modified AWPA E11-99 standard test method of determining the leachability of wood preservatives. Leaching of CCA components from treated wood blocks with 1% EDTA solution for 14 days caused more copper leaching compared to leaching with deionized water. Leaching with 1% EDTA for 14 days removed 53% copper from the blocks whereas 14% copper was leached from the blocks with deionized water. The results suggest that EDTA extraction removes significant quantities of copper from CCA-treated wood. Thus, EDTA could be important in the remediation of wood waste treated with the newest formulations of organometalic copper compounds and other water-borne wood preservatives containing copper.     

The Chartherm process,what’s in the name?

Earlier research has identified the Chartherm process (Thermya, France) as a candidate for the best available technology to treat chromated copper arsenate (CCA) impregnated wood waste. This paper presents the working principle, the characteristics and the current state-of-knowledge related to the process, illustrating clearly the differences with pyrolysis and carbonisation processes. To emphasise the specific nature of the process, it has been given its own name ‘chartherisation’. The avoidance of tar and dioxin release, the role of the solid matrix in the metal behaviour and the separation process are described. Furthermore, the possible benefits of working at elevated pressure are discussed, based on the experience with charcoal production from coal and biomass. This paper shows that more fundamental research is needed to understand and model all mechanisms contributing to the characteristic nature of chartherisation, in order to control the dynamic behaviour and tune the operating conditions in the reactor on the quality of the products requested.     

Leaching of heavy metals from chromated copper arsenate (CCA) treated wood after disposal

Wood treated by preservatives is commonly found in solid waste. Among the different types of preserved wood, chromated copper arsenate (CCA) treated wood recently has received much attention due to the scale of usage and its significant role in soil and water contamination. As the ash of CCA treated wood would be hazardous if the wood were to be incinerated, this is not a good alternative, and the best available disposal method is thus landfilling in the US, Canada and Australia. Leaching of the metals from preserved wood that is disposed in unlined landfills for construction debris pollutes the soil and water environments. Several factors affecting leaching of the metals from wood, including pH of the leachant, temperature, the duration of leaching and the type of leachant, were investigated. These factors affect each of the metals, chromium, copper and arsenic, differently. A comparison of these effects on each metal was performed. The results of the experiments showed that the pH of the leachants has a significant effect on the leaching process, and sulfuric acid (pH 3) is the most effective leachant compared to nitric and acetic acid (pH 3-4-5). The amounts of leached chromium, copper and arsenic by sulfuric acid (pH 3) during 15 days were, respectively, 0.2, 0.14 and 0.15 mg more than leachates by nitric acid (pH 5) on the basis of 1g of wood (initial contents of 1.03 mg, 0.42 g and 0.8 mg per g of wood). Most of the leaching occurs in the first 5 days, and the rate of leaching decreases significantly after 5 days. Increasing temperature increases the amount of leached metals, and arsenic is the least resistant metal to the leaching when the temperature increases. Increasing the temperature from 15 degrees C to 35 degrees C during 15 days increases the amount of leached chromium, copper and arsenic by acetic acid at pH 5 by about 0.1, 0.4 and 1.2mg per g of wood, respectively.     

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).     

Online sorting of recovered wood waste by automated XRF-technology. Part I: detection of preservative-treated wood waste

Waste wood is frequently contaminated with wood treatment preservatives including chromated copper arsenate (CCA) and alkaline copper quat (ACQ), both of which contain metals which contaminate recycled wood products. The objective of this research was to propose a design for online automated identification of As-based and Cu-based treated wood within the recovered wood waste stream utilizing an X-ray fluorescence (XRF) system, and to evaluate the detection parameters of such system. A full-scale detection unit was used for experimentation. Two main parameters (operational threshold (OT) and measurement time) were evaluated to optimize detection efficiencies. OTs of targeted metals, As and Cu, in wood were reduced to 0.02 and 0.05, respectively. The optimum minimum measurement time of 500 ms resulted in 98%, 91%, and 97% diversion of the As, Cu and Cr mass originally contained in wood, respectively. Comparisons with other detection methods show that XRF technology can potentially fulfill the need for cost-effective processing at large facilities (>30 tons per day) which require the removal of As-based preservatives from their wood waste stream.     

Clay-sewage sludge co-pyrolysis. A TG-MS and Py-GC study on potential advantages afforded by the presence of clay in the pyrolysis of wastewater sewage sludge

Wastewater sewage sludge was co-pyrolyzed with a well characterized clay sample, in order to evaluate possible advantages in the thermal disposal process of solid waste. Characterization of the co-pyrolysis process was carried out both by thermogravimetric-mass spectrometric (TG-MS) analysis, and by reactor tests, using a lab-scale batch reactor equipped with a gas chromatograph for analysis of the evolved gas phase (Py-GC).Due to the presence of clay, two main effects were observed in the instrumental characterization of the process. Firstly, the clay surface catalyzed the pyrolysis reaction of the sludge, and secondly, the release of water from the clay, at temperatures of approx. 450-500 °C, enhanced gasification of part of carbon residue of the organic component of sludge following pyrolysis.Moreover, the solid residue remaining after pyrolysis process, composed of the inorganic component of sludge blended with clay, is characterized by good features for possible disposal by vitrification, yielding a vitreous matrix that immobilizes the hazardous heavy metals present in the sludge.     

Evaluation of XRF and LIBS technologies for on-line sorting of CCA-treated wood waste

Contamination of wood waste with chromated copper arsenate greatly limits recycling opportunities for the wood waste as a whole. Separation of CCA-treated wood from other wood types is one means by which such contamination can be removed. The purpose of the current study was to evaluate two detector technologies for sorting CCA-treated wood from other wood types. The detector technologies evaluated included X-ray fluorescence spectroscopy (XRF) and laser induced breakdown spectroscopy (LIBS). The XRF detector system utilized in this study was capable of rapidly detecting the presence of CCA in painted wood, wet wood, heartwood, sapwood, and at portions of the wood containing knots. Furthermore, the XRF system was capable of distinguishing between CCA-treated wood and wood treated with alternative wood treatment preservatives, but was limited by the fact that it was not designed for on-line operation so tests were conducted in a batch mode on a conveyor. The analysis time used in this study (3 s) can be decreased significantly for an XRF system designed specifically for on-line operation. The LIBS system developed for this study was found to effectively identify CCA-treated wood for pieces ranging in thickness from 1 to 8 cm. High sorting efficiencies were noted when 10 laser shots were taken on a piece of wood. Furthermore, the LIBS system was found to be effective for identifying wood that has been coated with stains and paints in addition to identifying wood that has been CCA treated. The major drawback with the LIBS system developed in this study was the limited laser pulse energy. With an increase in laser pulse energy it is anticipated that the working focal length of the LIBS system can be increased to enable the monitoring of wood samples of more variable thicknesses. Limitations associated with analysis of very rotted pieces of wood and wet wood can also be overcome by using a higher pulse energy laser. Overall, both technologies show incredible promise for sorting CCA-treated wood from other wood types. The next recommended step would be to run an improved full-scale operation at one facility to document sorting efficiencies and fine-tune the improvements proposed in the current study. Such a study could potentially open-the-door for more widespread sorting of wood waste.     

Comparison of coal/solid recovered fuel (SRF) with coal/refuse derived fuel (RDF) in a fluidized bed reactor

An experimental study was undertaken to compare the differences between municipal solid waste (MSW) derived solid recovered fuel (SRF) (complying with CEN standards) and refuse derived fuel (RDF). Both fuels were co-combusted with coal in a 50 kW fluidised bed combustor and the metal emissions were compared. Synthetic SRF was prepared in the laboratory by grinding major constituents of MSW such as paper, plastic, textile and wood. RDF was obtained from a local mechanical treatment plant. Heavy metal emissions in flue gas and ash samples from the (coal + 10% SRF) fuel mixture were found to be within the acceptable range and were generally lower than that obtained for coal + 10% RDF fuel mixture. The relative distribution of heavy metals in ash components and the flue gas stream shows the presence of a large fraction (up to 98%) of most of the metals in the ash (except Hg and As). Thermo-gravimetric (TG) analysis of SRF constituents was performed to understand the behaviour of fuel mixtures in the absence and presence of air. The results obtained from the experimental study will enhance the confidence of fuel users towards using MSW-derived SRF as an alternative fuel.     

Evaluation of the potential of applying composting/bioremediation techniques to wastes generated within the construction industry

The objective of the present study was to evaluate the viability of reducing landfill requirements to satisfy EC Landfill Directive requirements by applying composting/bioremediation techniques to the construction and demolition (C&D) industry waste stream at laboratory scale. The experimental study was carried out in nine test rigs to examine different wood mixtures; untreated timber, creosote treated timber and chromated copper arsenate (CCA) treated timber. Several experimental variables affecting the process were characterised and optimised. These include the best nitrogen additive and optimum moisture content required for composting. Poultry manure was found to be the best nitrogen additive. The optimum moisture content was decreased after the addition of poultry manure. The composting/bioremediation process was evaluated through monitoring the microbial activity, carbon dioxide emissions and toxicity examination of the composted product. A typical temperature profile suggested that untreated and CCA treated mix could be classified as hot composting whereas creosote treated mix could be classified as cold composting. The paper reports on the results obtained during this investigation.     

Valorisation of waste tyre by pyrolysis in a moving bed reactor

The aim of this work is to assess the behaviour of a moving bed reactor, based on a screw transporter design, in waste tyre pyrolysis under several experimental conditions. Waste tyre represents a significant problem in developed countries and it is necessary to develop new technology that could easily process big amounts of this potentially raw material. In this work, the influence of the main pyrolysis process variables (temperature, solid residence time, mass flow rate and inert gas flow) has been studied by a thorough analysis of product yields and properties. It has been found that regardless the process operational parameters, a total waste tyre devolatilisation is achieved, producing a pyrolytic carbon black with a volatile matter content under 5 wt.%. In addition, it has been proven that, in the range studied, the most influencing process variables are temperature and solid mass flow rate, mainly because both variables modify the gas residence time inside the reactor. In addition, it has been found that the modification of these variables affects to the chemical properties of the products. This fact is mainly associated to the different cracking reaction of the primary pyrolysis products.     

Characteristics of gas and residues produced from electric arc pyrolysis of waste lubricating oil

An attempted has been made to recover high-calorific fuel gas and useful carbonaceous residue by the electric arc pyrolysis of waste lubricating oil. The characteristics of gas and residues produced from electric arc pyrolysis of waste lubricating oil were investigated in this study. The produced gas was mainly composed of hydrogen (35–40%), acetylene (13–20%), ethylene (3–4%) and other hydrocarbons, whereas the concentration of CO was very low. Calorific values of gas ranged from 11,000 to 13,000 kcal kg^?1 and the concentrations of toxic gases, such as NO_x, HCl and HF, were below the regulatory emissions limit. Gas chromatography–mass spectrometry (GC/MS) analysis of liquid-phase residues showed that high molecular-weight hydrocarbons in waste lubricating oil were pyrolyzed into low molecular-weight hydrocarbons and hydrogen. Dehydrogenation was found to be the main pyrolysis mechanism due to the high reaction temperature induced by electric arc. The average particle size of soot as carbonaceous residue was about 10 μm. The carbon content and heavy metals in soot were above 60% and below 0.01 ppm, respectively. The utilization of soot as industrial material resources such as carbon black seems to be feasible after refining and grinding.     

Pyrolysis of waste tyres: A review

Approximately 1.5 billion tyres are produced each year which will eventually enter the waste stream representing a major potential waste and environmental problem. However, there is growing interest in pyrolysis as a technology to treat tyres to produce valuable oil, char and gas products. The most common reactors used are fixed-bed (batch), screw kiln, rotary kiln, vacuum and fluidised-bed. The key influence on the product yield, and gas and oil composition, is the type of reactor used which in turn determines the temperature and heating rate. Tyre pyrolysis oil is chemically very complex containing aliphatic, aromatic, hetero-atom and polar fractions. The fuel characteristics of the tyre oil shows that it is similar to a gas oil or light fuel oil and has been successfully combusted in test furnaces and engines. The main gases produced from the pyrolysis of waste tyres are H₂, C₁–C₄ hydrocarbons, CO₂, CO and H₂S. Upgrading tyre pyrolysis products to high value products has concentrated on char upgrading to higher quality carbon black and to activated carbon. The use of catalysts to upgrade the oil to a aromatic-rich chemical feedstock or the production of hydrogen from waste tyres has also been reported. Examples of commercial and semi-commercial scale tyre pyrolysis systems show that small scale batch reactors and continuous rotary kiln reactors have been developed to commercial scale.     

Development of waste gasification and gas reforming system for municipal solid waste (MSW)

To achieve both high-efficiency power generation and high detoxification performance, advanced-type waste power generation plants such as pyrolysis and gas reforming plants are suggested. Further surveys on actual operational data of these plants are required in terms of reliability of the system when it is introduced to waste disposal sites. To verify the technical effectiveness of advanced-type waste power generation using the pyrolysis and gas reforming method, we evaluated 10?tons/day of municipal solid wastes (MSW) treated in a demonstration plant. A demonstration test was conducted over 100?days including 35?consecutive days of operation treating MSWs. The test results show high recycling performance and harmless nature of the plant which proves it to be an excellent waste recycling system. Major test results are as follows: (1) stabilization of waste treatment is possible with the wastes of various qualities, (2) clean gas is produced from the waste whose energy recovery ratio is approximately 40?%. (3) 99.3?% weight % of dried waste are recovered as valuable materials such as clean gas, char and metal, (4) total amount of dioxin emission to the outside of the plant is very small, down to 0.0051–0.018?μg?TEQ per ton waste.     

Evaluation of commercial landscaping mulch for possible contamination from CCA

Wood treated with chromated copper arsenate (CCA) is found in construction and demolition (C&D) debris, and a common use for wood recycled from C&D debris is the production of mulch. Given the high metals concentrations in CCA-treated wood, a small fraction of CCA-treated wood can increase the metal concentrations in the mulch above regulatory thresholds. The objective of this study was to determine the extent of contamination of CCA-treated wood in consumer landscaping mulch and to determine whether visual methods or rapid X-ray fluorescence (XRF) technology can be used to identify suspect mulch. Samples were collected throughout the State of Florida (USA) and evaluated both visually and chemically. Visual analysis focused on documenting wood-chip size distribution, whether the samples were artificially colored, and whether they contained plywood chips which is an indication that the sample was, in part, made from recycled C&D wood. Chemical analysis included measurements of total recoverable metals, leachable metals as per the standardized synthetic precipitation leaching procedure (SPLP), and XRF analysis. Visual identification methods, such as colorant addition or presence of plywood, were found effective to preliminarily screen suspect mulch. XRF analysis was found to be effective for identifying mulch containing higher than 75 mg/kg arsenic. For mulch samples that were not colored and did not contain evidence of C&D wood, none exceeded leachable metal concentrations of 50 microg/L and only 3% exceeded 10 mg/kg for recoverable metals. The majority of the colored mulch made from recycled C&D wood contained from 1% to 5% CCA-treated wood (15% maximum fraction) resulting in leachable metals in excess of 50 microg/L and total recoverable metals in excess of 10 mg/kg. The maximum arsenic concentration measured in the mulch samples evaluated was 230 mg/kg, which was above the Florida residential direct exposure regulatory guideline of 2.1 mg/kg.     

Auto shredder residue recycling: Mechanical separation and pyrolysis

Directive 2000/53/EC sets a goal of 85% material recycling from end-of-life vehicles (ELVs) by the end of 2015. The current ELV recycling rate is around 80%, while the remaining waste is called automotive shredder residue (ASR), or car fluff. In Europe, this is mainly landfilled because it is extremely heterogeneous and often polluted with car fluids. Despite technical difficulties, in the coming years it will be necessary to recover materials from car fluff in order to meet the ELV Directive requirement. This study deals with ASR pretreatment and pyrolysis, and aims to determine whether the ELV material recycling target may be achieved by car fluff mechanical separation followed by pyrolysis with a bench scale reactor. Results show that flotation followed by pyrolysis of the light, organic fraction may be a suitable ASR recycling technique if the oil can be further refined and used as a chemical. Moreover, metals are liberated during thermal cracking and can be easily separated from the pyrolysis char, amounting to roughly 5% in mass. Lastly, pyrolysis can be a good starting point from a "waste-to-chemicals" perspective, but further research should be done with a focus on oil and gas refining, in order both to make products suitable for the chemical industry and to render the whole recycling process economically feasible.     

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.     

热解温度对青霉素菌渣热解产物的影响

将青霉素菌渣在400~700 ℃进行热解,研究了产物中热解炭、热解油及气体的产率,以及热解油的组成变化。实验结果表明：600 ℃时热解油产率最高,随着温度升高,热解炭的产率降低,气体的产率升高;热解油中含量最高的是含氧化合物,在400 ℃时质量分数达到最高值69.69%,含氧化合物的含量随着热解温度的升高而降低,酸和醇类是热解油中含量最多的含氧化合物;含氮有机化合物的质量分数随着热解温度的升高而升高,在700 ℃时达到最高值30.64%,酰胺、吡啶、吲哚、含氮杂环是主要的含氮有机化合物。     

Improving the two-step remediation process for CCA-treated wood: Part II. Evaluating bacterial nutrient sources

Remediation processes for recovery and reuse of chromated-copper-arsenate- (CCA) treated wood are not gaining wide acceptance because they are more expensive than landfill disposal. One reason is the high cost of the nutrient medium used to culture the metal-tolerant bacterium, Bacillus licheniformis, which removes 70-100% of the copper, chromium, and arsenic from CCA-treated southern yellow pine (CCA-SYP) in a two-step process involving oxalic acid extraction and bacterial culture. To reduce this cost, the nutrient concentration in the culture medium and the ratio of wood to nutrient medium were optimized. Maximum metal removal occurred when B. licheniformis was cultured in 1.0% nutrient medium and at a wood to nutrient medium ratio of 1:10. Also, malted barley, an abundant by-product of brewing, was evaluated as an alternative nutrient medium. Tests were done to determine absorption of metals by barley, and the results indicate that the barley acted as a biosorbent, removing heavy metals from the liquid culture after their release from CCA to SYP. For comparison, tests were also performed with no nutrient medium. Following bacterial remediation, 17% copper and 15% arsenic were removed from an aqueous slurry of CCA-SYP (no medium). When oxalic acid extraction preceded the aqueous bacterial culture, 21% copper, 54% chromium, and 63% arsenic were removed. The two-step process (oxalic acid extraction and bacterial culture with nutrient medium) appears to be an effective, yet costly, way to remove metals.