水对垃圾焚烧飞灰二(噁)英从头合成的影响

采用垃圾焚烧飞灰在小型管式炉上进行了二(口恶)英的从头合成试验,通过控制水分在气流中的比例,研究不同的水分对二(口恶)英的总量,毒性当量以及分布特性的影响。结果表明,水分整体上对二(口恶)英从头合成具有促进作用,并提高了二(口恶)英排放的毒性当量,但没有发现对分布特性有明显的影响。可能的反应途径水分通过活化飞灰的活性位置,从而促进了二(口恶)英的生成。在氮气反应气氛中的试验表明,水分可以为二(口恶)英的生成提供氧。     

Ash formation and deposition during combustion of pulverized torrefied wood and coal in a 100 kW downflow combustor

Torrefied wood originating from beetle-killed trees is an abundant biomass fuel that can be co-fired with coal for power generation. In this work, pulverized torrefied wood, a bituminous coal (Sufco coal) and their blended fuel with a mixing ratio of 50/50 wt.%, are burned in a 100-kW rated laboratory combustor under similar conditions. Ash aerosols in the flue gas and ash deposits on a temperature-controlled surface are sampled during combustion of the three fuels. Results show that ash formation and deposition for wood combustion are notably different from those for coal combustion, revealing different mechanisms. Compared to the coal, the low-ash torrefied wood produces low concentrations of fly ash in the flue gas but significantly increased yields (per input ash) of ash that has been vaporized. All the mineral elements including the semi- or non-volatile metals in the wood are found to be more readily partitioned into the PM₁₀ ash than those in the coal. The inside layer deposits sticking to the surface and the loosely bound outside deposits exposed to the gas both show a linear growth in weight during torrefied wood test. Unlike coal combustion, in which the concentration of (vaporized) ash PM₁ controls the inside deposition rate, wood combustion shows that the formation of porous bulky deposits by the condensed residual ash dominates the inside deposition process. Co-firing removes these differences between the wood and coal, making the blended fuel to have more similar fly ash characteristics and ash deposition behavior to those of the bituminous coal. In addition, results also show some beneficial effects of co-firing coal with torrefied wood, including reduction of the total deposition rate and the minimization of corrosive alkali species produced by wood.     

褐煤热解与燃烧时矿物转化和细灰形成的CCSEM研究

在沉降炉中进行了一种典型中国褐煤的热解与燃烧实验,热解气氛为N2,燃烧气氛为O₂/N₂=21:79,采用CCSEM分析原煤、煤焦与煤灰。CCSEM分析结果表明,铁氧化物、石英、黄铁矿、伊利石和高岭土是煤中主要的矿物成分,同时也是主要的外在矿成分,褐煤中57.26%的矿物粒径小于10μm。在热解与燃烧过程中,煤中主要矿物发生了明显转化。富Si矿物和硅铝酸盐在热解和燃烧过程中可能发生了破碎;而富Fe矿物部分明显破碎生成细小矿物,部分外在矿直接转化,未发生明显破碎。细灰少量来自于细小富硅矿、石英和铁氧化物等矿物的直接转化,70%以上的细灰由Ca、Fe含量很高的混合硅铝酸盐组成。     

In-situ gasification chemical looping combustion of plastic waste in a semi-continuously operated fluidized bed reactor

Conventional air incineration of plastic waste has been considered as one of important sources of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) through de novo synthesis and precursor conversion. Chemical looping combustion (CLC) is an attractive technology for the conversion of plastic wastes to energy with the potential to drastically suppress the formation of PCDD/Fs. In this paper, the iG-CLC (in-situ gasification CLC) experiments of plastic waste were implemented in a semi-continuously operated fluidized bed reactor, which actually simulates the fuel reactor of a continuously-operated interconnected fluidized bed reactor. A kind of low-cost material, natural iron ore without/with 5 wt% CaO adsorbent through the ultrasonic impregnation method, was used as oxygen carrier (OC). Firstly, some key performances of the reactor system, such as the relevance of the bed inventory to the flow rate of fluidizing agent as well as the relationship between the feeding rate and overflow rate of OC, were calibrated. Then, 90 min of single experiment was conducted for each experimental case and an accumulative operation of more than 10 h was attained. Typically, the combustion efficiency can reach at about 98%, and both the carbon conversion and CO₂ yield can approach to 95% at 900 °C and input thermal power of 150 W with a mixture of 5 vol% H₂O and 95 vol% N₂ as the fluidizing agent (U_FR/U_mf = 3). Moreover, the results obtained in the semi-continuously operated fluidized bed reactor demonstrated that CaO decoration to iron ore is conductive to suppressing the formation of chlorobenzene (as a toxic matter and precursor/intermediate of PCDD/Fs) and does not obviously deteriorate the OC performance.     

基于TG-FTIR的杨木热解过程中脲醛树脂影响机理的模型物研究

热解是废弃人造板高效回收利用的方式,人造板中所含胶黏剂是其不同于生物质的主要特征。为了有效环保地利用热解技术处理废弃人造板,解明人造板热解过程中其所含脲醛树脂胶黏剂(UF)对木材热解特性的影响,深入探索UF对人造板中木材各组分的作用机制,以杨木及木材的三种主要组分(纤维素、半纤维素、木素)为研究对象,创新性地依据杨木的化学组成,以纤维素、木聚糖和木素配制成模型物,并加入UF模拟人造板的构成。利用热重红外光谱联用(TG-FTIR)分析法,对比分析了加入UF前后模型物以及杨木各主要组分的热失重特性及气相演变规律。热重及红外结果表明,UF促进了纤维素热解过程中水和羧酸类物质的生成。UF与木素结合生成热不稳定的含氮结构,释放大量氨气,并且在200～300 ℃区间内参与了木素的热解并直接影响木素热解产物的生成。由此推测,在人造板热解过程中,木材三种主要组分中与UF作用的主要成分是木素。     

LC-DAD/ESI-MS/MS study of phenolic compounds in ash (Fraxinus excelsior L. and F. americana L.) heartwood. Effect of toasting intensity at cooperage

The phenolic composition of heartwood extracts from Fraxinus excelsior L. and F. americana L., both before and after toasting in cooperage, was studied using LC-DAD/ESI-MS/MS. Low-molecular weight (LMW) phenolic compounds, secoiridoids, phenylethanoid glycosides, dilignols and oligolignols compounds were detected, and 48 were identified, or tentatively characterized, on the basis of their retention time, UV/Vis and MS spectra, and MS fragmentation patterns. Some LMW phenolic compounds like protocatechuic acid and aldehyde, hydroxytyrosol and tyrosol, were unlike to those for oak wood, while ellagic and gallic acid were not found. The toasting of wood resulted in a progressive increase in lignin degradation products with regard to toasting intensity. The levels of some of these compounds in medium-toasted ash woods were much higher than those normally detected in toasted oak, highlighting vanillin levels, thus a more pronounced vanilla character can be expected when using toasted ash wood in the aging wines. Moreover, in seasoned wood, we found a great variety of phenolic compounds which had not been found in oak wood, especially oleuropein, ligstroside and olivil, along with verbascoside and isoverbascoside in F. excelsior, and oleoside in F. americana. Toasting mainly provoked their degradation, thus in medium-toasted wood, only four of them were detected. This resulted in a minor differentiation between toasted ash and oak woods. The absence of tannins in ash wood, which are very important in oak wood, is another peculiar characteristic that should be taken into account when considering its use in cooperage.     

垃圾焚烧炉氯源对氯化氢和二噁英排放的影响

本文研究了150 t/d垃圾与煤混烧流化床锅炉在不同含氯水平和添加钙基脱硫时氯化氢和二噁英的排放特性。实验结果表明烟气中的氯化氢和二噁英浓度随燃料中垃圾比例的增加而上升,在含氯量一定的情况下,炉内燃烧状况决定了二噁英的生成量,烟气中的二噁英随燃料中含氯量的增加而增加,飞灰中的二噁英则随燃烧状况的改善而增加。钙基的加入可以有效降低氯化氢和二噁英的排放。在我国目前的垃圾组分条件下,全煤工况和垃圾与煤混烧工况的二噁英排放量很低。     

XPS characterization of naturally aged wood

Wood deterioration over time (by a simultaneously biological, chemical or physical attack) is an inevitable continuous process in the environment. This process destroys all heritage resulting in a loss of valuable old wooden structures and their properties. What type of deterioration occurs and how these processes impact the wood are important questions that need consideration if old wooden structures are to be studied and properly preserved.X-ray photoelectron spectroscopy (XPS) was employed to analyze the undegraded (sound wood of ∼6 years) and degraded lime wood (∼150 years, ∼180 years, ∼250 years) from painting supports, differing in terms of the provenance, conservation status and environmental conditions of storage. Elaborated XPS analysis (comparison of C and O individual spectra, decomposition for each atomic component, calculation of O/C ratio) provided a view of the composition of the sample surfaces analyzed. On the basis of these results, it was confirmed that significant changes occurred in the first period of ageing, the ∼150 years lime wood sample having the highest percent of the carbon atoms and the lowest percentage of oxygen atoms and, respectively O/C ratio. According to our previous studies (X-ray diffraction, FTIR spectroscopy, analytical pyrolysis combined with gas chromatography/mass spectrometry and ESR-spectroscopy results), these features could be attributed to the fact that hemicelluloses and amorphous cellulose are degraded in time, whereas the crystalline fraction of cellulose decreases more slowly than the amorphous one. Consequently, the observation may be made that lignin is not so easily degraded under the environmental conditions where paintings are frequently exposed.     

Effect of high CO2 concentration on char formation through mineral reaction during biomass pyrolysis

O₂/CO₂ combustion has attracted considerable attention as a promising technology for CO₂ capture. Using biomass for fuel is considered carbon neutral, and O₂/CO₂ biomass combustion can mitigate the deleterious environmental effect of greenhouse. In this study, the effect of CO₂, the main component gas in O₂/CO₂ combustion, on the pyrolysis characteristics of biomass is investigated. Cellulose, lignin, and metal-depleted lignin pyrolysis experiments were performed using a thermobalance. Information on the surface chemistry of the chars was obtained by Fourier transform infrared (FTIR) spectroscopy to investigate changes in the surface chemistry during pyrolysis under different surrounding gasses. When the temperature increased to 1073 K at heating rate of 1 K s^?1, the char yield of lignin in the presence of CO₂ increased by about 10% compared with that under Ar. However, for cellulose and metal-depleted lignin, no significant difference appeared between pyrolysis under CO₂ and that under Ar. FT-IR showed that a strong peak corresponding to carbonate ions appeared in the char derived from lignin under CO₂. Therefore, salts such as Na₂CO₃ or K₂CO₃ formed during the lignin pyrolysis under CO₂. At around 1650–1770 cm^?1, a significant difference appeared in the FTIR spectra of chars formed under CO₂ and those formed under Ar. C=O groups not associated with an aromatic ring were found only in chars formed under CO₂. It was suggested that these salts affected the char formation reaction, in that the char formed during lignin pyrolysis under CO₂ had unique chemical bands that did not appear in the lignin-derived char prepared under Ar.     

Analytical Instrumental Techniques to Study Archaeological Wood Degradation

Abstract

Historically, a very large variety of everyday artifacts were made of wood, which makes them representative of their historical period or social context and valuable for archaeologists and historians. In order to preserve degraded wood and to develop and apply suitable conservation treatments, chemical and physical characterization of archaeological wood is needed. This review provides the reader with a survey on state-of-the-art of instrumental analytical tools available to understand the morphology and the chemical composition of archaeological wood. The focus is on microscopic and spectroscopic techniques such as scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), Raman, nuclear magnetic resonance (NMR) and analytical techniques based on pyrolysis, such as direct exposure–mass spectrometry (DE-MS), pyrolysis–mass spectrometry (Py-MS), pyrolysis–gas chromtography–mass spectrometry (Py-GC/MS), with emphasis on their respective potentialities and limitations. The advantages of techniques based on synchrotron radiation are also discussed. In addition, the applicability of each examined technique is illustrated and discussed through specific examples from the literature.     

基于TG-FTIR的落叶松木材热失重与热解气相演变规律研究

采用热重红外光谱联用分析法考察了落叶松木材在不同升温速率下的热失重特性及气相演变规律,并与其组分模混物的热解特性进行了对比分析。结果表明,落叶松的主要失重区域相对于模混物较宽,落叶松残炭率(18.97%)相对于模混物(29.83%)较低;在低温段,模混物的活化能高于落叶松木材,而在高温段二者差别不大;落叶松木材热解过程经历了水分析出、主成分热分解、后期炭化等阶段,气体析出主要集中在375℃左右;落叶松在热解反应过程中,主要气体产物生成量顺序为CO2>H2O>CH4>CO,随着升温速率的增加,上述气体产物的生成量明显增多;模混物与落叶松木材热解生成气体规律基本相似,但模混物中各气体析出强度均相对较高。     

Study of the competing chemical reactions in the initiation and spread of smouldering combustion in peat

Smouldering combustion of natural fuel layers such as peatlands leads to the largest fires on Earth and posses a possible positive feedback mechanism to climate change. In this paper, we use an experimental methodology to study the smouldering combustion of samples of peat under a wide range burning conditions. Vertical samples (30 mm deep and 125 mm in diameter) are ignited by radiation on the top free surface and the smouldering front propagates downward against a forced flow of oxidizer. By varying the oxygen concentration ([O₂]) and the ignition conditions we investigate the competing pyrolysis and oxidation reactions. A reaction framework with two regimes is consistently observed. The measurements show that a char species is formed by the competing pyrolysis and oxidation reactions in the first regime resulting in net char production and in the second regime char oxidation results in conversion of the char to ash. Lower mass loss rates and the larger residual mass at lower [O₂] suggest that a wider smouldering front is required to sustain combustion as the [O₂] is decreased. These results improve our understanding of smouldering phenomena and the role of the competing chemical reactions.     

Proton spin-lattice relaxation time measurements of solid wood and its constituents as a function of pH: part II

The proton spin-lattice relaxation times (T1H) for isolated cuoxam lignin and fully bleached cellulose were measured as a function of pH in the solid-state. These experiments provided the opportunity to examine for possible macromolecular connectivities that may be present between lignin and carbohydrates within softwood. These studies have shown that the molecular mobilities of the isolated polymeric constituents of wood are affected by the ionization of their functional groups at different pHs. The shapes of the plots of T1H as a function of pH for the two isolated polymers were dramatically different, while those for softwood were similar. This fact provides evidence supporting the notion that in wood, lignin and carbohydrates are intimately associated with each other.     

Erratum

Modelling of pulverised wood flames in a laboratory vertical furnace was carried out. The aim was to gain deeper understanding of the combustion process and to validate a mathematical model to simulate the process. Pulverised wood combustion involves many different processes such as two-phase flow dynamics, drying and devolatilisation of the particles, oxidation of the volatile and formation and oxidation of char. It is desirable to know which are the most dominating/sensitive processes that control the combustion behaviour and in particular the emissions of unburned hydrocarbons and carbon monoxide. To achieve this goal, a comprehensive devolatilisation model based on the functional group concept is applied to predict the details of the devolatilisation products including tar. The solid-gas coupling is made using the Eulerian/Lagrangian approach. A ‘rocket force’ model is developed to account for the influence of drying and devolatilisation on the particle motion. The present mathematical model successfully simulated the flame temperature and detailed species distributions including CH₄ and CO. These two species were shown to be sensitive to the fate of tar. Major paths for the CO formation were identified as the devolatilisation of the wood particles and the char oxidation. Influences of the initial functional group yield, the char oxidation and gasification reactions, the turbulence mixing rate and the fuel particle size on the flame structures andb emissions were examined.     

Effect of Fe2O3 nanoparticles on combustion of coal surrogate (Anisole): Enhanced ignition and formation of persistent free radicals

This contribution explores the effect of nanoparticles of iron (III) oxide (Fe₂O₃) on the combustion of coal surrogate, i.e., anisole, identifying the changes in ignition features as well as the occurrence of persistent organic pollutants in the initiation channels. The method applies packed-bed reactor coupled with Fourier transform infrared (FTIR) spectroscopy to quantitate the ignition temperature under typical fuel-rich conditions, in-situ electron paramagnetic resonance (EPR) to elucidate the formation of environmentally-persistent free radicals (EPFR), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to monitor the chemisorption of organic substrates on the nanoparticles, as well as X-ray diffraction for particles characterisation (PXRD). We employ cluster-based quantum mechanical calculation to map the reaction pathway within the scope of the density functional theory. The results of Fe₂O₃-mediated combustion of anisole depict an excessive reduction in ignition temperature from 500?°C around 220?°C at λ?=?0.8. As confirmed both from EPR and DRIFTS measurements, the chemisorption of anisole on α-Fe₂O₃ surfaces follows the direct dissociation of the O–CH₃ (and OCH₂–H), leading to the formation of surface-bound phenoxy radicals at temperatures as low as 25?°C and incurring an estimated energy barrier of E_a?=?18?kJ mol^?1 and a preexponential factor of A?=?2.7?×?10¹² M^?1 s^?1. This insight applies to free-radical chain reactions that induce spontaneous fires of coal, as coal comprises ferric oxide nanoparticles, and equally to coexistence of aromatic fuels with thermodynamically reactive Fe₂O₃ surface, e.g., in fly ash, at the cooled-down tail of combustion stacks.     

A functional-group-based approach to modeling real-fuel combustion chemistry – III: Application to biodiesels

Real biodiesel fuels are mixtures comprising many high molecular weight components, making it a challenge to predict their combustion chemistry with detailed kinetic models. Our group previously proposed a functional-group approach (FGMech) to model the combustion chemistry of real gasoline and jet fuels; this approach has now been extended to model real biodiesel combustion and mixtures with petroleum fuels. As in our previous work, a decoupling philosophy is adopted for construction of the model. A lumped reaction mechanism describes the (oxidative) pyrolysis of fuels, while a detailed base chemistry model represents the oxidation of key pyrolysis intermediates. However, due to the presence of the ester group, several oxygenated species are identified as additional primary products and incorporated into the lumped reaction steps. In addition to the lumped reactions initiated by unimolecular decomposition and H-atom abstraction reactions, a lumped H-atom addition-elimination reaction is also incorporated as a new reaction class to account for the presence of double bonds. Stoichiometric parameters are obtained based on a multiple linear regression (MLR) model, which establishes relationships between the fuel's functional group distributions and the stoichiometric parameters of the lumped reactions. Global rate constants are developed from consistent rate rules obtained from pure fuels. New pyrolysis experimental data for methyl pentanoate/methyl nonanoate and methyl heptanoate/n-heptane mixtures (50%/50% in mol) are obtained in a jet-stirred reactor at atmospheric pressure. In general, kinetic models developed using the FGMech approach can reasonably reproduce all the validation targets obtained in this work, as well as those in the literature, confirming that functional-group-modeling is a promising approach to simulate combustion behavior of diesel/biodiesel surrogate fuels and real biodiesels.     

城市生活垃圾流化床焚烧时PCDD/Fs排放特性的研究

城市生活垃圾焚烧处理已逐渐在我国推广应用．垃圾焚烧所产生的二恶英污染问题日益被人们所关注,浙江大学基于我国城市生活垃圾的特点（高水份、多组份、低热值等）,成功开发了异重流化床焚烧技术并应用于一座 １５０ ｔ／ｄ垃圾流化床焚烧锅炉．木文首先介绍了二恶英的分析方法,其次在小型流化床上进行了ＰＣＤＤ／Ｆｓ的生成机理试验、在此基础上,对１５０ｔ／ｄ垃圾焚烧炉烟气中二恶英排放进行了分析,实验结果将指导焚烧炉优化运行并为进一步研究打下坚实基础。     

Comparative study of the photo-discoloration of moso bamboo (Phyllostachys pubescens Mazel) and two wood species

Bamboo or bamboo products undergo surface degradation during outdoor exposure resulting in lower quality in service. In this study, the effect of UV-vis light irradiation on changes in color and surface chemistry of moso bamboo (Phyllostachys pubescens Mazel) was investigated. For comparison purpose, two wood species (a soft and a hardwood) were also studied to present their differences in degradation performance. Color characterization was performed by measuring CIELab parameters (L*, a*, b* and ΔE*), and Fourier transform infrared (FTIR) spectroscopy was used to analyze the chemical changes induced by irradiation. The results showed that the surface color of bamboo changed rapidly during the irradiation process. Compared with the wood species, bamboo was less influenced by photo-irradiation. Chemical analysis indicated that irradiation altered the chemical structures of bamboo surfaces. Lignin was the most sensitive component to photo-degradation and the intensities of its characteristics bands decreased significantly during the irradiation process. This was accompanied by formation of new carbonyl groups at 1735 cm⁻¹. The rate of lignin degradation and carbonyl formation in bamboo was relatively lower compared with the wood species. The color changes (ΔE*) was well correlated with lignin degradation and carbonyl formation regardless bamboo or the wood species.     

木质装饰板材贫氧条件下燃烧和热解特性研究

本文利用热重差热分析仪,在各种不同的氧气浓度下对落叶松、红木和红松样品进行实验。通过对TG、DTG和DTA曲线的分析,样品干燥基要经历两个失重过程,第一个失重过程主要是纤维素和半纤维素的热解,第二个失重过程主要是木质素的炭化分解和燃烧。在各氧气浓度条件下,热解失重的第一个阶段TG和DTG曲线差异很小;在各样品失重的第二个阶段,随着氧气浓度的增加,TG和DTG曲线左移,反应结束的温度明显降低。氧气能使木质素的炭化物氧化并进而可能使其着火燃烧,从而使反应进程加快。当氧气浓度大于6.32%时,各样品DTA曲线上均有两个明显放热峰,并且随着氧气浓度的增加,DTA曲线放热峰越尖锐,放热峰面积越大,说明氧气浓度越大,在两阶段失重过程中更多的挥发分物质和固体炭化物参与燃烧。