Abundance of 14C in biomass fractions of wastes and solid recovered fuels

In recent years thermal utilization of mixed wastes and solid recovered fuels has become of increasing importance in European waste management. Since wastes or solid recovered fuels are generally composed of fossil and biogenic materials, only part of the CO₂ emissions is accounted for in greenhouse gas inventories or emission trading schemes. A promising approach for determining this fraction is the so-called radiocarbon method. It is based on different ratios of the carbon isotopes ¹⁴C and ¹²C in fossil and biogenic fuels. Fossil fuels have zero radiocarbon, whereas biogenic materials are enriched in ¹⁴C and reflect the ¹⁴CO₂ abundance of the ambient atmosphere. Due to nuclear weapons tests in the past century, the radiocarbon content in the atmosphere has not been constant, which has resulted in a varying ¹⁴C content of biogenic matter, depending on the period of growth. In the present paper ¹⁴C contents of different biogenic waste fractions (e.g., kitchen waste, paper, wood), as well as mixtures of different wastes (household, bulky waste, and commercial waste), and solid recovered fuels are determined. The calculated ¹⁴C content of the materials investigated ranges between 98 and 135 pMC.     

Mathematical modeling to predict residential solid waste generation

One of the challenges faced by waste management authorities is determining the amount of waste generated by households in order to establish waste management systems, as well as trying to charge rates compatible with the principle applied worldwide, and design a fair payment system for households according to the amount of residential solid waste (RSW) they generate. The goal of this research work was to establish mathematical models that correlate the generation of RSW per capita to the following variables: education, income per household, and number of residents. This work was based on data from a study on generation, quantification and composition of residential waste in a Mexican city in three stages. In order to define prediction models, five variables were identified and included in the model. For each waste sampling stage a different mathematical model was developed, in order to find the model that showed the best linear relation to predict residential solid waste generation. Later on, models to explore the combination of included variables and select those which showed a higher R(2) were established. The tests applied were normality, multicolinearity and heteroskedasticity. Another model, formulated with four variables, was generated and the Durban-Watson test was applied to it. Finally, a general mathematical model is proposed to predict residential waste generation, which accounts for 51% of the total.     

Influence of physical properties of solid biomass fuels on the design and cost of storage installations

The aim of this work consists on determining biomass fuels properties and studying their relation with fixed and variable costs of stores and handling systems. To do that, dimensions (length and diameter), bulk density, particle density and durability of several brands and batches of wood pellets and briquettes were tested, according to international standards. Obtained results were compared with those in literature. Bulk density tests were applied for several other biomass fuels too, and later used to determinate which ones of all the biomass-fuels tested are economically more profitable for a typical transport/store system made of a screw conveyor and a concrete bunker silo.     

Mathematical modelling of the composting process: a review

In this paper mathematical models of the composting process are examined and their performance evaluated. Mathematical models of the composting process have been derived from both energy and mass balance considerations, with solutions typically derived in time, and in some cases, spatially. Both lumped and distributed parameter models have been reported, with lumped parameter models presently predominating in the literature. Biological energy production functions within the models included first-order, Monod-type or empirical expressions, and these have predicted volatile solids degradation, oxygen consumption or carbon dioxide production, with heat generation derived using heat quotient factors. Rate coefficient correction functions for temperature, moisture, oxygen and/or free air space have been incorporated in a number of the first-order and Monod-type expressions. The most successful models in predicting temperature profiles were those which incorporated either empirical kinetic expressions for volatile solids degradation or CO2 production, or which utilised a first-order model for volatile solids degradation, with empirical corrections for temperature and moisture variations. Models incorporating Monod-type kinetic expressions were less successful. No models were able to predict maximum, average and peak temperatures to within criteria of 5, 2 and 2 degrees C, respectively, or to predict the times to reach peak temperatures to within 8 h. Limitations included the modelling of forced aeration systems only and the generation of temperature validation data for relatively short time periods in relation to those used in full-scale composting practice. Moisture and solids profiles were well predicted by two models, but oxygen and carbon dioxide profiles were generally poorly modelled. Further research to obtain more extensive substrate degradation data, develop improved first-order biological heat production models, investigate mechanistically-based moisture correction factors, explore the role of moisture tension, investigate model performance over thermophilic composting time periods, provide more information on model sensitivity and incorporate natural ventilation aeration expressions into composting process models, is suggested.     

Renewable hydrocarbons through biomass hydropyrolysis process: challenges and opportunities

Considering the current issues of carbon control and the desire to become less dependent on imported oil, the utilization of renewable hydrocarbons for the reduction of CO₂ emission and production of liquid synthetic fuels/chemicals has been proposed by researchers worldwide. Efforts to make chemicals/fuels from renewable resources have escalated over the past few years. Biomass-based renewable hydrocarbons are considered to be one of the sources with the highest potential to contribute to the energy needs of modern society for both developed and developing economies worldwide. Fast pyrolysis is becoming an important thermal route to convert biomass to liquid fuels; however, the raw bio-oils obtained have a number of negative properties such as high acidity, high water content, and variable viscosity over time. To overcome this problem and produce bio-oil of good quality, process of ‘hyropyrolysis’ has been developed. The scope for using pyrolysis under hydrogen pressure and also by process of hydropyrolysis followed by in situ hydroconversion of vapors to give oils with much lower oxygen contents has been reviewed.     

Mathematical modelling of a composting process, and validation with experimental data

The present study aimed to develop a mathematical model of composting which, while not overlooking the fundamental principles of physical and microbiological chemistry, could be easily applied in practice and be validated by experimental data. The experimental results of the biological aerobic decomposition of a mixture consisting of rice and rice husks, could be explained in terms of the parameter aggregation model, assuming a set of pseudo-first-order reactions in series, in which a hydrolysis step is followed by a biochemical oxidative step with formation of compost, biomass and biological gases (CO2, O2). The corresponding kinetic parameters and their temperature dependence were determined. These parameters indicated that the hydrolysis step was always the slowest one, and, therefore, the overall rate-determining step. This is in substantial agreement with our experimental observations of a non-dependency of the overall rate on the oxygen concentration, and suggests that rather than using mesophilic and thermophilic bacteria and fungi for seeding or accelerating the process, adequate hydrolytic enzymes (or related micro-organisms) should be added, instead.     

Conversion of LDPE into transportation fuels by a two-stage process using Ni/Al-SBA-15 as catalyst

Ni/Al-SBA-15 catalysts with Si/Al atomic ratios within the 20–135 range were prepared by a post synthesis grafting procedure, having nickel contents between 6 and 11 %. The addition of Ni to the Al-SBA-15 support caused a decrease of the BET surface area and pore volume. Additionally, larger Ni particles were attained over the catalysts with higher Si/Al atomic ratios, indicating the existence of some interaction between aluminium species and nickel particles. Ni/Al-SBA-15 catalysts displayed remarkable properties for the preparation of diesel fuels in the hydroreforming of the oils obtained from the LDPE thermal cracking. On increasing the Si/Al atomic ratios of the Ni/Al-SBA-15 catalysts, higher share of light and heavy diesel were attained, the sum reaching a maximum (67.3 %) for Ni/Al-SBA-15(70). This was caused by the higher extent of oligomerization reactions on enhancing the Si/Al atomic ratio. Additionally, around 85–90 % of the starting olefins were successfully hydrogenated and the aromatic content was rather low (below 5 %), without almost any polyaromatic compound (<0.1 %).     

Comparison of different procedures to stabilize biogas formation after process failure in a thermophilic waste digestion system: influence of aggregate formation on process stability

Following a process failure in a full-scale biogas reactor, different counter measures were undertaken to stabilize the process of biogas formation, including the reduction of the organic loading rate, the addition of sodium hydroxide (NaOH), and the introduction of calcium oxide (CaO). Corresponding to the results of the process recovery in the full-scale digester, laboratory experiments showed that CaO was more capable of stabilizing the process than NaOH. While both additives were able to raise the pH to a neutral milieu (pH>7.0), the formation of aggregates was observed particularly when CaO was used as the additive. Scanning electron microscopy investigations revealed calcium phosphate compounds in the core of the aggregates. Phosphate seemed to be released by phosphorus-accumulating organisms, when volatile fatty acids accumulated. The calcium, which was charged by the CaO addition, formed insoluble salts with long chain fatty acids, and caused the precipitation of calcium phosphate compounds. These aggregates were surrounded by a white layer of carbon rich organic matter, probably consisting of volatile fatty acids. Thus, during the process recovery with CaO, the decrease in the amount of accumulated acids in the liquid phase was likely enabled by (1) the formation of insoluble calcium salts with long chain fatty acids, (2) the adsorption of volatile fatty acids by the precipitates, (3) the acid uptake by phosphorus-accumulating organisms and (4) the degradation of volatile fatty acids in the aggregates. Furthermore, this mechanism enabled a stable process performance after re-activation of biogas production. In contrast, during the counter measure with NaOH aggregate formation was only minor resulting in a rapid process failure subsequent the increase of the organic loading rate.     

Fluidized bed gasification of waste-derived fuels

Five alternative waste-derived fuels obtained from municipal solid waste and different post-consumer packaging were fed in a pilot-scale bubbling fluidized bed gasifier, having a maximum feeding capacity of 100 kg/h. The experimental runs utilized beds of natural olivine, quartz sand or dolomite, fluidized by air, and were carried out under various values of equivalence ratio. The process resulted technically feasible with all the materials tested. The olivine, a neo-silicate of Fe and Mg with an olive-green colour, has proven to be a good candidate to act as a bed catalyst for tar removal during gasification of polyolefin plastic wastes. Thanks to its catalytic activity it is possible to obtain very high fractions of hydrogen in the syngas (between 20% and 30%), even using air as the gasifying agent, i.e. in the most favourable economical conditions and with the simplest plant and reactor configuration. The catalytic activity of olivine was instead reduced or completely inhibited when waste-derived fuels from municipal solid wastes and aggregates of different post-consumer plastic packagings were fed. Anyhow, these materials have given acceptable performance, yielding a syngas of sufficient quality for energy applications after an adequate downstream cleaning.     

The presence of zinc in Swedish waste fuels

Zinc (Zn) is a chemical element that has gained more attention lately owing to its possibility to form corrosive deposits in large boilers, such as Waste-to-Energy plants. Zn enters the boilers in many different forms and particularly in waste, the amount of Zn is hard to determine due to both the heterogeneity of waste in general but also due to the fact that little is yet published specifically about the Zn levels in waste. This study aimed to determine the Zn in Swedish waste fuels by taking regular samples from seven different and geographically separate waste combustion plants over a 12-month period. The analysis shows that there is a relation between the municipal solid waste (MSW) content and the Zn-content; high MSW-content gives lower Zn-content. This means that waste combustion plants with a higher share of industrial and commercial waste and/or building and demolition waste would have a higher share of Zn in the fuel. The study also shows that in Sweden, the geographic location of the plant does not have any effect on the Zn-content. Furthermore, it is concluded that different seasons appear not to affect the Zn concentrations significantly. In some plants there was a clear correlation between the Zn-content and the content of other trace metals.     

Construction and demolition waste management process modeling: a framework for the Brazilian context

Journal of Material Cycles and Waste Management - In Brazil, municipal public authorities are responsible for construction and demolition (C&amp;D) waste management. However, there is a lack of...     

Biogas production from malt bagasse from craft beer industry: kinetic modeling and process simulation

Journal of Material Cycles and Waste Management - In this work, biogas was synthesized from malt enriched-craft beer bagasse with the objective to generate clean energy. Thus, a kinetic model based...     

Mathematical modeling of MSW combustion and SNCR in a full-scale municipal incinerator and effects of grate speed and oxygen-enriched atmospheres on operating conditions

The rising popularity of incineration of municipal solid waste (MSW) calls for detailed mathematical modeling and accurate prediction of pollutant emissions. In this paper, mathematical modeling methods for both solid and gaseous phases were employed to simulate the operation of a 450 t/d MSW-burning incinerator to obtain detailed information on the flow and combustion characteristics in the furnace and to predict the amount of pollutant emissions. The predicted data were compared to on-site measurements of gas temperature, gas composition and SNCR de-NO_X system. The major operating conditions considered in this paper were grate speed and oxygen concentration. A suitable grate speed ensures complete waste combustion. The predictions are as follows: volatile release increases with increasing grate speed, and the maximal value is within the range of 700–800 kg/m² h; slow grate speeds result in incomplete combustion of fixed carbon; the gas temperature at slow grate speeds is higher due to adequate oxygenation for fixed carbon combustion, and the deviation reaches 200 K; NO_X emission decreases, but CO emission and O₂ concentrations increase, and the deviation is 63%, 34% and 35%, respectively. Oxygen-enriched atmospheres promote the destruction of most pollutants due to the high oxygen partial pressure and temperature. The furnace temperature, NO production and CO emission increase as the oxygen concentration increases, and the deviation of furnace exit temperature, NO and CO concentration is 38.26%, 58.43% and 86.67%, respectively. Finally, oxygen concentration is limited to below 35% to prevent excessive CO and NO_X emission without compromising plant performance. The current work greatly helps to understand the operating characteristics of large-scale MSW-burning plants.     

并流加料沉淀法处理含铜锌废水同时形成类水滑石污泥

分别采用传统沉淀法和并流加料沉淀法处理含铜锌废水,考察了废水进样速率、废水pH、搅拌速率对重金属离子残留质量浓度的影响。采用FTIR、XRD和SEM表征了所得污泥的物相和形貌。实验结果表明:并流加料沉淀法所得滤液中Zn~(2+)、Cu~(2+)和Al3+的质量浓度远低于传统沉淀法;在废水进样速率1.0 mL/min、废水pH 9、搅拌速率500 r/min的最佳工艺条件下,滤液中Cu~(2+)和Zn~(2+)基本没有残留,Al3+质量浓度仅为0.2 mg/L,达到工业排放标准;所得污泥结晶度良好,为类水滑石Cu_3Zn_3Al_2(OH)_(16)CO_3·4H_2O(PDF#37-0629)结构。     

生物质转化利用技术研究进展

综述了当前国内外生物质转化利用技术的原理和特点,分析了生物质转化利用技术的研究现状以及存在的问题,展望了生物质利用的发展前景     

生物质直接燃烧发电技术的探索

介绍了生物质直接燃烧发电技术原理及其设备的工作过程,着重讨论了生物质锅炉燃烧过程中的燃料收集和存储、送料堵塞以及受热面结焦等问题,并提出了优化运行和提高锅炉效率的改进措施。     

Decreased PCDD/F formation when co-firing a waste fuel and biomass in a CFB boiler by addition of sulphates or municipal sewage sludge

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are formed during waste incineration and in waste-to-energy boilers. Incomplete combustion, too short residence times at low combustion temperatures (<700 °C), incineration of electronic waste and plastic waste containing chlorine are all factors influencing the formation of PCDD/Fs in boilers. The impact of chlorine and catalysing metals (such as copper and iron) in the fuel on PCDD/F formation was studied in a 12 MW_th circulating fluidised bed (CFB) boiler. The PCDD/F concentrations in the raw gas after the convection pass of the boiler and in the fly ashes were compared. The fuel types were a so-called clean biomass with low content of chlorine, biomass with enhanced content of chlorine from supply of PVC, and solid recovered fuel (SRF) which is a waste fuel containing higher concentrations of both chlorine, and catalysing metals. The PCDD/F formation increased for the biomass with enhanced chlorine content and it was significantly reduced in the raw gas as well as in the fly ashes by injection of ammonium sulphate. A link, the alkali chloride track, is demonstrated between the level of alkali chlorides in the gas phase, the chlorine content in the deposits in the convection pass and finally the PCDD/F formation. The formation of PCDD/Fs was also significantly reduced during co-combustion of SRF with municipal sewage sludge (MSS) compared to when SRF was fired without MSS as additional fuel.     

Recycle of plastic residues in cellular phones through catalytic hydrocracking to liquid fuels

Plastics from cellular phones, an important contribution to electronic waste, have been studied for catalytic recycling to liquid fuels through hydrocracking. High impact polystyrene and polybutadiene, a component of high impact polystyrene and acrylonitrile–butadiene–styrene terpolymer, majority components in these residues according to literature, have been also studied in the process, using a bifunctional Pt/Hβ catalyst and under kinetic control. The results show a high yield to liquid fuels in the gasoline range with high impact polystyrene and polybutadiene, with a high content of naphthenics and isoparaffins in the catalytic process. Plastics from cellular phones, with a complex composition, require a previous removal of silicone, to prevent to formation of solids. Once silicone is removed, these residues, with a majority yield to liquids, could be treated together with other plastic wastes in catalytic hydrocracking.     

Recovery of biomass cellulose from waste sewage sludge

In our previous work, the primary sludge from wastewater treatment plants was shown to contain a considerable amount of cellulose (about 20%, based on suspended solids) owing to the discharge of toilet paper. For the purpose of using the cellulose as a biomass resource, this study examined a simple method for its recovery. When fibrous cellulose was suspended in 0.3% sulfuric acid and autoclaved at 130°C for 60 min, 85%–88% of the initial solids remained without dissolving. Under these conditions, an activated sludge sample not containing cellulose was strongly hydrolyzed and only 7% of the initial solids remained. The prescribed amounts of cellulose added to the activated sludge sample were quantitatively recovered by the autoclaving treatment. In the treatment of primary sludge containing >20% cellulose, residual solids with relatively high levels of cellulose (>69%) could be obtained. The results indicate that the method proposed here could recover cellulose practically from waste sewage sludge for biomass utilization. Received: July 17, 2000 / Accepted: July 4, 2001