Investigation of the pyrolysis behaviour of brown algae before and after pre-treatment using PY-GC/MS and TGA

The pyrolysis behaviour of a number of brown macroalgae (seaweeds) collected in the UK such as Laminaria hyperborea and Fucus vesticulosus, are compared with the tropical algae Macrocystis pyrifera. Macroalgae contain a significant amount of alkali earth metals, halogens and a range of trace heavy metals. Pre-treatment of the algae has been performed to remove mineral matter in both water and weak acid. The pyrolysis behaviour of the residues has been investigated and the effect of processing on ash content and mineral composition has been determined. The pyrolysis behaviour of the raw samples and the residues from processing has been studied using thermal gravimetric analysis (TGA) and pyrolysis-GC/MS (Py-GC/MS). Total mineral matter has been determined using inductively coupled plasma-optical emission spectroscopy (ICP-OES) before and after pre-treatment. The Py-GC/MS pyrograms at 500 °C indicate the presence of a range of ketones, pentosans, nitrogen containing compounds and phenols. The residues from pre-treatment have different pyrolysis behaviours, particularly after acid treatment. The pre-treatment schemes investigated can remove a significant proportion of the mineral matter and halogens although they also selectively extract polymeric material. The residues have lower ash content and lower nitrogen content. Results for pre-treatment in water are consistent with the removal of mannitol, while results for pre-treatment in acid are consistent with the removal of fucoidan, mannitol and the partial removal of laminarin. Py-GC/MS of the residue from pre-treatment in acid produces a similar pyrogram to alginic acid in which furfural is a dominant product. There appears to be potential for the production of fuels and chemicals from brown algae by pyrolysis although the reduction of mineral matter and halogens by pre-treatment is advantageous.     

Characterization and thermal behavior of residues from industrial sugarcane processing

The increase in sugarcane production and processing in order to obtain important products such as sugar and ethanol has the negative aspect of also increasing industrial residues. The most important residues originated during processing are bagasse, hydrolyzed bagasse, filter cake, vinasse, and ash. Thermal analysis revealed that these residues have peculiar properties, such as the presence of lignocellulosic material, except in the ash. The amount of organic matter decreases during the treatment process, due to the addition of chemical products to the residues, which are responsible for some alteration in their thermal properties. Colorimetric analysis showed considerable K and P concentrations in the vinasse and filter-cake residues. EDX and infrared spectroscopy showed the presence of Si in the residues. A higher percent of Si in ash sample was also observed, as a product of the thermal decomposition, by TG, FTIR, and X-ray diffractometry.     

煤与生物质混烧灰荷电特性研究

对玉米秸分别与两种煤以不同比例混烧生成的混烧灰进行了荷电特性研究。利用法拉第杯荷电量检测系统和静电低压撞击器(ELPI)测量了混烧灰的总体荷质比及分级荷质比,并借助于成分分析及形貌分析结果讨论了其影响机理。结果表明,随着生物质掺入量在混烧燃料中的增加,混烧灰的成分组成发生变化,使得其介电常数变大,比电阻增大,表面吸附能力增强,从而使混烧灰的总体荷质比有一定的上升趋势。对混烧灰的分级荷质比测量结果表明,排除灰样粒径的影响,生物质的掺入使得混烧灰的荷电能力得以增强,但影响相对较小,颗粒粒径是影响混烧灰荷电能力的主要因素。     

Determining the melting behaviour of ashes from incineration plants via thermal analysis

The ash behaviour comprises one major obstacle towards the efficient utilization of municipal solid wastes, (MSW), in incineration plants. The presence of large amounts of inorganic constituents such as alkali and alkali earth metals, chlorine, sulfur and zinc increase significantly the ash reactivity and lead to severe ash-related problems such as fouling, slagging, corrosion and erosion during their thermal treatment. In this paper, the melting behaviour of various ash fractions originating from the incineration of MSW is studied using simultaneous, (DSC/TG), thermal analysis methods. The produced results provide the basis for improved modelling of the ash behaviour during the incineration of MSW. This revised version was published online in July 2006 with corrections to the Cover Date.     

Kinetics of thermal decomposition of PVC/fly ash composites

In this study, the kinetics and mechanisms of thermal degradation of Poly Vinyl Chloride (PVC) composites reinforced with class-F fly ash are studied experimentally and numerically using Flynn–Wall model. The addition of fly ash to the polymer matrix results in a decrease in the primary degradation temperature and an increase in the secondary degradation temperature. The metal oxides in the fly ash act as acid absorbers, which results in the destabilization of PVC during its dehydrochlorination process. However, they also react with the chlorine free radicals, which prevents the formation of HCl during degradation. In addition, it is observed that calcium and iron oxides, present in fly ash, are more reactive to the chlorine radicals rather than the silicon and aluminum oxides. The effect of fly ash chemical composition on the degradation of PVC composites was studied by comparing the thermal properties of composites containing two different classes of fly ashes, class-F and class-C, at similar levels. Thermal stability of the composites is found to be dependent on the chemical composition of fly ash. Higher dehydrochlorination rate is observed in the case of composites filled with class-F fly ash than those reinforced with class-C fly ash.     

Development and application of an analytical protocol for evaluation of treatment processes for landfill leachates. II. Evaluation of leachate treatment efficiency of different steps in a constructed pilot plant

Different methods for treatment of leachate from a municipal solid waste (MSW) landfill were tested in a pilot plant. Raw leachate was pre-treated with aeration and sedimentation, followed by several parallel individual steps such as bioremediation, chemical oxidation, ozonation, and geo-bed filters. The efficiency of different treatment steps was evaluated according to one previously developed protocol, which includes measurements of several parameters such as conductivity, pH, nutrients, chloride, metals, organic compounds, and acute toxicity before and after a treatment step. The treatment steps which showed the highest efficiency towards organic pollutants in leachate were ozone treatment and chemical oxidation. The use of an adsorption filter, a geo-bed with a mixture of peat and bottom ash with ca 10% remaining carbon, also had good effects. A combination of pre-treatment and a geo-bed filter with peat and carbon ash gave the best overall treatment results when water-quality parameters such as total organic carbon and ammonia-nitrogen were also considered.     

The hydraulic activity of high calcium fly ASH

Cementitious mixtures with so-called high calcium fly ash show better strength parameters as compared to the ones with conventional siliceous fly ash. This practical feature is the consequence of improved hydraulic activity. Differential thermal analysis and thermogravimetry were used, together with the other methods, to evaluate the reactivity of high calcium fly ash in mixtures with cements. This type of fly ash exhibits hydraulic properties (setting and hardening on hydration) and durability, after hardening, in the presence of water. The so-called pozzolanic activity is the feature of high active silica containing fly ash while the hydraulic activity is related to the high calcium ones. However, the chemical and phase composition is variable and related to the particle size. The hydraulic/ pozzolanic properties are strongly improved by additional grinding (specific surface increase).     

Extraction and characterization of new natural lignocellulosic fiber Cyperus pangorei

This research is focused on the study of the physical, chemical, mechanical, and thermal properties of a newly identified natural stem fiber, Cyperus pangorei. The chemical composition of Cyperus pangorei fibers (CPF) such as cellulose, lignin, ash, moisture, and wax contents was evaluated. Besides these, the fiber density was determined and the apparent diameter was measured using an optical microscope. Further, tensile, thermal, XRD, and FT-IR studies were performed to evaluate the suitability of the fiber as a reinforcement. The surface topography of CPF was analyzed using scanning electron microscopy (SEM). Encouraging properties such as increased stiffness, fiber texture, and higher thermal stability suggest the suitability of CPF as reinforcement in polymer matrices.     

Mineralogical and Geochemical Characteristics of the Human Body Ash Residue

The article is devoted to the element composition of the human body ash residue of some Russian cities. It presents the element composition of the human body ash residue, the distribution of elements in the ash residue depending on age and sex. The specific elements of different cities, showing the possible influence of the environmental conditions on the element composition of the human body ash residue. The main objective of this paper is to study the element composition of the human body ash residue and determine the regional characteristics. The methods of instrumental neutron activation analysis and inductively coupled plasma mass spectrometry were applied, an electronic microscope being used as a tool. The result of the research is 63 elements identified within in the human body ash residue. The issue is topical as it expands the knowledge of rare and radioactive elements within the human body and contributes to medicine, for example, by identifying the chemical elements to be included in a person's diet.     

Flame retardancy of polycarbonate enhanced by adding fly ash

We have developed a flame‐retardant polycarbonate resin whose flame retardancy is greatly enhanced by adding fly ash (a by‐product from thermal power plants). Fly ash with comparatively small average particle sizes (<10 µm) raised the flame retardancy of polycarbonate because of the hydrogen bond that forms between the polycarbonate and the hydroxy group on the fly ash surface. This bond primarily improves the heat resistance of the polycarbonate and also isomerizes the polycarbonate to promote carbonization. The polycarbonate with 25 wt% of the fly ash showed good other main characteristics, such as mechanical properties and moldability, comparable to those of a flame retardant polycarbonate reinforced with glass fiber, used for electronic products such as desktop computers, etc. Applying the fly ash eliminates the need to use current retardants such as organic halogen compounds and thus promotes the perceived environmental safety of flame‐ retardant polycarbonate. In addition, being able to use less raw resin by adding the fly ash means that less energy is required to manufacture flame‐retardant polycarbonate. Copyright © 2007 John Wiley & Sons, Ltd.     

Effect of sample preparation on the thermal degradation of metal-added biomass

The present study investigates the effect of different sample preparation methods on the pyrolysis behaviour of metal-added biomass; Willow samples were compared in the presence of two salts of zinc and lead containing sulphate and nitrate anions which were added to the wood samples with three different techniques as dry-mixing, impregnation and ion-exchange. The effect of acid and water wash as common demineralisation pre-treatments were also analysed to evaluate their roles in the thermal degradation of the biomass. Results from thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR) and pyrolysis-mass spectrometry (Py-MS) measurements indicated that these pre-treatments change the matrix and the physical–chemical properties of wood. Results suggested that these structural changes increase the thermal stability of cellulose during pyrolysis. Sample preparation was also found to be a crucial factor during pyrolysis; different anions of metal salts changed the weight loss rate curves of wood material, which indicates changes in the primary degradation process of the biomass. Results also showed that dry-mixing, impregnation or ion-exchange influence the thermal behaviour of wood in different ways when a chosen metal salt was and added to the wood material.     

Alkali pre-treatment of Sorghum Moench for biogas production

This work studies the influence of the alkali pre-treatment of Sorghum Moench — a representative of energy crops used in biogas production. Solutions containing various concentrations of sodium hydroxide were used to achieve the highest degradation of lignocellulosic structures. The results obtained after chemical pre-treatment indicate that the use of NaOH leads to the removal of almost all lignin (over 99 % in the case of 5 mass % NaOH) from the biomass, which is a prerequisite for efficient anaerobic digestion. Several parameters, such as chemical oxygen demand, total organic carbon, total phenolic content, volatile fatty acids, and general nitrogen were determined in the hydrolysates thus obtained in order to define the most favourable conditions. The best results were obtained for the Sorghum treated with 5 mass % NaOH at 121°C for 30 min The hydrolysate thus achieved consisted of high total phenolic compounds concentration (ca. 4.7 g L^?1) and chemical oxygen demand value (ca. 45 g L^?1). Although single alkali hydrolysis causes total degradation of glucose, a combined chemical and enzymatic pre-treatment of Sorghum leads to the release of large amounts of this monosaccharide into the supernatant. This indicates that alkali pre-treatment does not lead to complete cellulose destruction. The high degradation of lignin structure in the first step of the pre-treatment rendered the remainder of the biomass available for enzymatic action. A comparison of the efficiency of biogas production from untreated Sorghum and Sorghum treated with the use of NaOH and enzymes shows that chemical hydrolysis improves the anaerobic digestion effectiveness and the combined pre-treatment could have great potential for methane generation.     

Thermal characterization of biomass smoke particles

In this paper we present results on characterization of filter-collected redwood (Sequoia sempevirens)-needle and eucalyptus smoke particles by thermal, optical, and solvent extraction methods. Our results show that black carbon and a significant fraction of organic carbon in biomass smoke particles have similar volatility and combustion temperatures. Combustion temperatures of both black carbon and this organic fraction critically depend on the concentrations of common constituents of biomass smoke such as Na and K. These species are also known to catalyze the combustion and therefore lower the combustion temperatures by more than 100 °C. Consequently, thermal methods that rely on a specific temperature to separate organic from black carbon may either underestimate or overestimate the black and organic carbon concentrations, depending on the amounts of Na and K and on the composition and concentration of organic material present in a sample. These results suggest that more than one method must be used to accurately determine the organic and black carbon concentrations in biomass smoke particles.     

Thermal conductivity of lightweight aggregate based on coal fly ash

The article presents the results of physical and chemical properties of lightweight aggregates (LWA) obtained by the thermal treatments of raw composition based on fly ash, supplied by electric plants from Serbia. The production process of LWA consists of raw material preparation, plastic shaping?Cextrusion, granulation, and thermal treatment at three temperatures: 1100, 1150, and 1200?°C. The final firing temperature (T?=?1150?°C) is chosen based on the mechanical and physical properties of the designed aggregates. The particle-size distribution of the LWAs is unimodal (d????16?mm) while the density value varies from 0.98 to 1.99?g/cm³. The water absorption values are determined by use of two methods: 24?h of soaking in cold water and 5?h of boiling. The thermal conductivity of unbound, fired LWA particles is determined by measuring the amount of axially transferred heat in the stationary state. The obtained value of the LWA thermal conductivity (???=?0.0872?W/mK, T?=?1150?°C) is suitable for the production of structural concrete blocks with improved thermal insulating properties. Because of their high-porosity and -compressive strength values, the designed LWA could be used instead of the conventional aggregates in the production of concrete blocks. Consequently, a real valorization of the waste material such as fly ash in Serbia was established.     

Analyse des molecules organochlorées piegées dans la matrice minérale des REFIOM

Analysis of the chloroorganic trapped in the mineral matrix of fly ash. Incineration is often considered as the most efficient process for urban waste destruction. Although it is a rather clean technique, it is often suspected to be the source of severe pollutions such as metal pollution or dioxin and furan emissions. In order to reduce hazardous emissions, various operating furnace parameters can be controlled, like gas residence time, flame temperature and excess air flow rate, among others. According to European regulations, incineration fly ash corresponds to class I disposal landfills, which demonstrates that it is considered as a toxic waste. The aim of this work was to develop a non equilibrium plasma process in order to study the behaviour of chloroorganics trapped on fly ash by on-line mass spectrometric analysis. The identification of the desorption of chloroorganics trapped within the mineral matrix presents juridical and scientific aspects. This study shows the existence of chemical reactions between the excited species produced from the plasma and the molecules desorbed from the mineral matrix of fly ash during the plasma treatment through the chemical analysis of the gaseous effluent. Special emphasis was put on the physicochemical properties of fly ash (composition of mineral matrix, particles size…)     

Pyrolysis of various biomass residues and char utilization for the production of activated carbons

Biomass samples (almond shell, walnut shell, almond tree pruning and olive stone) were subjected to thermoanalytical investigation to evaluate their thermal behaviour and its correlation with their lignocellulosic composition. Then, the pyrolysis process of these materials was studied in terms of the energy content of the phases generated (gas and liquid). Finally, the feasibility of obtaining effective adsorbents from the char generated was studied. With this aim, the char was used to prepare activated carbons (ACs) by steam gasification at fixed activation temperature and time, identical for the four chars. The differences found in the porosity development of the activated carbons were related to the lignocellulosic composition of the raw material. It is shown that the four biomass residues used are versatile precursors that allow the preparation of adsorbent materials with different textural characteristics.     

Energetic study of residual forest biomass using calorimetry and thermal analysis

Summary The European policy on energy focus on the search for alternative and renewable sources of energy where forest biomass plays a significant role. In this article, calorific values of different kinds of forest residues (leaves, thin branches, barks, etc.) are reported. These values were measured by combustion bomb calorimetry with the objective of understanding, through different risk indices, the behaviour of forest waste in the case of wildfires, and also to study the use of forest residues as raw materials to be used as energy sources. The study was complemented with determination of elemental analysis, flammability using a standard epiradiator, thermodegradation analysis, and different mechanical tests trying to get relationships between thermal behaviour and some physical properties. The study was carried out on Eucalyptus globulus Labill and Pinus pinaster Aiton, because these forest formations have both high economical and ecological interest in Galicia (NW Spain).     

Thermal ignition behaviour of ammonium perchlorate in presence of fuel-rich compounds

The thermal ignition behaviour of ammonium perchlorate has been investigated in the presence of fuel-rich compounds such as tetramethylammonium perchlorate, trimethylammonium nitrate, carbon and cellulose. The ignition characteristics, as studied by differential thermal analysis, have been found to be strongly influenced by self-decomposition and other physicochemical properties of the additives. For a simple system, an analytical model proposed on the basis of the coupling of two exothermic decomposition reaction kinetics and a heat-balance equation, appears to explain to some extent the observed trend in peak ignition temperature when the composition is varied. The salient features of the analysis, as regards its application to fuel-oxidizer interactions in general, have been pointed out.     

Prediction of the Behaviour of Biomass Ash in Fluidized Bed Combustors and Gasifiers

Two types of agricultural residues (wheat straw and olive residue) in untreated and pretreated (fractionation, leaching) form were tested as concerns their ash melting behaviour during fluidized bed combustion and gasification by means of thermal analysis techniques. The techniques applied included DSC, simultaneous DSC/TG and TG-MS for the determination of low-temperature ash melts and losses caused by the volatilization of alkali material. In combination with ash elemental analyses on the materials, the applied techniques proved to offer valuable information for prediction of the ash behaviour in fluidized bed reactors. This revised version was published online in August 2006 with corrections to the Cover Date.     

Triglycerides as Novel Phase-Change Materials: A Review and Assessment of Their Thermal Properties

Latent Heat Storage (LHS) with Phase-Change Materials (PCMs) represents a high energy density storage technology which could be applied in a variety of applications such as waste heat recovery and integration of renewable energy technologies in energy systems. To increase the sustainability of these storage solutions, PCMs have to be developed with particular regard to bio-origin and biodegradability. Triglycerides represent an interesting class of esters as the main constituents of animal and vegetable fats, with attractive thermal properties. In order to be used as PCMs, the thermal behaviour of triglycerides has to be fully understood, as in some cases they have been reported to show polymorphism and supercooling. This study assesses the suitability of triglycerides as PCMs by reviewing the literature published so far on their behaviour and properties. In particular, melting points, enthalpies of fusion, polymorphism, thermal conductivities, heat capacities and thermal cycling stabilities are considered, with a focus on LHS and thermal energy storage applications. In addition, the efforts conducted regarding modelling and the prediction of melting points and enthalpies based on chemical structures are summarized and assessed.