蔗渣的热解与燃烧动力学特性研究

利用热重分析仪对蔗渣在不同升温速率下的热解、燃烧失重特性进行了研究。采用Friedman法对反应过程中可能存在的反应机理进行初步判断，蔗渣热解过程由其主要组分半纤维素、纤维素和木质素热解的三个独立的平行反应来描述，相应的反应活化能分别为203.92 kJ·mol-1、238.50 kJ·mol-1和77.11 kJ·mol-1； 蔗渣燃烧过程分为两段，第一段类似于其热解过程，第二段由木质素热解和残焦燃烧共同组成的连续反应，反应活化能为255.57 kJ·mol-1和159.11 kJ·mol-1。通过非线性回归法拟合获得的曲线与实验曲线基本一致，证实了蔗渣的热解、燃烧过程中存在着上述假定的反应机理。     

Application of off-line pyrolysis with dynamic solid-phase microextraction to the GC–MS analysis of biomass pyrolysis products

Pyrolysis coupled with dynamic solid-phase micro extraction (Py-SPME) followed by GC–MS analysis was applied to the determination of volatile compounds evolved by a micro-scale off-line pyrolysis apparatus, in order to extend the information affordable with this type of analytical equipment. The Py-SPME method with a carboxen/PDMS fiber working in the retracted mode was tested on four biomass samples (switchgrass, sweet sorghum, corn stalk and poplar) for qualitative analysis of semi-volatile pyrolysis products and quantitative determination of main volatiles (C₁–C₄) pyrolysis products. The developed procedure allowed capturing and analysis of all GC analyzable compounds, without memory effects and with good peak resolution also for early GC-eluting compounds. Twelve main volatile pyrolysis products, including hydroxyacetaldehyde and acetic acid, were successfully quantified; in spite of the intrinsic variability introduced by dynamic SPME sampling, results were relatively accurate and consistent with literature data on bench pyrolysis reactors.     

Thermal and kinetic study of tyre waste pyrolysis via TG-FTIR-MS analysis

The world production of tyre waste amounts to 5·10⁶ ton year^–1, 2·10⁶ tons of which are produced in Europe, but the final destination of nearly 65–70% of them is the landfill, despite the high added value materials lost and the consequent environmental impact. Treatments alternative to landfilling take into account reconstruction and reuse of the tyres or the matter and/or energy recovery by means of thermal treatment processes (incineration, gasification and pyrolysis). Among these, pyrolysis seems to be a promising and realistic alternative to attain the conversion of tyre waste into valuable and reusable products. Present work relates to experimental tests and results obtained for the study of tyre waste pyrolysis, conducted by means of thermo-gravimetric analysis (TG) of the material and the simultaneous determination, through Fourier transform infrared (FTIR) and mass spectrometry (MS), of the decomposition products. The analysis of the volatile fraction allows to isolate, within the thermograms, the evolution of products referable to specific tyre components and therefore it suggests the application of a multi-component decomposition model. The kinetic model consequently developed agrees fairly well with the experimental data.     

碱性条件下废轮胎真空热裂解研究

研究了废轮胎橡胶粉在450℃～600℃真空热解系统中热解的特性,以及温度和添加Na2CO3、NaOH对热解气液态产物的影响。实验表明,真空下废轮胎热解油收率在550℃时达到最大值,为48%左右。添加3%的NaOH能明显促进废轮胎橡胶热解,480 ℃时油产率达到最大值49.66%,随后随着温度的升高油产率呈现下降趋势。添加3%的Na2CO3对热解的促进作用不明显。热解气体产物主要有H2、CO、CH4、CO2、C2H4、C2H6以及少量其他化合物。NaOH的加入使气体产品中的H2相对体积分数明显增加,而CH4、CO、C2等的体积分数降低。通过GC和GC-MS分析热解石脑油发现,热解油品中含有11%以上的柠檬油精。     

射频等离子体热解废轮胎的研究

Disposal of the huge piles of used tires is increasingly becoming a problem all over the world. Incineration may utilize the energy content of waste tires, but it is associated with the generation of SO2, NOx and other hazardous emissions. Pyrolysis is an alternative disposal method with the possibility for recovery of valuable products from used tires. Recently, waste processing technology based on plasma processes has received much attention due to a number of advantages such as high treatment rate, small space volume, etc. In this paper, the pyrolysis of waste tire using a capacitively coupled radio-frequency （RF） plasma reactor was investigated. The lab-scale RF plasma reactor was operated with RF powers between 1 600 W and 2 000 W, pressures between 3 000 Pa and 8 000 Pa （ absolute pressure） and temperatures between 1 200 K and 1 800 K. In the tire powder pyrolysis experiments, two product streams are obtained： combustible gas and char. The physical properties （surface area, porosity, particle morphology） as well as chemical properties （elemental composition, heating value and surface functional groups） of char were examined to exploit the potential applications of the char. The results indicate that the RF plasma pyrolysis would be a useful technology for waste disposal.     

Pyrolysis of solid waste in a rotary kiln: influence of final pyrolysis temperature on the pyrolysis products

Temperature is one of the most important parameters in pyrolysis reaction. In present work, an externally heated laboratory-scale rotary-kiln pyrolyser was designed and developed. The influence of final pyrolysis temperature (FPT) on the pyrolytic products of solid wastes has been studied. Raising FPT caused increasing gas yield and decreasing semi-coke yield. The average heat value of the gas also changed with FPT. The content of aliphatic hydrocarbons in PE tar increased initially and then decreased with increasing FPT. Parallel to this, the content of aromatic ring changed conversely. FPT had obvious influence on the primary and elemental analysis data of the semi-cokes. The CO₂ reactivity of the semi-cokes also varied with the FPT. The kinetic parameters of the semi-cokes were different for the same material at the different FPT.     

木质纤维类生活垃圾热解过程矿物质和碳结构的演化规律

使用水平管式炉,在不同热解温度(500~1 000 ℃)条件下对废纸屑和樟树叶两种木质纤维类生活垃圾进行了热解实验,分别采用X射线衍射(XRD)和拉曼光谱研究了样品所含矿物质和碳结构随热解温度的变化。结果表明,废纸屑和樟树叶含有的主要矿物分别为方解石和草酸钙,在500 ℃之前草酸钙全部转化为方解石,焦样中的方解石在800 ℃以后逐渐分解并形成生石灰。拉曼光谱对生活垃圾焦的碳结构变化非常敏感,低温热解时生活垃圾的大分子结构发生缩合和解聚,产生了孤立sp²碳原子,导致峰参数D1峰半高宽和峰面积比值I_D1/I_G逐渐增大;高温热解时晶体sp²碳原子增多,导致D1峰半高宽和I_D1/I_G逐渐减小。焦样的碳结构有序度随热解温度升高先降低后提高。     

废弃印刷电路板材料裂解产物的高分辨裂解气相色谱-质谱分析

采用高分辨裂解气相色谱-质谱法(PyGC-MS)分析了FR-4型印刷电路板粉末样品的裂解产物。在氦气氛围中,分别在350,450,550,650和750 ℃下对印刷电路板粉末样品进行热裂解,并通过毛细管气相色谱-质谱对裂解产物进行分析,研究了不同裂解温度下裂解产物分布以及主要裂解产物的产率与裂解温度的关系,根据热分解产物的组成,探讨了热分解反应机理。     

典型城市固体废弃物热解动力学机理研究

利用热重（TGA）技术研究了城市固体废弃物中塑料橡胶类、木质纤维素类、织物类和厨余类四大类可燃组分中七种典型固体废弃物热解反应过程。实验结果表明,塑料类和织物类最难热解,厨余类组分最易热解;采用Freeman-Carroll法对七种典型固体废弃物热解进行数据处理,从20种常用的固相反应机制函数中遴选出最优解,利用优化的数学函数和动力学参数建立动力学模型,结果表明,PE和羊毛线热解主要反应阶段的最优固相反应模型是球形相界面反应模型;橡胶粉、杨树枝热解反应模型遵循化学反应规律;米饭和本白棉布热解曲线遵循幂函数法则;白菜的最优模型是三维扩散模型。     

Comparison of contact and radiant ablative pyrolysis of biomass

Ablation characterizes the phenomena occurring when a solid, submitted to a high external heat flux density, gives rise to solids, liquids and/or gases that can be rapidly and continuously eliminated. Ablation can be exploited for carrying out the fast pyrolysis of materials such as biomass. This paper describes and compares, on a fundamental point of view, two methods of biomass ablative pyrolysis. In the first one, biomass is pressed against a hot surface (contact ablative pyrolysis). In the second one, biomass intercepts a concentrated radiation (radiant ablative pyrolysis). The comparison is made on the basis of the values of ablation thickness and velocity (derived from experiments and modelling), and of product fractions and compositions. The results can be very different in spite of the fact that biomass may be subjected to similar heat flux densities in both cases. The paper shows the advantages, drawbacks and complementarities of each technology.     

棉秆催化热解特性及动力学建模研究

通过不同添加剂处理棉秆的热重实验,分析NaOH、Na₂CO₃、Na₂SiO₃、NaCl、TiO₂、HZSM-5六种添加剂催化棉秆热解动力学特性,结合原料的组分分析,建立三组分独立平行一级反应热解动力学模型对试样热失重行为进行模拟,采用非线性最小平方算法求解热解动力学参数。研究发现,添加剂的加入改变了三组分动力学参数,在碱性添加剂作用下,纤维素和半纤维素热解活化能都有较大程度降低,且碱性越强,纤维素热解活化能越低,而半纤维素热解活化能越高;中性添加剂NaCl对纤维素和半纤维素热解活化能的影响不大;酸性添加剂使纤维素和半纤维素的热解活化能有所增大,但所有添加剂对木质素热解活化能的影响不明显。     

不同活性炭负载的镍基催化剂上废塑料裂解制碳纳米管性能

以椰壳炭、竹炭和木炭三种活性炭为载体,采用浸渍法制备炭负载金属镍的催化剂,考察其在废塑料裂解制备碳纳米管过程中的催化反应性能;采用X射线衍射、扫描电镜、透射电镜、拉曼光谱仪、同步热分析仪、比表面积分析仪等手段分析了催化剂和产物碳纳米管的形貌和结构。结果表明,椰壳活性炭为载体制备的镍基催化剂上碳纳米管产量最高、石墨化程度最好。以椰壳活性炭为载体制备的镍基催化剂为例,研究了反应温度和镍负载量对其催化性能的影响。     

Determination of kinetic parameters and potential residence of phenol degradation on C-felt electrode

The electrooxidation of phenol has been studied on C-felt electrode by using cyclic voltammetry (CV) technique. The kinetic parameters electrooxidation reaction such as oxidation potential at zero scan rate (E ₀), temperature coefficient (dE/dt), reaction order (n), activation energy (E _a), calculated from variation of oxidation peak potentials and current with potential scan rate, phenol concentration and related temperature. Phenol reaction path way (either degradation or polymerization and forming high molecular weight species) and potential residence of phenol degradation are determined by applying different electrolysis voltage values (0.630, 1, 2 and 3 V) in acidic phenol solution (0.0125 M Phenol + 0.5 M H₂SO₄). In addition, decrease in the phenol concentration is monitored in this solution during 6 hours with 1 hour time period and from this data linear relation ship was found to between applied potential and phenol removal efficiency. Published in Russian in Elektrokhimiya, 2009, Vol. 45, No. 3, pp. 281–288. The article is published in the original.     

Preliminary study of the pyrolysis of steam classified municipal solid waste

Steam classified municipal solid waste (MSW) has been studied for use as a combustion fuel, feedstock for composting, and cellulytic enzyme hydrolysis. A preliminary study has been conducted using a prototype plasma arc pyrolysis system (in cooperation with Plasma Energy Applied Technology Inc., Huntsville, AL) to convert the steam classified MSW into a pyrolysis gas and vitrified material. Using a feed rate of 50 lbs/h, 300 lbs of the material was pyrolysized. The major components of this pyrolysis gas were H₂, CO, and CO₂. A detailed presentation of the emission data along with details on the system used will be presented.     

烟草中克百威和抗蚜威残留量测定

采用液相色谱-质谱联用技术(LC-MS-MS)检测了烟草中的克百威和抗蚜威两种氨基甲酸酯类农药的残留量。样品用乙腈超声波提取,以甲醇-50mmol甲酸铵为梯度流动相,C18柱分离,电喷雾正离子选择反应监测(SRM)模式定量分析。结果表明,克百威和抗蚜威的平均加标回收率为96.05%~104.0%,相对标准偏差为2.8%~5.7%。样品前处理不含净化和浓缩步骤,操作简单。     

Isothermal and non-isothermal pyrolysis kinetics of Kapton polyimide

The kinetics involved in the thermal decomposition of Kapton^® polyimide 100HN under nitrogen atmosphere were studied by applying various fitting techniques to the isothermal and non-isothermal gravimetric data. The correlation of the reaction mechanism fitting, the analytical model fitting and the isoconversional method to these data was examined in relation to the kinetic parameters and the kinetic predictions. The mechanisms for solid-state reactions fit the isothermal data very well but result in highly uncertain values for the kinetic parameters when applied to the non-isothermal data. Isoconversional methods show that the apparent activation energy depends on the extent of conversion but do not provide information for the reaction order and the pre-exponential factor. Three single heating-rate analytical models by Coats-Redfern, MacCallum-Tanner and van Krevelen were analysed using the non-isothermal data. A multi-heating rate model is proposed and its validity is compared to the single-heating rate models on the basis of kinetic predictions.     

Evaluation of the Sorptive Capacity of Sugarcane Bagasse and Its Coal for Heavy Metals in Solution

Recycling of sugarcane bagasse and its coal as metal sorbents to capture metal ions from wastewater is the aim of this study. Thus, stability of sugarcane bagasse and its coal, in addition to the solubilities of metal ions in synthetic solution, were determined in this study at different pH values. Also, sorption of Fe, Mn, Cd, and Pb ions with different concentrations (10‐100 mg L^?1) on different grain size fractions of sugarcane bagasse (< 150 > μm) and its coal (< 80 > μm) was carried out under different pH values (2, 4 and 6), dosage (2, 6, and 10 g L^?1), time intervals (15‐300 min.) and temperature (20‐50 °C). The results indicated that the sugarcane bagasse and its coal were more stable at pH 6, and the solubilities of metal ions in the synthetic solution exhibited high values at pH 2 more than pH 4 and 6, respectively. Generally, removal of metal ions using the sorbents increased with the decreasing of grain size fractions and with increasing of pH values (6 > 4 > 2), sorbent doses (10 > 6 > 2 g L^?1) and initial concentrations of metal ions (10‐100 mg L^?1). Coal of sugarcane bagasse was more effective than the sugarcane bagasse for removal of the metal ions from solution. Positive values of ΔH° suggest the endothermic nature of sorption in all cases. The negative Gibb's free energy values indicate the feasibility of the process and spontaneous nature of sorption (Fe‐bagasse coal system), while the positive value of ΔG° suggests the non‐spontaneous character of adsorption of all metals. The negative values of entropy change ΔS° (Pb‐bagasse system) indicate the highly ordered adsorption process in this case, while the positive values of ΔS° show the increased randomness at solid/solution interface during the sorption metal ion on bagasse. The results of activation energy values indicate the order of sorption feasibility is: Pb > Fe > Cd > Mn in the case of bagasse and Fe > Pb > Cd > Mn in the case of coal. Generally, the results of this study suggest that the sugarcane bagasse and its coal might provide an economical method for the removal of metal ions from wastewater.     

A novel kinetic determination of dissolved chromium species in natural and industrial waste water

A highly sensitive, selective and simple kinetic method was developed for the determination of dissolved chromium species based on the catalytic effect of Cr(III) and/or Cr(VI) on the oxidation of 2-amino-5-methylphenol (AMP) with H₂O₂. The fixed time and initial rate variants were used for kinetic spectrophotometric measurements by tracing the oxidized product at 400 nm for 10 min after starting the reaction. Boric acid and Tween-40 exerted pronounced activating and micellar sensitizing effects on the studied redox reaction, respectively. The optimum reaction conditions were: 3.0 mmol l⁻¹ AMP, 0.45 mol l⁻¹ H₂O₂, 0.50 mol l⁻¹ boric acid, 4 v/v% Tween-40, 10 mmol l⁻¹ phosphate buffer and pH 6.45 ± 0.02 at 35 °C. Both Cr(III) and Cr(VI) ions exerted the same catalytic effect on the studied reaction. Linear calibration graphs were obtained for the determination of up to 6.0 ng ml⁻¹ Cr with detection limits of 0.054 and 0.10 ng ml⁻¹ Cr; following the fixed time and initial rate methods, respectively. The proposed method was successfully applied to the speciation and determination of trace levels of dissolved Cr(III) and Cr(VI) in natural and effluents of industrial waste water. The total dissolved Cr(III) and Cr(VI) species was determined first. In a second run, Cr(VI) was determined alone after precipitation of Cr(III) ions in presence of Al(OH)₃ collector, where Cr(III) is then determined by difference. Moreover, published catalytic-spectrophotometric methods for chromium determination were reviewed.     

Isolation of mono-caffeoylquinic acids from tobacco waste using continuous resin-based pre-separation and preparative HPLC

Three isomers of mono-caffeoylquinic acid, specifically, 3-O-caffeoylquinic acid, 4-O-caffeoylquinic acid and 5-O-caffeoylquinic acid, were successfully isolated from a crude extract of tobacco (Nicotiana tobaccum L.) wastes using continuous resin-based pre-separation and preparative high-performance liquid chromatography (HPLC). The extract of tobacco wastes was continuously pre-separated by resin-based columns packed with D101 and XAD-4, yielding total mono-caffeoylquinic acids with a purity of 67.71% and a recovery rate of 90.06%. Variables affecting resolution and productivity of three mono-caffeoylquinic acid isomers in preparative HPLC (i.e. mobile-phase composition, pH, flow rate and loading amount) were studied. The optimum chromatographic conditions were determined to be a mobile phase consisting of 15% (v/v) methanol and aqueous acetic acid with a pH of 4.5, a flow rate of 4.0 mL/min, a loading amount of 4 mL and a detection wavelength of 360 nm. From 300 mg of loading sample, 56.3 mg of 3-O-caffeoylquinic acid, 92.8 mg of 5-O-caffeoylquinic acid and 73.1 mg of 4-O-caffeoylquinic acid were obtained in a single run, each with a purity of over 98% by HPLC. The structures of the isolated compounds were elucidated by ESI-MS, (1) H-NMR and (13) C-NMR spectral data.