真空条件下高分辩质谱对不同煤质热解释放CO2分析

煤的热解机理和热解物质的形成与释放特征是煤田火灾研究领域的重要基础问题.本文以淮北不同煤种(烟煤,无烟煤,天然焦)为研究对象,在高真空条件下对样品进行热解,利用分子泵即时将热解气体产物抽入高分辨质谱检测器,在线分析热解过程中CO2的释放规律.研究结果表明:天然焦热解过程中产生的CO2,主要是样品和体系中残留以及吸附在煤微孔隙中O2分子反应生成;烟煤和无烟煤热解产生的CO2,主要是其内部含氧官能团在受热过程中分解形成,为不同煤种自燃发火防治提供资料.     

An assessment of how distance and diesel oxidation catalyst will impact thermal decomposition behaviors of particles

Decomposition mass loss and pyrolysis products analyses of particles sampled at various locations along the tailpipe of a Euro-IV diesel engine were performed using a thermogravimetry in conjunction with Fourier transformation infrared spectrometry-mass spectrum. Diesel particles were collected at the same location with and without diesel oxidation catalyst (DOC) mounted on the test engine separately. The three poles in thermal gravity-differential thermal gravity images suggested that the decomposition process of diesel particles could be divided into three stages which correspond to the decompositions of lower boiling substances, higher boiling substances and soot respectively. It is noticed that no matter whether DOC was mounted or not, the further the particles were sampled away from the engine block, the lower the peak temperatures and the heavier the mass losses within the first two stages, which indicated that the soluble organic fraction in the particle samples increased and therefore lowering the activation energy of thermal decomposition. Hydroxyl, ammonia, C_xH_y fragments, benzene, toluene, and phenol were found to be the primary products of particle decomposition, which didn't change with the location of particle sample point. The employment of DOC increased the activation energy for particle oxidation and resulted in a higher peak temperature and lower mass loss within the first-stage. Moreover, the CO stretching bands of aldehyde and ketone at 1771 cm^?1 was only detected without a DOC, while the NO₂ peak at 1634 cm^?1 was solely noticed with the presence of DOC. Compared to the first-stage pyrolysis products, more polycyclic aromatic hydrocarbons and less C_xH_y fragments were seen in the second-stage.     

PBDF and PBDD from the combustion of bromine containing flame retarded polymers: A survey

The formation of polybrominated dibenzofurans (PBDF) and dibenzodioxins (PBDD) during the pyrolysis of different polymers containing brominated organic flame retardants was investigated. The pyrolyses were conducted at two different temperatures (600°C and 800°C) using three different oven configurations. Both the pyrolysis gases and the solid residues were analysed for PBDF and PBDD.

PBDF were found in almost all samples, but both the concentration and the degree of bromination varied greatly. The largest yields of PBDF in the percent range were measured in the pyrolysis products of polymers containing brominated diphenyl ethers. The other flame retardants generally yielded only a few ppm of PBDF. PBDD are formed only in a few samples and related to the PBDF in very low concentrations.     

Miscanthus × Giganteus straw and pellets as sustainable fuels and raw material for activated carbon

Miscanthus × Giganteus is an excellent candidate for energy cultivation. Here we report, for the first time, the results of the pyrolysis of Miscanthus × Giganteus straw or pellets both in tubular reactor (3–6 g) and in rotary kiln (10–30 g). At 400–600°C the fractions obtained from both reactors are: solid 16–25 (wt.%); liquids 25–40; water 15–20 and gases 15–50. GC-MS analyses of pyrolysis liquids reveal the occurrence of phenolic derivatives and ethanol from lignin, furanic and linear oxygenated compounds from cellulose and hemicellulose. Finally the chars produced by the pyrolysis of M×G pellets in rotary kiln present good calorific values close to 29,000 J/g. Additionally, activated carbons with a BET surface area as high as 800–900 m²/g are produced from pellets. These results indicate that chars have a good potential either for energy production, e.g. briquetting, or as adsorbents precursors.     

热重法研究模化城市生活垃圾燃烧和热解特性

利用热重技术研究了模化城市生活垃圾(model municipal solid waste，MMSW)的热解和燃烧过程的特性。结果表明，在小于300℃的温度范围内，热解和燃烧的失重曲线基本一致，不同升温速率对失重特性有影响。利用分峰拟合处理技术对MMSW热处理过程的DSC曲线进行分析，发现MMSW燃烧和热解的失重特性基本上是所含物质失重特性的叠加。对MMSW热处理过程进行动力学分析，计算结果表明反应级数在1．2～1．8之间，化学反应的平均活化能在30～50kJ／mol之间。     

Preparation of jet engine range fuel from biomass pyrolysis oil through hydrogenation and its comparison with aviation kerosene

The Bio-oil was produced from the pyrolysis of agricultural wastes (Eucalyptus sawdust) and discarded soybean frying oil. The temperature of the pyrolysis system was initiated at 28°C and increased to 850°C. Atmospheric distillation of crude bio-oil was performed and a fraction at a temperature range 160–240°C (pyrolysis oil) was separated and subjected to GC-MS, ¹H-NMR, TGA and FTIR analysis to identify the different properties and compounds present in pyrolysis oil. It was noticed that there was an abundance of oxygen and nitrogen containing compounds as well as other reactive species in pyrolysis oil. To reduce the amount of these species, the pyrolysis oil was subjected to hydrogenation in the presence of NiMo as a catalyst. After hydrogenation, the atmospheric distillation of hydrogenated bio-oil was performed and another fraction at temperature range 160–240°C (hydrogenated bio-oil) was separated and analyzed by the same techniques. It was noticed that during hydrogenation, more than 60% oxygenated and other reactive species were converted into hydrocarbons. Hydrogenated bio-oil showed very similar physico-chemical properties such as distillation curve, density, viscosity, freezing point, flash point, the presence of hydrocarbons and enthalpy of combustion as aviation kerosene also known as QAV-1.     

High efficiency chlorine removal from polyvinyl chloride (PVC) pyrolysis with a gas–liquid fluidized bed reactor

In this research a gas–liquid fluidized bed reactor was developed for removing chlorine (Cl) from polyvinyl chloride (PVC) to favor its pyrolysis treatment. In order to efficiently remove Cl within a limited time before extensive generation of hydrocarbon products, the gas–liquid fluidized bed reactor was running at 280–320 °C, where hot N₂ was used as fluidizing gas to fluidize the molten polymer, letting the molten polymer contact well with N₂ to release Cl in form of HCl. Experimental results showed that dechlorination efficiency is mainly temperature dependent and 300 °C is a proper reaction temperature for efficient dechlorination within a limited time duration and for prevention of extensive pyrolysis; under this temperature 99.5% of Cl removal efficiency can be obtained within reaction time around 1 min after melting is completed as the flow rate of N₂ gas was set around 0.47–0.85 Nm³ kg^?1 for the molten PVC. Larger N₂ flow rate and additives in PVC would enhance HCl release but did not change the final dechlorination efficiency; and excessive N₂ flow rate should be avoided for prevention of polymer entrainment. HCl is emitted from PVC granules or scraps at the mean time they started to melt and the melting stage should be taken into consideration when design the gas–liquid fluidized bed reactor for dechlorination.     

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.     

Evaluation of beech for production of bio-char,bio-oil and gaseous materials

Evaluation of Oriental beech (Fagus orientalis L.) was investigated with aspect of thermo-chemical conversion to obtain bio-char, bio-oil and gaseous. When the pyrolysis temperature increased, the bio-char yield decreased. A high temperature and smaller particles increase the heating rate resulting in a decreased bio-char yield. The bio-char obtained are carbon rich, with high heating value and relatively pollution-free potential solid biofuel. The liquefaction yield sharply increased with increasing the temperature near critical temperature and after that. In the pyrolysis, increases of liquid yields are considerably sharply for all of the samples with increasing of pyrolysis temperature from 690 K to 720 K. The beechnut oil was converted to biodiesel in supercritical methanol without using the catalyst. Experiments have been carried out in an autoclave at 493, 523 and 593 K, and with molar ratios of 1:6–1:40 of the oil to methanol. The yield of alkyl ester increased with increasing the molar ratio of oil to alcohol.     

Effects of temperature and composite alumina on pyrolysis of sewage sludge

An interactive dual-circulating fluidized bed system has been proposed in which the pyrolysis of sewage sludge(SS) and incineration of biomass proceed simultaneously, and alumina is used as the bed material and heat carrier. The alumina coated with biomass ash would mix with sewage sludge in the pyrolysis reactor of this device. It is important to know the influence of composite alumina(CA) on the pyrolysis progress. Sewage sludge was pyrolyzed in a fixed bed reactor from 400 to 600°C using CA as catalyst. The effects of temperature and CA additive ratio on the products were investigated. The product yields and component distribution of non-condensable gas were more sensitive to the change of temperature, and the maximum liquid yield of 48.44 wt.% and maximum Useable Energy of Liquid of 3871 k J/kg sludge were observed at 500°C with 1/5 CA/SS(mass ratio). The gas chromatography–mass spectrometry results showed that the increase of temperature enhanced devolatilization of organic matter and promoted cyclization and aromatization of aliphatics. The presence of CA could strengthen secondary cracking and interaction among primary products from different organic compounds, such as acid–amine condensation,and reduce the content of oxygenated compounds. When the CA additive amount exceeded a certain proportion, the aromatization was clearly strengthened. The effects of CA on decomposition of fatty acids and formation of aromatics were similar to that of temperature. This means that the reaction temperature could be lowered by introducing CA, which has a positive effect on reducing energy consumption.