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。     

Energy potential and thermogravimetric study of pyrolysis kinetics of biomass wastes

The use of agricultural wastes for energy conversion has been widely studied as renewable and carbon neutral energy sources. This paper aims to evaluate the energetic potential of six agricultural wastes—sugarcane bagasse, bean pods, corn stover, pineapple crown leaves, white cotton and natural coloured cotton stalks, through their characterization and pyrolysis kinetic study. The energetic potential of biomasses was evaluated by ultimate and proximate analysis, higher heating value (HHV), apparent density, and kinetic parameters of conversion and apparent activation energy (E_a) determined by Model-Free kinetics though thermogravimetric analysis data. The results indicate energetic density for dry basis biomasses, such as moisture content less than 7%, volatiles higher than 77% and moderate ash content. The HHVs were higher for the biomass with low O:C ratio. The E_a values increased with increasing O:C ratio and were also influenced by the biomass ash content. Among the studied biomasses, PCL are less explored for energy application, although the results confirm its potential for application in thermochemical processes such as pyrolysis or combustion.

     

Anaerobic bioconversion of municipal solid wastes

Applied Biochemistry and Biotechnology - The anaerobic bioconversion of municipal solid wastes (MSW) produces both a valuable fuel product (methane) and a residue useful as a soil amendment. The...     

Liquid chromatographic-electrospray ionization mass spectrometric analysis of neutral and charged polyethylene glycols

Poly(ethylene glycols) (PEGs) are widely used water soluble and biocompatible polymers. PEGs are suitable as paracellular probes in biomembrane permeability studies because they are hydrophilic and various oligomers have defined molecular sizes. In previous studies corneal and conjunctival permeability for neutral PEGs has been measured, and the results were used to calculate the number and size of the cellular pores. In this study we have developed a high-performance liquid chromatographic-electrospray ionization-mass spectrometric method for analysis of neutral PEGs and positively changed amino PEGs simultaneously. The new method is fast, accurate, sensitive and specific for high throughput analysis. The method was used to evaluate the paracellular permeability of PEGs through a corneal epithelial cell culture. Paracellular pores are negatively charged and it was in our interest to characterize the interactions of positive charge and size of the molecules with the paracellular pores.     

A mass spectrometric study of the pyrolysis of gibberellic acid

The behaviour of gibberellic acid (GA₃) under electron impact and chemical ionization conditions has been examined. The tendency of GA₃ to undergo pyrolysis by the loss of the elements of water and carbon dioxide has been identified. Two methods of sample introduction can be used to minimize the occurrence of this pyrolysis. Accurate mass measurement allows the composition of the pyrolysis product to be determined and metastable techniques confirm the structure of this product to be epi-allogibberic acid rather than its isomer allogibberic acid. This result corrects a misconception in the literature and illustrates the advantage of metastable methods compared with accurate mass measurements, for the determination of small structural differences within a molecule.     

Kinetic analysis of catalytic slurry oil pyrolysis using thermogravimetric analysis

Journal of Thermal Analysis and Calorimetry - Pyrolysis is an important process for converting unconventional fuels, such as heavy oil, residues and oil sand, to high-value-added light products....     

Thermal and catalytic degradation of pyrolytic oil from pyrolysis of municipal plastic wastes

Thermal and catalytic degradation of pyrolytic oil obtained from the commercial rotary kiln pyrolysis plant for municipal plastic waste was studied by using fluid catalytic cracking (FCC) catalyst in a bench scale reactor. The characteristics of raw pyrolytic oil and also thermal and catalytic degradation of pyrolytic oil using FCC catalyst (fresh and spent FCC catalyst) under rising temperature programming was examined. The experiments were conducted by temperature programming with 10 °C/min of heating rate up to 420 °C and then holding time of 5 h. During this programming, the sampling of product oil was conducted at a different degradation temperature and also different holding time. The raw pyrolytic oil showed a wide retention time distribution in GC analysis, from 5 of carbon number to about 25, and also different product characteristics with a comparison of those of commercial oils (gasoline, kerosene and diesel). In thermal degradation, the characteristics of product oils obtained were influenced by reaction temperature under temperature programming and holding time in the reactor at 420 °C. The addition of FCC catalyst in degradation process showed the improvement of liquid and gas yield, and also high fraction of heavy hydrocarbons in oil product due to more cracking of residue. Moreover, the characteristic of oil product in catalytic degradation using both spent and fresh FCC catalysts were similar, but a relatively good effect of spent FCC catalyst was observed.     

Determination of the pseudocomponents and kinetic analysis of selected combustible solid wastes pyrolysis based on Weibull model

The application of thermal analysis to meat products, like all materials, is governed by energy transfer, from which invaluable information on thermodynamics of processes is obtained. Various meat systems have been analyzed with different success ratios. Proteins in meat formed the key area of interest due to their effect on product quality, shelf life, functionality and also their ability to interact with other components. Initially success rates were low owing to lack of sensitivity, results with complex curves, complications in interpretation and a large number of factors affecting the biological system. Later with developments in instrumentation and computer models for better resolution and reproducibility, wider horizons could be covered with easy solutions to complex results. Though thermal analysis has been used exhaustively in meat, research in this area has become stagnant and new areas are being left untouched. This review emphasizes the importance of thermal analysis in the meat industry and also the need to use more advanced equipment for better understanding of the biological changes occurring in muscle during processing and storage.     

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.     

油棕废弃物热解的TG-FTIR分析

利用热重分析(TGA)和傅里叶红外光谱(FTIR)联用技术对油棕废弃物的热解特性及其气体产物的释放特性进行了研究,采用一级反应计算了油棕废弃物的热解动力学参数。研究表明,油棕废弃物较易于热解,失重集中在220℃～400℃,其热解活化能较小,约为60kJ/mol;气体产物的析出与生物质的热解失重有着相似的特性,气体产物主要在200℃～400℃析出,主要成分为H2O、CO2、CO、CH4和有机碳水化合物的混合物, 其中CO2和有机混合物的析出温度较低,而CO和CH4的析出温度相对较高。随着温度的进一步升高(>400℃),除少量的CO2和CO外,无其他气体产物析出。气体产物的析出量与生物质样品的化学组成和结构有关,CO2和有机混合物的析出与生物质的热解失重曲线(DTG)有着相似的特性,是引起油棕废弃物热解失重的主要原因。     

适用于质谱分析的在线固相萃取除盐方法

建立了一个简单、快速、有效的适用于质谱或液相色谱-质谱联用的在线固相萃取(SPE)高通量除盐方法。方法分为单柱和双柱模式,借助于包含双梯度泵(上样泵/分析泵)、自动进样器和配有十通切换阀的柱温箱的高效液相色谱系统,完成样品的自动化在线除盐。单柱模式通过上样泵实现在SPE柱上进样和除盐,被分析物则保留在SPE柱上;除盐完成后,通过阀切换利用分析泵洗脱富集在SPE柱上的被分析物。双柱模式则在单柱模式基础上增加了1根SPE柱,在色谱管理软件控制下2根SPE柱轮流工作,高效率完成样品的在线除盐。该方法在结合质谱分析蛋白质、多肽等领域具有较好的应用前景。     

Conversion of municipal solid wastes to carboxylic acids by thermophilic fermentation

The purpose of this research is to generate carboxylic acids from the biodegradable fraction of municipal solid wastes (MSW) and municipal sewage sludge (MSS) by using a thermophilic (55°C), anaerobic, high-solid fermentation. With terrestrial inocula, the highest total carboxylic acid concentration achieved was 20.5 g/L, the highest conversion obtained was 69%, and the highest acetic acid selectivity was 86.4%. Marine inocula were also used to compare against terrestrial sources. Continuum particle distribution modeling (CPDM) was used to predict the final acid product concentrations and substrate conversions at a wide range of liquid residence times (LRT) and volatile solid loading rates (VSLR). “Maps” showing the product concentration and conversion for various LRT and VSLR were generated from CPDM. The predictions were compared to the experimental results. On average, the difference between the predicted and experimental values were 13% for acid concentration and 10% for conversion. CPDM “maps” show that marine inocula produce higher concentrations than terrestrial inocula.     

Simultaneous thermal analysis/mass spectrometric investigations on the thermal behaviour of noble metal complexes

The results of investigations on the thermal behaviour of three selected noble metal complexes, performed by means of simultaneous thermal analysis/mass spectrometry are discussed. The thermal analysis data, such as the initial temperatures for the beginning of the weight loss, the amounts of the weight loss, as well as the characteristic DTG and DTA temperatures, are tabulated and the simultaneously recorded electron impact mass spectra are interpreted. The temperature-dependent formation and cleavage of typical complex-structure-related substituents is described and established by the evaluation of the course of the corresponding ion-current intensities.     

Vibrational analysis of polyethylene terephthalate and its deuterated derivatives

The Vibrational analysis of polyethylene terephthalate, polyethylene-d₄ terephthalate, and polyethylene terephthalate-d₄ has been carried out using a valence force field calculated from the infrared and Raman spectra of a series of low molecular weight aromatic esters. The Raman spectra for polyethylene-d₄ terephthalate and polyethylene terephthalate-d₄ are presented and band assignments for these compounds and polyethylene terephthalate are discussed.     

Treatment of municipal solid wastes by steam classification for recycling and biomass utilization

A patented method of steam classification (the Holloway Process) and a prototype process unit have been investigated. The process treats municipal solid wastes (MSW) with steam and pressure to yield sterilized recyclable metals, glass, and plastics and a cellulosic pulp. After processing, the components of the mixture are separated into three sizes by vibratory screening. The recyclable materials must be subsequently separated from the screened fractions. Process conditions have been optimized to maximize the yield of a sterile cellulosic fraction that has a variety of possible end uses, such as compost, combustion fuel, and feedstock for conversion to fuels and chemicals.     

Study of the pyrolysis of municipal solid waste for the production of valuable products

To obtain information on the potential of thermal conversion (pyrolysis) of municipal solid waste (MSW), a thermogravimetric study (TGA) is performed in a stream of nitrogen. Based on TGA results, pyrolysis experiments are carried out in a semi-batch reactor under inert nitrogen atmosphere. Slow pyrolysis is performed up to 550 °C (heating rate of 4 °C/min). Fast pyrolysis is performed at 450, 480, 510 and 550 °C and different input transfer rates (12 or 24 g material/min). The pyrolysis products are studied on composition and yield/distribution and investigated for their use as valuable product.The liquid obtained by slow pyrolysis separates spontaneously in a water rich product and an oily product. For all fast pyrolysis conditions, a viscous, brown oil which contains a poly(ethylene-co-propylene) wax is obtained. Composition analyses by GC/MS of the oil products (slow/fast pyrolysis) show that aliphatic hydrocarbons are the major compounds. The pyrolysis oils have high calorific value (between 35 and 44 MJ/kg), low wt% of water (around 6 wt%) and a low O/C value (between 0.2 and 0.3). The presence of waxy material is probably due to incomplete breakdown of poly(ethylene-co-propylene) present in MSW under study. The optimal pyrolysis conditions, regarding to oil yield, fuel properties, and wax yield is fast pyrolysis at 510 °C with 24 g material/min input transfer rate. The fast pyrolysis gases contain mainly hydrocarbons and have an averaged LHV around 20 MJ/Nm³. ICP-AES analyses of pyrolysis products reveal that almost none of the metals present in MSW are distributed within the liquid fractions.