A preliminary investigation into the physical and chemical properties of biomass ashes used as aggregate fillers for bituminous mixtures

Fly and bottom ashes are the main by-products arising from the combustion of solid biomass. Since the production of energy from this source is increasing, the processing and disposal of the resulting ashes has become an environmental and economic issue. Such ashes are of interest as a construction material because they are composed of very fine particles similar to fillers normally employed in bituminous and cementitious mixtures. This research investigates the potential use of ash from biomass as filler in bituminous mixtures. The morphological, physical and chemical characteristics of 21 different ashes and two traditional fillers (calcium carbonate and “recovered” plant filler) were evaluated and discussed. Leaching tests, performed in order to quantify the release of pollutants, revealed that five ashes do not comply with the Italian environmental re-use limits. Experimental results show a wide range of values for almost all the investigated properties and a low correlation with biomass type in terms of origin and chemical composition. Furthermore, sieving and milling processes were found to improve the properties of the raw material in terms of grading and sample porosity. The effectiveness of these treatments and the low content of organic matter and harmful fines suggest that most of the biomass ashes investigated may be regarded as potential replacements for natural filler in bituminous mixtures.     

Influence of the composition of the initial mixtures on the chemical composition,physicochemical properties and humic-like substances content of composts

The influence of the proportion of C- and N-rich raw materials (initial C/N ratio) and bulking agent on the chemical functional groups composition, humic-like substances (HS-like) content and physicochemical properties of composts was assessed. To achieve these goals, seven initial mixtures (BA1–6 and C1) of dog food (N-rich raw material) were composted with wheat flour (C-rich raw material). Composts were analyzed in terms of chemical functional groups, physicochemical, maturity and stability parameters.The C-rich raw material favored the formation of oxidized organic matter (OM) during the composting process, as suggested by the variation of the ratios of the peaks intensity of FT-IR spectra, corresponding to a decrease of the polysaccharides and an increase of aromatic and carboxyl-containing compounds. However, although with high proportion of C-rich raw material, mixtures with low initial C/N seems to have favored the accumulation of partially oxidized OM, which may have contributed to high electrical conductivity values in the final composts. Therefore, although favoring the partial transformation of OM into stabilized HS-like, initial mixtures with high proportion of C-rich raw material but with low initial C/N led to unstable composts.On the other hand, as long as a high percentage of bulking agent was used to promote the structure of biomass and consequently improve of the aeration conditions, low initial C/N was not a limiting factor of OM oxidation into extractable stabilized humic-like acids.     

Reprocessing of metallurgical slag into materials for the building industry

Several methods of reprocessing metallurgical (blast furnace) slag into materials for the building industry, based on melting aggregates with submerged combustion, were developed and tested. The first method involves melting hot slag with some additives directly in a slag ladle with a submerged gas-air burner, with the objective of producing stabilized slag or glass-ceramic. The second method involves direct draining of melted slag from a ladle into the slag receiver, with subsequent control of the slag draining into the converter where special charging materials are added to the melt, with the objective of producing glass-ceramic. A third method involves melting cold slag with some additives inside a melting converter with submerged gas-air burners, with the objective of producing glass-ceramic fillers for use in road construction. Specific to the melting process is the use of a gas-air mixture with direct combustion inside the melt. This feature provides melt bubbling to help achieve maximum heat transfer from combustion products to the melt, improve mixing (and therefore homogeneity of the melt), and increases the rate of chemical reactions. The experimental data for different aspects of the proposed methods are presented. The reprocessed blast-furnace slag in the form of granules can be used as fillers for concretes, asphalts, and as additives in the production of cement, bricks and other building materials. As well, reprocessed blast-furnace slag can be poured into forms for the production of glass-ceramic tiles.     

氟化工“三废”的资源化利用

结合我国氟化工行业发展现状,分析了含氟"三废"产生情况及处置方法的最新研究进展,并通过实际工程案例进行论述。氟化工生产过程污染物主要有含氟废气及副产氯化氢、含氟高沸物及含氟污泥等。通过将氯化氢用于工业清洗及制备氯化钙、氯化铝等化学品能够合理消耗副产盐酸。焚烧处理含氟有机废气产生的氟化氢气体经水洗后副产氢氟酸。含氟高沸物通过精馏分离出高沸物组分生产高附加值产品。含氟污泥可制成建筑材料,最优工业化利用途径仍在积极研究中。     

Effect of water washing on the thermal behavior of rice straw

Rice straw can be used as a renewable fuel for heat and power generation. It is a viable mean of replacing fossil fuels and preventing pollution caused by open burning, especially in the areas where this residual biomass is generated. Nevertheless, the thermal conversion of rice straw can cause some operating problems such as slag formation, which negatively affects thermal conversion systems. So, the main objective of this research is studying the combustion behavior of rice straw samples collected from various regions by applying thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). In addition, the thermal behavior of ashes from rice straw was also analyzed in order to detect their melting points, and ash sintering was detected at different temperatures within the range between 550 and 1000 °C. Since washing rice straw with water could reduce the content of undesirable inorganic compounds related to the ash fusibility, samples of washed rice straw were analyzed under combustion conditions to investigate its differences regarding the thermal behavior of rice straw. The results showed that rice straw washing led to a significant improvement in its thermal behavior, since it reduced the ash contents and sintering formation.     

Toxicity of char residues produced in the co-pyrolysis of different wastes

Char residues produced in the co-pyrolysis of different wastes (plastics, pine biomass and used tyres) were characterized using chemical and toxicity assays. One part of the solid chars was submitted to extraction with dichloromethane (DCM) in order to reduce the toxicity of the char residues by removing organic contaminants. The different volatility fractions present in the extracted char (Char A) and in the raw char (Char B) were determined by progressive weight loss combustion. A selected group of heavy metals (Cd, Pb, Zn, Cu, Hg and As) was determined in both chars.The chars were subjected to the leaching test ISO/TS 21268 – 2, 2007 and the resulting eluates were further characterized by determining a group of inorganic parameters (pH, conductivity, Cd, Pb, Zn, Cu, Hg and As contents) and the concentrations of several organic contaminants (volatile aromatic hydrocarbons and alkyl phenols). An ecotoxicological characterization was also performed by using the bio-indicator Vibrio fischeri.The chemical and ecotoxicological results were analyzed according to the Council Decision 2003/33/CE and the criteria on the evaluation methods of waste ecotoxicity (CEMWE).The results obtained in this work indicated that the extraction with DCM is an effective method for the removal of organic contaminants of high to medium volatility from pyrolysis solid residues, thus decreasing their toxicity potential. Zn can be leached from the chars even after the DCM extraction treatment and can contribute to the ecotoxicity of the eluates obtained from chars.Both chars (treated and non treated with DCM) were classified as hazardous and ecotoxic wastes.     

An overview on olive mill wastes and their valorisation methods

Olive mill wastes represent an important environmental problem in Mediterranean areas where they are generated in huge quantities in short periods of time. Their high phenol, lipid and organic acid concentrations turn them into phytotoxic materials, but these wastes also contain valuable resources such as a large proportion of organic matter and a wide range of nutrients that could be recycled. In this article, recent research studies for the valorisation of olive mill wastes performed by several authors were reviewed: second oil extraction, combustion, gasification, anaerobic digestion, composting and solid fermentation are some of the methods proposed. Special attention was paid to the new solid waste generated during the extraction of olive oil by the two-phase system. The peculiar physicochemical properties of the new solid waste, called two-phase olive mill waste, caused specific management problems in the olive mills that have led to the adaptation and transformation of the traditional valorisation strategies. The selection of the most suitable or appropriate valorisation strategy will depend on the social, agricultural or industrial environment of the olive mill. Although some methods are strongly consolidated in this sector, other options, more respectful with the environment, should also be considered.     

Combustible and incombustible speciation of Cl and S in various components of municipal solid waste

Chlorine (Cl) and sulfur (S) in municipal solid waste (MSW) are important reactive elements during combustion. They generate the acidic pollutants HCl and SOx, and, furthermore, produce and suppress organic chlorinated compounds. Nevertheless, few practical reports about Cl and S content in MSW have been published. In combustion and recycling processes, both combustible Cl and S, and incombustible Cl and S species are equally important. This paper presents the results of a comprehensive study about combustible and incombustible Cl and S in MSW components, including kitchen garbage, paper, textiles, wood and leaves, plastics and small chips. By integrating this collected data with data about MSW composition, not only the overall content of Cl and S in MSW, but also the origins of both combustible and incombustible Cl and S were estimated. The average Cl content in bulk MSW was 3.7 g/kg of raw MSW, of which 2.7 and 1.0 g/kg were combustible and incombustible, respectively. The Cl contribution from plastics was 76% and 27% with respect to combustible and incombustible states. The average S content in bulk MSW was 0.81 g/kg of raw MSW, of which 0.46 g/kg was combustible and 0.35 g/kg was incombustible. Combustible S was mainly due to synthetic textiles, while incombustible S was primarily from paper.     

Influence of combustion temperature on the performance of sewage sludge ash as a supplementary cementitious material

The potential for using sewage sludge ash (SSA) as a supplementary cementitious material (SCM) has been investigated. Controlled combustion of sewage sludge collected in Croatia from two wastewater treatment plants produced SSA with different characteristics. These were used to substitute for cement in mortar samples. The chemical composition and physical properties of SSA depend on wastewater composition, the sludge treatment process and the combustion temperature. These factors influence the suitability of SSA to be used as a SCM. For three different combustion temperatures (800, 900 and 1000 °C), it was concluded that properties of fresh mortar were not affected while in the hardened state, the most favorable combustion temperature is 900 °C regarding mechanical properties. Regardless of combustion temperature, for all types of SSA used in mortars as cement replacement (up to 30%), the average decrease in both compressive and flexural strength values was less than 8% for every 10% of added SSA. The results presented indicate that using up to 20% replacement of cement by SSA produces mortars that meet the specific technical requirements analyzed in this work.     

Steam gasification of tyre waste, poplar, and refuse-derived fuel: a comparative analysis

In the field of waste management, thermal disposal is a treatment option able to recover resources from "end of life" products. Pyrolysis and gasification are emerging thermal treatments that work under less drastic conditions in comparison with classic direct combustion, providing for reduced gaseous emissions of heavy metals. Moreover, they allow better recovery efficiency since the process by-products can be used as fuels (gas, oils), for both conventional (classic engines and heaters) and high efficiency apparatus (gas turbines and fuel cells), or alternatively as chemical sources or as raw materials for other processes. This paper presents a comparative study of a steam gasification process applied to three different waste types (refuse-derived fuel, poplar wood and scrap tyres), with the aim of comparing the corresponding yields and product compositions and exploring the most valuable uses of the by-products.     

Predicting the heating value of MSW with a feed forward neural network

The influence of the heating value of municipal solid waste (MSW) is very important on the combustion efficiency of MSW incinerators. The heating value of MSW is determined by the elementary chemical composition of its various components. Commonly, calorimetric measurement and empirical methods are available for this determination. In this analysis, the relationship between the physical composition and the low heating value (LHV) was studied. A feed forward neural network (FFNN) can be very helpful in predicting the heating value of MSW from its physical composition. The results of this analysis show that the prediction of LHV of MSW with FFNN is much better than conventional models.     

Cellulose Fiber Isolation and Characterization from Sweet Blue Lupin Hull and Canola Straw

In this study, cellulose fibers were removed from crop by-products using a combination of sodium hydroxide treatment followed by acidified sodium chlorite treatment. The objective was to obtain high recovery of cellulose by optimizing treatment conditions with sodium hydroxide (5–20%, 25–75 °C and 2–10 h) followed by acidified sodium chlorite (1.7%, 75 °C for 2–6 h) to remove maximum lignin and hemicellulose, as well as to investigate the effect of lignin content of the starting materials on the treatment efficiency. Samples were characterized for their chemical composition, crystallinity, thermal behavior and morphology to evaluate the effects of treatments on the fibers’ structure. The optimum sodium hydroxide treatment conditions for maximum cellulose recovery was at 15% NaOH concentration, 99 °C and 6 h. Subsequent acidified sodium chlorite treatment at 75 °C was found to be effective in removing both hemicellulose and lignin, resulting in higher recovery of cellulose in lupin hull (~?95%) and canola straw (~?93%). The resultant cellulose fibers of both crop by-products had increased crystallinity without changing cellulose I structure (~?68–73%). Improved thermal stabilities were observed with increased onset of degradation temperatures up to 307–318 °C. Morphological investigations validated the effectiveness of treatments, revealing disrupted cell wall matrix and increased surface area due to the removal of non-cellulosics. The results suggest that the optimized combination of sodium hydroxide and acidified sodium chlorite treatments could be effectively used for the isolation of cellulose fibers from sweet blue lupin hull and canola straw, which find a great number of uses in a wide range of industrial applications.     

Contribution of the lignocellulosic fraction of two-phase olive-mill wastes to the degradation and humification of the organic matter during composting

One of the main disadvantages in the composting of two-phase olive mill wastes (TPOMW) is the long time required for its transformation (up to 40 weeks). The aim of this work was to evaluate the relationship between the degradation of the lignocellulosic fraction of TPOMW and the organic matter (OM) mineralisation rate in four composting piles prepared with different bulking agents and N-sources used to enhance OM degradation. The kinetics of degradation of the lignocellulosic fraction was compared to conventional maturation and stability indices to evaluate its impact on the duration of the composting process. The composition of bulking agents mainly affected the water-soluble fraction which influenced the OM degradation rate (linear or exponential OM degradation pattern) at early stages of the composting process but it neither modified the duration of the process (between 34 and 36 weeks) nor the total OM degradation underwent by the piles. The high initial mineral N availability was a key factor to significantly enhanced microbial activity. The mixture with urea as N-source registered the most efficient degradation of hemicellulose, cellulose and lignin, reducing the thermophilic phase and the total duration of TPOMW composting.     

Comparative Study of Xylan Extracted by Sodium and Potassium Hydroxides (NaOH and KOH) from Bagasse Pulp: Characterization and Morphological Properties

Xylan is the second most abundant polysaccharide and the predominant hemicellulose component of soda bagasse pulp. The present endeavor focuses on increasing the value addition to underutilized agro-industrial residue such as bagasse. For this purpose, xylan was isolated by two conventional alkali extraction methods i.e. NaOH and KOH. The recovery rate and sugar composition of different reaction times and alkali consumptions were monitored with advanced method such as High Performance Liquid Chromatography (HPLC). The Fourier Transform Infrared Spectroscopy (FTIR) and Wide Angle X-ray spectroscopy (WAXS) were respectively employed to characterize the functional groups and Crystallinity Index (CrI) changes during the extraction process. It was explored that highest xylan recovery rates were obtained with 6% of NaOH at 120 min and 6% KOH at 45 min. The xylan morphology via WAXS was found that its structure to be amorphous. HPLC results also showed KOH had higher effectiveness than NaOH in terms of extracted xylan purity. Highest XGRs (Xylose to Glucose Ratios) were also achieved by KOH processes. Hence, this study contributes to the adequate utilization of agricultural residues, with promising potential for applications in the production of certain novel materials and chemical conversion industries.     

Eco-Compatible Use of Olive Husk as Filler in Thermoplastic Composites

A study on the possibility of recycling waste materials, such as olive husk, the solid phase derived from an olive oil mill, in blend with thermoplastic polymers to produce new materials for manufacturer of, for example, containers and formworks, has been carried out. The present paper describes the methodology used for the preparation and the characterization of composite samples prepared by mixing various percentages of olive husk and polypropylene. A screening on the chemical-physical characteristics of the olive husk is reported, as well as a set of tests applied to evaluate the mechanical properties of the manufactured products obtained.     

Chemically Modified Banana Fiber: Structure,Dielectrical Properties and Biodegradability

Banana fibers, as well as other lignocellulosic fibers, are constituted of cellulose, hemicellulose, lignin, pectin, wax and water soluble components. The abundance of this fiber combined with the ease of its processing is an attractive feature, which makes it a valuable substitute for synthetic fibers that are potentially toxic. In this work, the structure characterization of the banana fiber modified by alkaline treatment was studied. Some important properties of this fiber changed due to some chemical treatments, such as the crystalline fraction, dielectric behavior, metal removal (governed by solution pH) and biodegradation. Our results showed that treated banana fiber is a low cost alternative for metal removal in aqueous industry effluents. Thus, for regions with low resources, the biosorbents are an alternative to diminish the impact of pollution caused by local industries, besides being a biodegradable product.     

Effect of some environmentally degradable materials on the pyrolysis of plastics II: influence of cellulose and lignin on the pyrolysis of complex mixtures

Pyrolysis of polymer mixtures with a composition similar to that of municipal plastic waste containing polyvinyl chloride (PVC) and of municipal plastic waste free of PVC was performed in the presence of components of biomass, namely lignin, cellulose, or both. The pyrolysis products were characterized by standard methods utilized in the petrochemical industry, i.e., paraffins-isoparaffinsolefins-naphthenes-aromatics analysis, proton nuclear magnetic resonance and infrared spectroscopy, and gas chromatography-mass spectrometry. Up to 3 wt% lignin, cellulose, or both in mixed polymers changed the material balance of pyrolysis by decreasing the amount of waxy products. The presence of both PVC and biomass components significantly changed the material balance by decreasing the waxy product yield and increasing the gas and coke yield. The composition of all pyrolysis products was also modified with the addition of PVC, components of biomass, or both.     

Combustion studies of high moisture content waste in a fluidised bed

The combustion of three high moisture content waste materials in a fluidised bed combustor has been investigated and a comparison with co-firing of these materials with coal in the same combustor has been made. Waste materials burnt were olive oil waste, municipal solid waste and potato, which is representative of vegetable waste. Mixtures of up to 20% mass concentration water in the waste were fed to the combustor. Above that value the moisture content was too high to sustain combustion without addition of coal. Measurements of CO, NOx, SO2 temperatures were made and the carbon combustion efficiency evaluated. Co-firing with coal resulted in markedly higher combustion efficiencies with an increase of approximately 10-80% when burning the simulated MSW. However, this was much lower than the value of 93% when coal was burnt on its own. It was also much lower than the value obtained, average 90%, when co-firing potato and olive oil waste with coal and there was little difference in the combustion efficiency between the two types of waste and with increasing moisture content. It was concluded that the high ash content of the simulated MSW 26%, compared with 5% in the other two waste materials resulted in slower burning and consequently the char particles were elutriated from the bed without being fully burnt. In term of gaseous emissions during co-combustion, CO emission is relatively insensitive to change in waste fraction. While emission of SO2 can be reduced as the waste fraction increases as a result of fuel-S dilution. But in terms of percent fuel-S converted, it is actually increased by increasing waste fraction. Emissions of NO and N2O increase slightly with MSW fraction.     

A study of Cr(VI) in ashes from fluidized bed combustion of municipal solid waste: leaching, secondary reactions and the applicability of some speciation methods

The use of the fluidized bed technique for the combustion of municipal solid waste is a rather new concept. This type of combustor produces ash residues with somewhat different properties than the residues generated from the traditional mass burn techniques. Therefore, chemical characterization and the investigation of toxic metals behavior during ash water reactions are necessary for the safe disposal of these residues. In the present work, the total elemental composition, mineralogy and leaching behavior of ashes from the combustion of municipal solid waste in a fluidized bed combustion boiler have been investigated. The cyclone ash and, in particular, the filter ash contained considerable amounts of soluble substances, thus giving leachates with high levels of Cl-, Na+, K+, Ca2 + and Al(IIl). On the other hand, the two ash fractions taken in the boiler, the bottom and hopper ashes, were much more stable with respect to the release of salts and heavy metals. Since Cr(VI) is mobile and toxic its release from combustion residues can pose environmental problem. Even though the total Cr contents were similar in all ashes studied, the bottom ash gave about a thousand times higher levels of Cr(VI) in test leachates than the hopper, cyclone and filter ashes. However, it was found that the leached amount of Cr(VI) from the bottom ash decreased significantly when bottom ash was mixed with the hopper ash. The most probable cause for this decrease is the coupled oxidation of Al(0) to Al(III) and reduction of dissolved Cr(VI) to Cr(III). This finding that the mixing of two ash streams from the same boiler could result in the immobilization of Cr may point at a simple stabilization method. Selective extraction of water soluble, exchangeable and sparingly soluble forms of Cr(VI) was also investigated. Extraction methods were evaluated for their suitability for ash matrixes. It was found that interferences due to the presence of reducing substances in some ash materials may occur.     

Methane and carbon dioxide emission in a two-phase olive oil mill sludge windrow pile during composting

The aim of this work was to make some preliminary evaluations on CO(2) and CH(4) emissions during composting of two-phase olive oil mill sludge (OOMS). OOMS, olive tree leaves (OTL) and shredded olive tree branches (OTB) were used as feedstock for Pile I and Pile II with a 1:1:1 and 1:1:2v/v ratio, respectively. Each pile was originally 1.2m high, 2.0m wide and approximately 15.0m long. Four 500 ml volume glass funnels were inverted and introduced in each pile, two in the core (buried 50-60 cm from the surface) and two near the surface under a thin 10-15 cm layer of the mixture. Thin (0.5 cm diameter) plastic, 80 cm long tubes were connected to the funnels. A mobile gas analyser (GA2000) was used to measure the composition (by volume) of O2, CO2 and CH4 on a daily basis. The funnels were removed prior to each turning and reinserted afterwards. From each pair of funnels (core and surface) of both piles, one was kept closed between samplings. Two way ANOVA was used to test differences between piles and among the tubes. Post hoc Tukey tests were also used to further investigate these differences. There was a significant difference (at p<0.001) in the two piles for all three gases. The average concentrations of O2, CO2 and CH4 in Pile I, from all four funnels was 16.86%, 3.89% and 0.25%, respectively, where for Pile II the average values were 18.07%, 2.38% and 0.04%, respectively. The presence of OOMS in larger amounts in Pile I (resulting in more intense decomposing phenomena), and the larger particle size of OTB in Pile II (resulting in increasing porosity) are the probable causes of these significant differences. Samples from open funnels presented lower, but not significantly lower, O2 composition (higher for CO2 and CH4) in comparison with closed funnels in both depths and both piles. Not significant were also the different mean gas compositions between core and surface funnels in the same pile.