TGA modeling of the thermal decomposition of CCA treated lumber waste

 To guide the development of thermal decomposition methods for disposal of CCA treated wood, reactions during the thermal decomposition of CCA treated wood were modeled using thermogravimetric analysis (TGA), with special focus placed on arsenic volatilization. Simple inorganic compounds, such as As₂O₅, CuO, and Cr₂O₃, were used to model the thermal behavior of the inorganics in CCA treated wood. In air and nitrogen, arsenic (V) oxide began to volatilize at 600 °C during temperature ramps at 5 °C/min. During a 5 °C/min ramp in a hydrogen mix, arsenic (V) oxide began decomposition at 425 °C. Arsenic volatile loss from CCA treated wood can depend strongly on the gases produced by wood thermal decomposition. In the presence of As₂O₅, chromium (III) oxide and copper (II) oxide formed arsenates in air and nitrogen. Chromium arsenates began decomposition as low as 790 °C. This suggested that chromium arsenates in CCA treated wood formed during original preservative fixation may decompose as low as 790 °C. Copper arsenates were stable up to 900 °C in air, but showed only a limited range of stability in nitrogen. Depending on process conditions, the formation of copper arsenates may limit arsenic loss during thermal decomposition of CCA treated wood up to 900 °C. The thermal decomposition of inorganic oxides was influenced by interactions with wood and wood decomposition products. In a dry YP sawdust/As₂O₅ mix, arsenic (V) oxide volatilized at 370 °C during inert pyrolysis at 5 °C/min and at 320 °C during smoldering combustion at 5 °C/min. Thermal dwells of a dry YP/As₂O₅ mix showed no arsenic loss at 250 °C, but significant loss occurred during higher temperature dwells. During inert pyrolysis at 5 °C/min, the formation of complexes and hydrates were shown to prevent arsenic loss up to 400 °C. Received 14 July 1999     

Characterization of residues from thermal treatment of treated wood and extraction of Cu, Cr, As and Zn

Thermal treatment of chromated copper arsenate (CCA) impregnated waste wood is a way to utilize the energy resource of the wood and at the same time to reduce the volume of the waste. An issue of concern in relation to the thermal treatment is As emission to the air. Meanwhile, there is still a matter to cope with when methods to avoid As emission are implemented: the residues with increased concentrations of Cu, Cr and As. In the present paper two different residues after thermal treatment are characterized: a mixed bottom and fly ash from combustion of CCA impregnated wood, and a charcoal from pyrolysis of treated waste wood. By SEM/EDX it was seen that the charcoal still showed wood structure with both tracheids and rays and that Cu, Cr and As were found inside this wood structure. Cu was found alone while Cr and As were often found together. By chemical analysis it was found, too, that the charcoal contained a high concentration of Zn, probably from paint. Chemical extraction experiments in HNO₃ were conducted with the charcoal and it was found that the order of extraction (in percentage) was Zn > Cu > As > Cr. A SEM/EDX investigation of the mixed ash from combustion showed the presence of small particles with wood structure with elevated Cu and Cr concentrations, but most particles were irregular shaped matrix particles rich in Si, Al and K. Cr was abundant in many different particles including the lignin skeleton of the small, unburned wood pieces, but also inside silica-based matrix particles. Ca was often found associated with char-like (porous) particles, indicating that Ca-arsenates had been formed during combustion. Cu was often associated with Cr in the unburned wood pieces, whereas it was less abundant inside the silica-based matrix particles. Cu was also found in an almost pure form in a small layer on the surface of some matrix particles indicating condensation of volatile Cu species. Chemical extraction with inorganic acids showed the order of percentages mobilized as: As > Cu > Cr.     

Rapid identification of CCA-treated wood using laser-induced breakdown spectroscopy

As chromated copper arsenate (CCA) contains copper, chromium and arsenic, waste CCA-treated wood must be separated from other treated wood because of environmental pollution by chromium and arsenic when it is incinerated and the regulation. Therefore, a method to identify CCA-treated wood was developed using laser-induced breakdown spectroscopy (LIBS). Using the LIBS apparatus assembled in our laboratory, plasma on a wood surface was generated by a 4?ns pulse of 1064?nm (55?mJ/mm²) emitted from Nd:YAG laser. Fluorescence from the plasma was collected by an ellipsoidal mirror and analyzed by a spectrometer in the range of 190–300?nm. The results showed that the 228.7?nm line from As and 267.6?nm line from Cr were useful for the identification of CCA-treated wood. As the discrimination capacity was confirmed by the elemental composition analysis by X-ray fluorescence, it was concluded that LIBS can specifically identify CCA-treated wood.     

Treatment of Softwoods with CCA at High Moisture Levels

A literature study on the feasibility of treating wood with aqueous solutions at high moisture levels revealed a positive indication. The objective of the present study was to determine treatability of Pinus radiata and P. pinaster lumber at high moisture levels with commercial CCA in controlled experiments. The wood samples were treated at levels of moisture content ranging from 20 to 100%.

A statistical analysis of the data showed that specific gravity and moisture content influence solution-absorption, the effect being different for different species. Chemical analyses showed a screening out of copper- and arsenic compounds. The effect of higher moisture contents on screening out was negligible. The results indicated that certain wood species can be treated satisfactorily with CCA at moisture levels higher than 25%.     

Effects of wood species and retention levels on removal of copper,chromium, and arsenic from CCA-treated wood using sodium hypochlorite

Chemical extraction, bioremediation, and electrodialytic processes have been extensively studied for removal of copper, chromium, and arsenic from wood treated with chromated copper arsenate(CCA). However,one problem has not been addressed: the effects of wood species and retention levels on remediation efficiency. The objectives of this study were to investigate the effects of wood species and retention levels on removal of copper,chromium, and arsenic from CCA-treated wood samples using sodium hypochlorite. Our results showed that sodium hypochlorite(Na OCl) was very effective for removal of copper, chromium, and arsenic from CCA-C treated milled wood samples for all three species used in this study. The Cu, Cr, and As extraction efficiencies for red pine were95 % Cu, 97 % Cr and 94 % As, for maple were 95 % Cu,97 % Cr, and 98 % As at 4.0 kg m-3retention levels, and for aspen were 95 % Cu, 92 % Cr, and 91 % As at9.6 kg m-3retention level, respectively. However, the results showed that wood species and initial retention levels of CCA-treated wood products played very important roles in terms of removal of Cu, Cr, and As.     

EXAFS study of chromated copper arsenate timber preservative in wood

Copper and arsenic K-edge X-ray absorption fine structure spectroscopy (EXAFS) of pine wood (Pinus radiata) treated with chromated copper arsenate (CCA) timber preservative have been measured. Refinement of the data is consistent with arsenate anions bound to chromium and copper ions isolated from other heavy elements, regardless of depth into the wood. This constitutes the first substantive analysis of CCA's fixation products and has a number of implications for models of fixation.     

Evolution of CO2 during the fixation of chromium containing wood preservatives on wood

Summary A titration procedure was used to confirm carbon dioxide evolution from wood treated with solutions containing chromic acid and to quantify the effects of species (red pine vs soft maple), solution concentration and reaction temperature on the rate and amount of CO₂ evolved. Small blocks or chips were vacuum treated with either chromated copper arsenate (CCA) wood preservative or chromic acid solutions and the release of CO₂ monitored until the reaction was complete. Significant volumes of CO₂ were measured. This is attributed to the oxidation and subsequent decarboxylation of primary hydroxyl groups on wood constituents. The ratio of moles of CO₂ produced to moles of chromium added to the wood ranged from about 0.07 to 0.24 depending on the wood species, solution properties and fixation conditions. This accounted for from 9 to 32% of the total oxidation potential of the hexavalent chromium applied. The relative amounts of CO₂ produced were higher for maple than for red pine. The rate of CO₂ evolution was also higher in the maple samples, consistent with the higher rate of chromium reduction in soft maple compared to red pine. The amount of C0₂ produced was approximately proportional to the amount of hexavalent chromium in the CCA treating solution although the ratio of CO₂ produced to chromium added to the wood increased slightly with increasing solution concentration. The relative amounts of CO₂ produced increased with increasing fixation temperature over the 50–90 °C range in both species. The rate of CO₂ evolution was accelerated as the fixation temperature was increased. The rates and amounts of CO₂ produced were similar for CCA and Cr0₃ treatments containing the same concentration of chromic acid. Copper and arsenic components of the CCA solution did not appear to have any effect on the decarboxylation reaction.We gratefully acknowledge the financial support of the Natural Sciences and Engineering Research Council of Canada, Natural Resources Canada;, LPB Poles Inc., Masson Quebec, Timber Specialties Ltd., Campbellville Ontario and Guelph Utility Pole Co. Ltd., Guelph Ont. for this study.     

Toxicity of emissions from combustion and pyrolysis of wood

Summary Fuels such as wood and forest residuals are becoming important sources of energy; furthermore, wood and wood products are major components of building construction. In both cases environmental impact and health hazard posed by the burning of these materials must be evaluated. Most death and injuries on exposure to burning wood are due to inhalation of toxic gases, smoke, and heat gases, usually carbon monoxide. Any wood or wood products used in building construction must be chosen so as to release the minimum amount of toxic materials as slowly as possible when heated or burned, to allow people time to escape. The emissions from wood burning power plants certainly have local short term and global long term environmental impacts. For example, massive carbon dioxide production from wood burning is believed to affect the earth's energy balance and therefore global climates. This review does not consider this aspect of wood burning, or other environmental hazards due to power plants utilizing wood, about which little seems to be known. The subject of this review is of the literature from 1971–1979 concerned with the toxicity of products of combustion and/or pyrolysis of wood, or wood products, untreated or treated with preservatives.     

木材阻燃剂FRW的阻燃机理

在综合分析热分析法、锥形量热仪法和FTIR法获得的FRW阻燃机理研究结果并吸收木材阻燃机理研究现有成果的基础上,推导进而提出了木材阻燃剂FRW的阻燃机理。其主要内容是:1)FRW阻燃木材受热时,阻燃剂FRW分解产生不燃性气体和不挥发的酸性熔融物质,具有降低体系温度和氧气浓度及屏蔽热辐射的作用,降低了木材的热解速度;2)FRW的组分硼酸和GUP的酸性分解产物催化木材脱水、降解,以及木材热解产物的缩合、聚合、芳构化等反应,能改变木材的热解途径并使其向着有利于炭化的方向变化,FRW显著的催化成炭作用,使阻燃木材的燃烧放热量大大降低,这是FRW阻燃机理的主要方面;3)硼酸与GUP起阻燃作用的温度和方式不同,并且有相互补充的作用,因而表现出阻燃协同效应。     

Adhesive performance of woods treated with alternative preservatives

The extended use of woods treated with traditional or alternative preservatives for exterior applications requires an assessment of wood adhesive performance. This study attempts to evaluate the performance of wood adhesives for woods treated with various waterborne preservatives. Two softwood species, i.e. Korean pine (Pinus koraiensis Sieb. et Zucc.) and Japanese Larch (Larix leptolepis [Sieb. et Zucc.] Gordon) were treated with copper–chrome–arsenic (CCA), CB-HDO, or copper azole (CY), and then bonded with four different wood adhesives such as urea–melamine–formaldehyde (UMF) resin, melamine–formaldehyde (MF) resin, phenol–formaldehyde (PF) resin, and resorcinol–formaldehyde (RF) resin. The performance of these adhesives was evaluated by measuring the dry shear strength of adhesive-bonded wood block on compression. Both UMF and MF resins produced a relatively strong adhesive strength for CY-treated pine and larch woods. The PF resin also produced good bond strength when bonded with either larch wood treated with CY or pinewood treated with CB-HDO. The best result was obtained when the CB-HDO-treated woods were bonded with RF resin. For a better bond strength development, a proper combination of adhesive, preservative, and wood species should be selected by taking into consideration of the characteristics of these three parameters as well as their interactions.     

用FTIR法研究木材阻燃剂FRW的阻燃机理

采用FTIR显微分析技术,对FRW阻燃处理红松木材限制燃烧固相产物的结构进行分析;采用GC_FTIR联机分析方法,对经FRW阻燃剂及其主要组分处理的紫椴木材试样的热解挥发性产物进行分析和鉴定;讨论FRW阻燃处理木材的热解炭化过程、阻燃剂的作用以及热解产物的结构特点。结果表明:FRW阻燃木材受热时,随着温度的升高,在FRW及其分解产物的催化下,木材逐步发生聚糖脱水、半纤维素脱乙酸、聚糖降解、木质素降解、木材热解产物聚合、脂肪族聚合物脱氧及芳构化等反应,最终炭化;FRW阻燃剂改变了木材的热解途径,并且显著降低了挥发性有机化合物的生成量。     

建筑材用防腐剂配方及其化学性能的试验

我国CCA系列配方与英国CCA(Tanalith C,Celcure K33)的对比试验表明:我国CCA_3、CCA_6配方抗流失和对金属腐蚀效果接近英国产品;砷含量范围低于美国CCA—C型;国产原料配制的CCA_(S)抗流失和对金属腐蚀性较好。浸渍处理试验显示,CCA类防腐剂宜采用加压法。PPA油性防腐剂中的五氯酚溶解度、抗“霜”、油漆性能良好;CCB宜于处理门窗及室内木结构。表层化学浸渍处理可使硼在木材中的保留率提高到60—70%。     

基于CONE法的热处理杨木燃烧特性研究

利用锥形量热仪CONE对不同热处理工艺下的杨木燃烧行为进行研究。结果表明:热处理后杨木中亲水的羟基、羰基数量明显减少,大量半纤维素降解。木材试样从外部热源引燃到燃烧结束,出现两个主要放热峰。热处理后杨木引燃和燃烧过程的发烟量较大,且热处理杨木引燃时间更短。热处理材的热释放峰值pk-HRR、平均热释放速率av-HRR和总热释放量THR均低于未处理材,表明其燃烧强度低于未处理材。热处理杨木燃烧过程的总烟释放量TSP较未处理材有所增加,同时其引燃时间也有所缩短。因此,对用于家具和室内装饰的热处理木材,建议进行恰当的阻燃处理。     

Effects of steam explosion processing and organic acids on CCA removal from treated wood waste

Chromated copper arsenate (CCA) is the primary wood preservative used in the United States. CCA products are used for decking, fencing, retaining walls, docks, poles, and highway sign posts. Since CCA became popular in the early 1970's, it is estimated that over 140 million cubic meters of these products are in service. Although the EPA allows disposal of spent CCA products in landfills, increasingly they are looking at the possibility of restricting its disposal. One method for potential re-use of CCA treated wood fiber would be to remove the treatment chemicals and process the fiber into energy or consumer products. The objectives of this research were to determine which method(s) can improve the removal of copper, chromium, and arsenate from spent CCA-treated lumber. The best material, in this research, for leaching chemicals from treated wood with organic acids, were particles (compared to chips and steam exploded wood). Without the functions of organic acids, the best method to remove chemicals proved to be steam explosion and further extraction by water. Citric acid was the most effective acid used in the removal of treatment chemicals of the three acids evaluated: acetic, citric, and sulfuric. The time effect on the extraction process indicated that most of the treatment chemicals were removed within the first seven days of treatment. This study also indicates that steam explosion does not increase the extractability of the chemical components. Other methods need to be examined which may lead to better removal of the chemicals or more effective methods to recycle spent CCA products.     

CCA 防腐剂在木材中的固着机理

加铬砷酸铜(CCA)作为木材防腐剂在世界范围内已经广泛使用了70余年,目前在我国其仍然是主要的木材防腐剂之一.然而.CCA 中有效成分铬和砷的氧化物所具有的剧毒性,使其在使用过程中流失到外界后会对环境及生物安全造成威胁,而防腐剂中有效成分的流失在很大程度上是由于防腐处理材在使用前防腐剂的有效成分与木材成分之间的固着反应不充分而造成的.对CCA中有效成分在处理材中的固着反应过程、监测方法及反应场所等做了详细介绍,旨在为水基木材防腐剂有效成分在处理材中的固着、流失研究提供借鉴,并为CCA防腐处理材的生产提供理论指导.     

贮木场木材剩余物阴燃过程研究

以木材剩余物构成阴燃床的燃烧材料,在阴燃实验装置中进行阴燃传播实验,利用热电偶测量阴燃传播速度,采用气相色谱仪检测阴燃特征气体组份.并分析了阴燃方式、空气流速和加热功率对阴燃传播过程的影响.研究结果表明:阴燃的传播速度随着氧气浓度、空气流速、加热功率的增加而提高,阴燃初期主要特征气体为CO<,2>和CO,氧气浓度是控制阴燃向有焰燃烧的关键参数,逆向阴燃在向有焰燃烧转变时需要的氧气浓度高于同向阴燃.     

非离子型石蜡乳液增强防腐木材尺寸稳定性的研究

以马尾松、厚荚相思木材为研究对象,将配方优化的非离子型石蜡乳液稀释液及其与木材防腐剂的混合液分别处理木材,增强木材的尺寸稳定性能。研究表明,制备的非离子石蜡乳液平均粒径0．107μm,木材渗透性能好;经石蜡乳液处理的马尾松木材尺寸稳定性可达85％;石蜡乳液能分别与CCA、ACQ木材防腐剂混溶达到稳定状态,耐强酸强碱;石蜡乳液对ACQ木材防腐剂的载药量影响不显著。     

The thermal reactivity of wood waste systems

The thermal decomposition of wood wastes obtained from jack pine has been studied in both oxidising and inert atmospheres using thermogravimetric techniques supported by gaseous and residue product analysis. The effects of selected sequences of chemical additives on the reaction rate parameters of both native and extracted bark samples have also been examined. The maximum rate of wood waste pyrolysis is believed to be related to the rapid decomposition of the cellulose constituent, which occurs at around 350°C in nitrogen. In air, this value is shifted to around 300°C and may be explained by the intervention of exothermic reactions involving other wood constituents present in the complex wood matrix. The trend shown in the analytical results for the various wood waste residues was similar to that established by previous workers for the pyrolysis of coalification products on the basis of H/C and O/C ratios which proceed towards the carbonisation and oxidation poles, respectively, for residues obtained from heating in inert and oxidising atmospheres. Isothermal weight-change data were found to fit model kinetic expressions which indicate that the pyrolysis process may be transport-controlled.We are pleased to acknowledge the award of support funds (C.F.) from the Ontario Ministry of the Environment.     

Fire-retardant mechanism of fire-retardant FRW by FTIR

The structures of the solid state products formed by the partial combustion of Korean pine wood treated with fire-retardant FRW were analyzed by microscopic FTIR. The volatile pyrolytic products of basswood (Tilia amurensis) specimens treated with FRW and its components guanylurea phosphate and boric acid were analyzed by GC-FTIR. The pyrolytic and charring process, the effects of fire-retardant, and the structural characteristics of the pyrolytic products were discussed. It was concluded that upon heating and by the catalysis of FRW and its decomposition products reactions of wood took place successively, namely the dehydration of polysaccharide, the elimination of acetic acid from hemicellulose, the degradation of polysaccharide, the degradation of lignin, the polymerization of the pyrolytic products of wood, reactions of oxygen-element-elimination of aliphatic polymers and the structural change of the latter to form aromatic structures, and charring. The pyrolysis process of wood was altered and the yield of volatile pyrolytic products was decreased by FRW treatment. __________ Translated from Scientia Silvae Sinicae, 2005, 41(4): 149–154 [译自: 林业科学, 2005, 41(4): 149–154]     

Protection and fastness of green color of moso bamboo (Phyllostachys pubescens Mazel) treated with chromium-based reagents

The attractive green color of moso bamboo (Phyllostachys pubescens Mazel) culms fades without chemical treatment. Chromated copper arsenate (CCA) has been used to protect the green color of bamboo, but CCA is harmful to factory workers and the environment. To overcome the toxicity of arsenic in CCA, two chromium-based formulas developed by the authors, chromated copper phosphate (CCP) and chromated phosphate (CP), were evaluated for their protection of the green color of moso bamboo. The results revealed that bamboo treated with CP had a greener color than those treated with CCA or CCP. The concentration, treatment time, and CrO₃/H₃PO₄ ratio in CP solution greatly affected the color of moso bamboo culms. The attractive green color, which resembles the color of fresh-cut moso bamboo, was obtained by treating bamboo with 2% CP solution at 60°C for 3h, using a 11 CrO₃/H₃PO₄ ratio in aqueous solution. In addition, the CP-treated moso bamboo exhibited excellent green color fastness in both accelerated ultraviolet lightfastness testing and outdoor weathering exposure.