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.     

生物质热解焦油脱除方法研究进展

生物质热解焦油的产生不仅降低了热解效率,影响设备运行,更危害着人类健康。通过介绍生物质热解焦油的特性及危害、对比分析目前各种不同除焦方法(文丘里法、旋风分离法、电捕焦法、高温裂解法和催化裂解法)的特点及应用前景,得出采用多种方法组合的形式进行联合除焦可显著提高焦油脱除效率。寻找用于湿法除焦的可再生利用的有机溶剂,开发经济、高效、长寿命的催化剂将成为生物质热解焦油脱除技术开发的重点。     

Method to recover and reuse chromated copper arsenate wood preservative from spent treated wood

The volume of chromated copper arsenate (CCA) treated wood products coming out of service is expected to increase dramatically during the next decade. There is a need for an alternative waste management approach to landfilling. This paper investigates the variables affecting extraction of CCA components from wood particles and the potential to oxidize and reuse the recovered chemicals. Most of the CCA components could be extracted by 10% H2O2 at 50 degrees C in 6 h with an average extraction efficiency of 95% for Cr, 94% for Cu and 98% for As. The extract containing Cr(III), Cu(II) and As(V) could be oxidized in several stages by aqueous 2.5% w/w H2O2 in less than 2 h to a condition where it was compatible with CCA treating solutions and could be reused for treating new wood. When the recovered extract was mixed with fresh CCA solution in different ratios, the mixed CCA-C solutions had similar solution stability as freshly prepared CCA-C solution and treated wood had similar leaching properties as wood treated with fresh solution.     

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.     

Influence of pine wood shavings on the pyrolysis of poultry litter

Poultry litter from broilers and turkeys are a mixture of manure, feathers, feed and wood shavings, thus pyrolysis oils produced from this material are influenced by the individual components. In order to determine the influence of wood shavings that are used as bedding material, we investigated the pyrolysis of pine wood shavings and poultry manure. Because manure from layer chickens are usually not contaminated with wood shavings, we made mixtures of layer manure and pine wood shavings in the following manure to wood ratios, 100:0, 75:25, 50:50, 25:75, and 0:100 w/w and pyrolyzed them in a fluidized bed reactor at 450 °C. The total liquid yield ranged from 43.3 to 62.7 wt.%. The layer manure oil had a HHV of 29.7 MJ/kg and pH of 5.89 compared to pine wood oil which had HHV of 25.6 MJ/kg and pH of 3.04. The addition of wood shavings to manure clearly influenced the physical properties of the oil, resulting in a decrease in pH and HHV and an increase in density. The oils had relatively high nitrogen content ranging from 1.36 to 5.88 wt.%. The ash (<0.07 wt.%) and sulfur (<0.28 wt.%) contents were very low. FTIR, ¹³C NMR and ¹H NMR spectrometric analysis of the oils showed that manure oil was rich in hydrocarbons and nitrogenous compounds such as primary, secondary amides, aromatic amines and N-heterocyclic. The properties of the oils were strongly influenced by the amount of wood in the mixture.     

Characterization of products obtained from pyrolysis and steam gasification of wood waste,RDF, and RPF

Pyrolysis and steam gasification of woody biomass chip (WBC) obtained from construction and demolition wastes, refuse-derived fuel (RDF), and refuse paper and plastic fuel (RPF) were performed at various temperatures using a lab-scale instrument. The gas, liquid, and solid products were examined to determine their generation amounts, properties, and the carbon balance between raw material and products.The amount of product gas and its hydrogen concentration showed a considerable difference depending on pyrolysis and steam gasification at higher temperature. The reaction of steam and solid product, char, contributed to an increase in gas amount and hydrogen concentration. The amount of liquid products generated greatly depended on temperature rather than pyrolysis or steam gasification. The compositions of liquid product varied relying on raw materials used at 500 °C but the polycyclic aromatic hydrocarbons became the major compounds at 900 °C irrespective of the raw materials used. Almost fixed carbon (FC) of raw materials remained as solid products under pyrolysis condition whereas FC started to decompose at 700 °C under steam gasification condition.For WBC, both char utilization by pyrolysis at low temperature (500 °C) and syngas recovery by steam gasification at higher temperature (900 °C) might be practical options. From the results of carbon balance of RDF and RPF, it was confirmed that the carbon conversion to liquid products conspicuously increased as the amount of plastic increased in the raw material. To recover feedstock from RPF, pyrolysis for oil recovery at low temperature (500 °C) might be one of viable options. Steam gasification at 900 °C could be an option but the method of tar reforming (e.g. catalyst utilization) should be considered.     

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.     

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.     

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.     

Concentrations of organic wood preservatives in wood chips produced from wood wastes

We investigated the concentrations of wood preservatives in the wood chips produced in wood-waste processing facilities in 1988, 1998–1999, and 2001–2002. Among the wood preservatives used in the past in Japan, halophenols, including PCP, chlordane, and chlorpyrifos, had comparatively high detection rates and high average concentrations in the wood chips produced in 2001–2002. Aldrin and endrin were rarely detected, and DDT was already in low concentrations in those wood chips. Although several types of wood preservative were contained in the wood chips, their concentration levels depended on the sources of the wood wastes. In chips produced from wooden pallets, wooden forms for concrete working, or wood discarded from nondemolition sources, no organochlorine wood preservatives were detected, and chlorpyrifos and chlorophenols were detected at one order of magnitude lower than the average concentrations in chips produced from wood wastes discarded in house demolitions.     

Pyrolysis of polyethylene mixed with paper and wood: Interaction effects on tar, char and gas yields

In the present study the interactions between the main constituents of the refuse derived fuel (plastics, paper, and wood) during pyrolysis were studied. Binary mixtures of polyethylene-paper and polyethylene/sawdust have been transformed into pellets and pyrolyzed. Various mixtures with different composition were analyzed and pyrolysis products (tar, gas, and char) were collected. The mixtures of wood/PE and paper/PE have a different behavior. The wood/PE mixtures showed a much reduced interaction of the various compounds because the yields of pyrolysis products of the mixture can be predicted as linear combination of those of the pure components. On the contrary, a strong char yield increase was found at a low heating rate for paper/PE mixtures. In order to explain the results, the ability of wood and paper char to adsorb and convert the products of PE pyrolysis into was studied. Adsorption and desorption tests were performed on the char obtained by paper and wood by using n-hexadecane as a model compound for the heavy products of PE pyrolysis.     

Material conversion from used oil sorbents by pyrolysis

Journal of Material Cycles and Waste Management - A lab-prepared cellulosic oil sorbent—used for oil spill cleanup—was pyrolyzed in a quartz, pipe-type horizontal furnace at different...     

Storage stability of biocrude oils from fast pyrolysis of poultry litter

The unstable nature of biocrude oils produced from conventional pyrolysis of biomass is one of the properties that limits its application. In the disposal of poultry litter via pyrolysis technology, the biocrude oil produced as a value-added product can be used for on farm applications. In this study, we investigated the influence of bedding material (wood shavings) on the storage stability of biocrude oils produced from the fast pyrolysis of poultry litter. The biocrude oils produced from manure, wood (pine and oak), and mixtures of manure and wood in proportions (75:25 50:50, and 25:75 w/w%) were stored under ambient conditions in sealed glass vials for a period of 6 months and their stability were monitored by measuring the changes in viscosity over time. The manure oil had the lowest rate of viscosity change and thus was relatively the most stable and the oils from the 50:50 w/w% litter mixtures were the least stable. The rate of viscosity change of the manure biocrude oil was 1.33 cP/day and that of the 50/50 litter mixture was 7.6 cP/day for pine and 4.17 cP/day for oak.The spectrometric analyses of the biocrude oils showed that the presence of highly reactive oxygenated functionalities in the oil were responsible for the instability characteristic of the litter biocrude oils. The poor stability of the biocrude oil from the 50:50 w/w% litter mixtures was attributed to reactions between nitrogenous compounds (amides) from protein degradation and oxygenated compounds from the decomposition of polysaccharides and lignin. The addition of 10% methanol and 10% ethanol to the oil from 50% manure and 50% pine reduced the initial viscosity of the oil and was also beneficial in slowing down the rate of viscosity change during storage.     

Biocrude oils from the fast pyrolysis of poultry litter and hardwood

The safe and economical disposal of poultry litter is becoming a major problem for the USA poultry industry. Current disposal methods such as land application and feeding to cattle are now under pressure because of pollution of water resources due to leaching, runoffs and concern for mad cow disease contamination of the food chain. Incineration or combustion is potentially applicable to large scale operations, but for small scale growers and EPA non-attainment areas, this is not a suitable option because of the high cost of operation. Thus, there is a need for developing appropriate technologies to dispose poultry litter.Poultry litters from broiler chicken and turkey houses, as well as bedding material were converted into biocrude oil in a fast pyrolysis fluidized bed reactor. The biocrude oil yields were relatively low ranging from 36 wt% to 50 wt% depending on the age and bedding material content of the litter. The bedding material (which was mostly hardwood shavings) biocrude oil yield was 63 wt%. The higher heating value (HHV) of the poultry litter biocrude oils ranged from 26 MJ/kg to 29 MJ/kg while that of the bedding material was 24 MJ/kg. The oils had relatively high nitrogen content ranging from 4 wt% to 8 wt%, very low sulfur (<1 wt%) content and high viscosity. The viscosities of the oils appeared to be a function of both the source of litter and the pyrolysis temperature. The biochar yield ranged from 27 wt% to 40 wt% depending on the source, age and composition of the poultry litter. The biochar ash content ranged from 24 wt% to 54 wt% and was very rich in inorganic components such as potassium and phosphorous.     

Bio-oil production from pyrolysis of waste sawdust with catalyst ZSM-5

Journal of Material Cycles and Waste Management - Slow pyrolysis is characterized by a low heating rate and high reaction time. The products are bio-char, bio-oil and bio-gas. In bio-oil, there are...     

Quality improvement of pyrolysis oil from waste rubber by adding sawdust

This work was aimed at improving the pyrolysis oil quality of waste rubber by adding larch sawdust. Using a 1 kg/h stainless pyrolysis reactor, the contents of sawdust in rubber were gradually increased from 0%, 50%, 100% and 200% (wt%) during the pyrolysis process. Using a thermo-gravimetric (TG) analyzer coupled with Fourier transform infrared (FTIR) analysis of evolving products (TG–FTIR), the weight loss characteristics of the heat under different mixtures of sawdust/rubber were observed. Using the pyrolysis–gas chromatography (GC)–mass spectrometry (Py–GC/MS), the vapors from the pyrolysis processes were collected and the compositions of the vapors were examined. During the pyrolysis process, the recovery of the pyrolysis gas and its composition were measured in-situ at a reaction temperature of 450 °C and a retaining time of 1.2 s. The results indicated that the efficiency of pyrolysis was increased and the residual carbon was reduced as the percentage of sawdust increased. The adding of sawdust significantly improved the pyrolysis oil quality by reducing the polycyclic aromatic hydrocarbons (PAHs) and nitrogen and sulfur compounds contents, resulting in an improvement in the combustion efficiency of the pyrolysis oil.     

Recovery of glass fibers from glass fiber reinforced plastics by pyrolysis

Fiber-reinforced plastic sheets containing unsaturated polyester cross-linked with styrene, CaCO₃ and glass fibers as fillers were pyrolyzed in a helium and steam atmosphere in order to recover glass fibers and valuable organic pyrolysis products. Glass fibers were separated from CaCO₃ and CaO by dissolving calcium salts in hydrochloric acid. Residual organic material was burnt afterwards. Best results were obtained at a pyrolysis temperature of 600 and 700 °C, resulting in a large liquid fraction high in styrene, leaving little residual organic material on the surface of the glass fibers. At a pyrolysis temperature of 500 °C, the degradation of the polymer matrix was incomplete, and at 900 °C, glass fibers were destroyed in the presence of CaO, leaving CaSiO₃ as a product.     

Tar-free fuel gas production from high temperature pyrolysis of sewage sludge

Pyrolysis of sewage sludge was studied in a free-fall reactor at 1000–1400 °C. The results showed that the volatile matter in the sludge could be completely released to gaseous product at 1300 °C. The high temperature was in favor of H₂ and CO in the produced gas. However, the low heating value (LHV) of the gas decreased from 15.68 MJ/N m³ to 9.10 MJ/N m³ with temperature increasing from 1000 °C to 1400 °C. The obtained residual solid was characterized by high ash content. The energy balance indicated that the most heating value in the sludge was in the gaseous product.     

Glass-ceramics from vitrified sewage sludge pyrolysis residues and recycled glasses

Pyrolysis of urban plant sewage sludge has been demonstrated to be an effective way to produce fuel gas. However, a complete disposal of this particular waste is not achieved if the solid residues from the treatment are not considered. In this paper we discuss the feasibility an integrated pyrolysis/vitrification/sintering approach, aimed at a “full” disposal: the pyrolysis residues are first converted into a glass, then transformed into glass–ceramics, by simple viscous flow sintering treatments, with or without additions of inexpensive recycled glasses and kaolin clay. The obtained products were demonstrated to constitute an alternative to natural stones, in terms of both mechanical strength and chemical stability.     

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...