Determination of the Thermal Efficiency of Pre-boilover Burning of a Slick of Oil on Water

The burning rate of a slick of oil on a water bed is calculated by a simple expression derived from a one-dimensional heat conduction equation. Heat feedback from the flame to the surface is assumed to be a constant fraction of the total energy released by the combustion reaction. The constant fraction (χ) is named the burning efficiency and represents an important tool in assessing the potential of in situ burning as a counter-measure to an oil-spill. The total heat release, as a function of the pool diameter, is obtained from an existing correlation. It is assumed that radiative heat is absorbed close to the fuel surface, that conduction is the dominant mode of heat transfer in the liquid phase and that the fuel boiling temperature remains constant. By matching the characteristic thermal penetration length scale for the fuel/water system and an equivalent single layer system, a combined thermal diffusivity can be calculated and used to obtain an analytical solution for the burning rate. Theoretical expressions were correlated with crude oil and heating oil, for a number of pool diameters and initial fuel layer thickness. Experiments were also conducted with emulsified and weathered crude oil. The simple analytical expression describes well the effects of pool diameter and initial fuel layer thickness permitting a better observation of the effects of weathering, emulsification and net heat feedback to the fuel surface. Experiments showed that only a small fraction of the heat released by the flame is retained by the fuel layer and water bed (of the order of 1%). The effect of weathering on the burning rate decreases with the weathering period and that emulsification results in a linear decrease of the burning rate with water content.     

Determination of the Burning Characteristics of a Slick of Oil on Water

The burning rate of a slick of oil on a water bed is characterized by three distinct processes, ignition, flame spread and burning rate. Although all three processes are important, ignition and burning rate are critical. The former, because it defines the potential to burn and the latter because of the inherent possibility of boilover. Burning rate is calculated by a simple expression derived from a one-dimensional heat conduction equation. Heat feedback from the flame to the surface is assumed to be a constant fraction of the total energy released by the combustion reaction. The constant fraction (χ) is named the burning efficiency and represents an important tool in assessing the potential of in situ burning as a counter-measure to an oil spill. By matching the characteristic thermal penetration length scale for the fuel/water system and an equivalent single layer system, a combined thermal diffusivity can be calculated and used to obtain an analytical solution for the burning rate. Theoretical expressions were correlated with crude oil and heating oil, for a number of pool diameters and initial fuel layer thickness. Experiments were also conducted with emulsified and weathered crude oil. The simple analytical expression describes well the effects of pool diameter and initial fuel layer thickness permitting a better observation of the effects of weathering, emulsification and net heat feedback to the fuel surface. Experiments showed that only a small fraction of the heat released by the flame is retained by the fuel layer and water bed (of the order of 1%). Ignition has been studied to provide a tool that will serve to assess a fuels ease to ignite under conditions that are representative of oil spills. Two different techniques are used, piloted ignition when the fuel is exposed to a radiant heat flux and flash point as measured by the ASTM D56 Tag Closed Cup Test. Two different crude oils were used for these experiments, ANS and Cook Inlet. Crude oils were tested in their natural state and at different levels of weathering, showing that piloted ignition and flash point are strong functions of weathering level.     

Assessment of plasma gasification of high caloric waste streams

Plasma gasification is an innovative technology for transforming high calorific waste streams into a valuable synthesis gas and a vitrified slag by means of a thermal plasma. A test program has been set up to evaluate the feasibility of plasma gasification and the impact of this process on the environment. RDF (refuse derived fuel) from carpet and textile waste was selected as feed material for semi-pilot gasification tests. The aim of the tests was: (1) to evaluate the technical feasibility of making a stable synthesis gas; (2) to characterize the composition of this synthesis gas; (3) to define a suitable after-treatment configuration for purification of the syngas and (4) to characterize the stability of the slag, i.e., its resistance to leaching for use as a secondary building material. The tests illustrate that plasma gasification can result in a suitable syngas quality and a slag, characterized by an acceptable leachability. Based on the test results, a further scale-up of this technology will be prepared and validation tests run.     

Characterisation of the physico-mechanical parameters of MSW

Following the basics of soil mechanics, the physico-mechanical behaviour of municipal solid waste (MSW) can be defined through constitutive relationships which are expressed with respect to three physical parameters: the dry density, the porosity and the gravimetric liquid content. In order to take into account the complexity of MSW (grain size distribution and heterogeneity larger than for conventional soils), a special oedometer was designed to carry out laboratory experiments. This apparatus allowed a coupled measurement of physical parameters for MSW settlement under stress. The studied material was a typical sample of fresh MSW from a French landfill. The relevant physical parameters were measured using a gas pycnometer. Moreover, the compressibility of MSW was studied with respect to the initial gravimetric liquid content. Proposed methods to assess the set of three physical parameters allow a relevant understanding of the physico-mechanical behaviour of MSW under compression, specifically, the evolution of the limit liquid content. The present method can be extended to any type of MSW.     

Micro-scale anaerobic digestion of point source components of organic fraction of municipal solid waste

The fermentation characteristics of six specific types of the organic fraction of municipal solid waste (OFMSW) were examined, with an emphasis on properties that are needed when designing plug-flow type anaerobic bioreactors. More specifically, the decomposition patterns of a vegetable (cabbage), fruits (banana and citrus peels), fresh leaf litter of bamboo and teak leaves, and paper (newsprint) waste streams as feedstocks were studied. Individual OFMSW components were placed into nylon mesh bags and subjected to various fermentation periods (solids retention time, SRT) within the inlet of a functioning plug-flow biogas fermentor. These were removed at periodic intervals, and their composition was analyzed to monitor decomposition rates and changes in chemical composition. Components like cabbage waste, banana peels, and orange peels fermented rapidly both in a plug-flow biogas reactor (PFBR) as well as under a biological methane potential (BMP) assay, while other OFMSW components (leaf litter from bamboo and teak leaves and newsprint) fermented slowly with poor process stability and moderate biodegradation. For fruit and vegetable wastes (FVW), a rapid and efficient removal of pectins is the main cause of rapid disintegration of these feedstocks, which left behind very little compost forming residues (2–5%). Teak and bamboo leaves and newsprint decomposed only to 25–50% in 30 d. These results confirm the potential for volatile fatty acids accumulation in a PFBR’s inlet and suggest a modification of the inlet zone or operation of a PFBR with the above feedstocks.     

Characteristics of liquid product from the pyrolysis of waste plastic mixture at low and high temperatures: influence of lapse time of reaction

Pyrolysis of a waste plastic mixture (high-density polyethylene: low-density polyethylene: polypropylene: polystyrene = 3:2:3:1) into a liquid product was carried out in a stirred semi-batch reactor at low (350 degrees C) and high (400 degrees C) temperatures. The effect of lapse time of reaction in the reactor and also degradation temperature on the characteristics of the liquid product from pyrolysis of the mixture was investigated. Liquid products were described by cumulative amount distribution, paraffin, olefin, naphthene and aromatic (PONA) distribution and molecular weight distribution. Their characteristic was quite differed with a lapse time of reaction and also at a low and high degradation temperatures, because of the different physicochemical properties of the plastic types in the mixture. With increase of lapse time of reaction, the order for the main products in PONA components obtained at 350 degrees C was firstly aromatic products and then olefin products, while at 400 degrees C the order was firstly aromatic products, then olefin products and finally paraffin products. The experiments also showed from the molecular weight distribution of liquid PONA components that the paraffin and olefin products had a wide distribution by mainly random scission of polymer, but in the case of olefin products were produced by an end-chain scission mechanism as well as random scission mechanism, as evidenced by much more light olefin products. This phenomenon was evident at a higher degradation temperature. Also, both the light olefin and naphthene products with a molecular weight of around 120, as a main product, showed a similar trend as a function of lapse time, which had a maximum fraction at 343 min (at 350 degrees C) and 83 min (at 400 degrees C). Among PONA components, the highest concentrations of aromatic products were obtained with a molecular weight of around 100 at the fastest lapse time of reaction, regardless of degradation temperature. It was concluded that the characteristics of liquid product on the pyrolysis of plastic mixtures were strongly influenced by lapse time of reaction and degradation temperature.     

Analytical determination of the suitability of different processes for the treatment of odorous waste gas

In order to determine the efficiency of different treatment systems for the reduction of odorous emissions, a gas chromatographic method followed by simultaneous mass spectrometry and olfactometry (GC-MS/O) was developed. Samples from a coffee bean roasting and a fat and oil processing plant were analyzed, respectively. The results were compared with the data obtained by olfactometric measurements. At a coffee bean roasting plant, cooling gases were analyzed prior to and after treatment in a full scale bioscrubber. The GC-MS/O analysis showed that the amounts of aldehydes and ketones decreased after treatment of cooling gases of coffee bean roasting in the bioscrubber, whereas the contents of the heterocyclic compounds, like pyridine and the pyrazines, and acetophenone and guaiacol remained almost unchanged. The amounts of dimethyl disulfide, 3-hydroxy-2-butanone, and the carboxylic acids increased after bioscrubber treatment. Furthermore, the performance of each stage of a combined experimental plant for the treatment of exhaust air of fat and oil processing was investigated. This treatment plant consisted of a bioscrubber, a biofilter, and an activated carbon adsorber. The important odor-active compounds of the exhaust air of fat and oil processing were the typical fat oxidation products (aldehydes, ketones) and with lower importance 2-pentylfuran, a few terpenes and aromates. Again, the key odor-active compounds, aldehydes and ketones, were degraded in the bioscrubber. Further degradation of aliphatic, unsaturated, methylated, and cyclic alkanes, as well as aromates, terpenes, and furans by the biofilter was observed. After the last treatment stage, the activated carbon filter, only small amounts of aliphatic, unsaturated, methylated, and cyclic alkanes and aromates remained in the waste gas. For both applications, the results of the developed GC-MS/O method correlated very well with olfactometric measurements.     

Use of cement dust in the manufacture of vitrified sewer pipes

Waste by-pass cement dust was added in different percentages ranging from 2% to 10% to a standard mix for sewer pipes manufacture, as a substitute for expensive feldspar. It was found that a mix consisting of 45% kaolin, 36% ball clay, 9% grog and 10% by-pass dust and fired at a temperature of 1300 degrees C for 4 h yielded samples that meet the standards. It was possible to reach a water absorption of 4%, a modulus of rupture of 7.8 MPa and a resistance to acids and alkalis conforming with standard values. A test pipe was fabricated by vacuum extrusion using the suggested composition and was found to withstand a hydraulic pressure of 14 MPa for one minute without the appearance of any cracks.     

Rheological study of biodegradable blends of starch and polyvinyl alcohol

The rheological behavior of biodegradable blends of starch and poly(vinyl alcohol) (PVOH) was measured as a function of temperature, shear rate, and moisture content using a capillary rheometer. An excellent correlation was found with a rheological model which was used as a means to characterize the influence of starch/PVOH content as well as a qualification of the viscosity for simulation studies. This model consisted of a power law dependence on shear rate, an Arrhenius dependence on temperature, and an exponential dependence on moisture.Paper presented at the Biodegradable Materials and Packaging Conference, September 22–23, 1993, Natick, Massachusetts.Guest Editor: Dr. Randall Shogren, USDA.     

Anoxic-aerobic treatment of the liquid fraction of cattle manure

Cattle manure from a dairy farm was treated in order to reduce its pollution potential. The manure came from a farm with 120 cows kept in stables in a free stall barn. As pretreatment, the manure is usually filtered on the farm using a screw press separator with a 0.5 mm mesh. Approximately 70% of the total filtered volume passes through the screen, thus constituting the liquid fraction. This fraction, with a composition of around 64,500 mg COD/l, 5770 mg total-N/l and 800 mg total-P/l, was subjected to centrifugation followed by a two-step biological treatment (anoxic-aerobic) to reduce organic matter (COD), nitrogen and phosphorus compounds. Centrifugation led to the following removal efficiencies: 35% total solids, 60% COD, 75% total phosphorus and 20% total nitrogen (mainly organic nitrogen). With the subsequent anoxic-aerobic treatment, average removal efficiencies of 85% for COD, 90% for total phosphorus and 75% for total nitrogen were achieved.     

Modeling of water quality downgradient of a mulch biowall

Groundwater treatment biowalls may be located close to a surface water body to prevent contaminant discharge from a groundwater plume into the surface water. Groundwater contaminants passing through the biowall are treated within the biowall or immediately downgradient of the biowall. Biowalls designed and constructed for the treatment of chlorinated solvents typically contain either a solid and/or liquid source of organic carbon to promote contaminant degradation by enhanced anaerobic reductive dechlorination. Common solid organic materials in biowalls include wood mulch or similar waste plant material, and common liquid organic materials are vegetable oil (possibly emulsified) or other long‐chain fatty acids. Such biowalls then develop anaerobic conditions in the constructed biowall volume, and potentially downgradient, as dissolved oxygen originally present in the aquifer is consumed. This groundwater condition can lead to the appearance of sulfide if groundwater influent to the biowall contains moderate to high sulfate concentrations. Other researchers have presented evidence for groundwater conditions downgradient of a biowall or a permeable reactive barrier (PRB) that are altered in relation to groundwater quality, besides the desired effect of contaminant degradation or removal by precipitation. The objective of this work was to investigate with modeling the changes in downgradient groundwater species chemistry as a result of a constructed biowall. This was accomplished with a chemical species model to predict levels of sulfate and sulfide present in groundwater in close downgradient proximity to the biowall. The results indicate that downgradient chemical changes could impact a surface water body to which groundwater discharges. The model described could be enhanced by incorporating additional design variables that should be considered in biowall feasibility assessments.     

Proposal for the integration of decentralised composting of the organic fraction of municipal solid waste into the waste management system of Cuba

Municipal solid waste (MSW) generation and management in Cuba was studied with a view to integrating composting of the organic fractions of MSW into the system. Composting is already included as part of the environmental strategy of the country as an appropriate waste management solution. However, no programme for area-wide implementation yet exists. The evaluation of studies carried out by some Cuban and international organisations showed that organic matter comprises approximately 60-70% of the MSW, with households being the main source. If all organic waste fractions were considered, the theoretical amount of organic waste produced would be approximately 1 Mio. Mg/a, leading to the production of approximately 0.5 Mio. Mg/a of compost. Composting could, therefore, be a suitable solution for treating the organic waste fractions of the MSW. Composting would best be carried out in decentralised systems, since transportation is a problem in Cuba. Furthermore, low technology and low budget composting options should be considered due to the problematic local economic situation. The location for such decentralised composting units would optimally be located at urban agricultural farms, which can be found all over Cuba. These farms are a unique model for sustainable farming in the world, and have a high demand for organic fertiliser. In this paper, options for the collection and impurity-separation in urban areas are discussed, and a stepwise introduction of source-separation, starting with hotel and restaurant waste, is suggested. For rural areas, the implementation of home composting is recommended.     

Kinetics of thermal de-chlorination of PVC under pyrolytic conditions

Although PVC-containing wastes are an important potential source of energy they are frequently disposed in landfill. In thermal treatment processes such as pyrolysis and gasification, the presence of poly(vinyl chloride) (PVC), a compound with 56.7% of chlorine, may cause problems concerned with environmental protection, as consequence of the formation of hydrochloric acid, chlorine gas and dioxins, as well as corrosion phenomena of the reactor/equipment materials. Thus, a possible solution may involve a previous removal of the chlorine from PVC containing waste through a pyrolysis process at low temperatures before the material being submitted to a subsequent thermal treatment, for energetic valorization. In this work, a kinetic model for the thermal decomposition of PVC has been developed, in view of its de-chlorination. DTA/TGA testing at different temperatures indicated a first order reaction and an activation energy of 133,800J/mol. An almost completed de-chlorination reaction was obtained at 340°C under an inert atmosphere. The resulted material is a C(n)H(n) type polymer with potential to be used in an energy recovery process. Validation test performed at laboratory scale indicate that the temperature of 340°C enables the removal of ～99.9% of the chlorine present in PVC. The chloride can be fixed in the form of an aqueous solution of HCl or calcium chloride, driving to an alternative full process with environmental benefits and reduction of the costs associated to the PCV - containing materials/wastes management.     

Model of technological alternatives of production of sodium chromate (VI) with the use of chromic wastes

This article presents a mathematical model which describes the sodium chromate (VI) production process with the use of chromic waste as a substitution of natural raw materials. This model is a function of selected process parameters common for all of the examined alternatives and based on equations of material balance. Optimization of the elaborated technological alternatives of the production process with use of recycling of chromic waste has been evaluated by determining the extreme value of the quality indicator WJ. This indicator defines the quantity of waste created in the process. Optimization results enabled the selection of the optimal technological solution from all of the alternatives possible for use in industrial practice. Negative values of the indicator prove that there is the possibility of introducing to the process a larger quantity of waste than the one obtained in the process and transported to the storage heaps.     

An overview of recovery of metals from slags

Various slags are produced as by-products in metallurgical processes or as residues in incineration processes. According to the origins and the characteristics, the main slags can be classified into three categories, namely ferrous slag, non-ferrous slag and incineration slag. This paper analysed and summarised the generation, characteristics and application of various slags, and discussed the potential effects of the slags on the environment. On this basis, a review of a number of methods for recovery of metals from the slags was made. It can be seen that a large amount of slags is produced each year. They usually contain a quantity of valuable metals except for blast furnace slag and they are actually a secondary resource of metals. By applying mineral processing technologies, such as crushing, grinding, magnetic separation, eddy current separation, flotation and so on, leaching or roasting, it is possible to recover metals such as Fe, Cr, Cu, Al, Pb, Zn, Co, Ni, Nb, Ta, Au, and Ag etc. from the slags. Recovery of metals from the slags and utilisation of the slags are important not only for saving metal resources, but also for protecting the environment.     

Assessment of the leaching of metallic elements in the technology of solidification in aqueous solution

Results are presented of experiments performed to optimize the solidification/stabilization system for metallic elements in aqueous solution. This system involves mixing cement and a solution of metallic elements in a conventional mixer: the paste thus obtained is transferred drop by drop into a recipient filled with an aqueous solution of NaOH at 20% by weight, in which it solidifies immediately. The separate use of chloride solutions of Li+, Cr3+, Pb2+ and Zn2+ makes it possible to obtain granules displaying various levels of compressive strength. Three different inertization matrices were used in the experiments, the first consisting solely of Portland cement, the second of Portland cement and a superplasticizer additive, and the third of Portland cement partially replaced with silica-fume and superplasticizer. The results of the tests performed showed a very low level of leaching into the alkaline solidification solution for Cr3+, the quantity leached being under 2% as against higher levels for the other metallic elements. For all the considered elements, the best results were obtained by using silica-fume in the inertization matrix.     

Pyrolysis of tyres. Influence of the final temperature of the process on emissions and the calorific value of the products recovered

A study was made of the pyrolysis of tyre particles, with the aim of determining the possibilities of using the products resulting from the process as fuel. Three final temperatures were used, determined from thermogravimetric data. The design of the experiment was a horizontal oven containing a reactor into which particles of the original tyre were placed. After the process, a solid fraction (char) remained in the reactor, while the gases generated went through a set of scrubbers where most of the condensable fraction (oils) was retained. Finally, once free of this fraction, the gases were collected in glass ampoules. Solid and liquids fractions were subjected to thermogravimetric analyses in order to study their combustibility. The gas fraction was analysed by means of gas chromatography to establish the content of CO, CO2, H2 and hydrocarbons present in the samples (mainly components of gases produced in the pyrolysis process). A special study was made of the sulphur and chlorine content of all the fractions, as the presence of these elements could be problematic if the products are used as fuel. Tyre pyrolysis engenders a solid carbon residue that concentrates sulphur and chorine, with a relatively high calorific value, although not so high as that of the original tyre. The liquid fraction produced by the process has a high calorific value, which rises with the final temperature, up to 40 MJ/kg. The chlorine content of this fraction is negligible. Over 95% of the gas fraction, regardless of the final temperature, is composed of hydrocarbons of a low molecular weight and hydrogen, this fraction also appearing to be free of chlorine.     

Bio-Treatment of Natural Fibers in Isolation of Cellulose Nanofibres: Impact of Pre-Refining of Fibers on Bio-Treatment Efficiency and Nanofiber Yield

Biodegradability, renewability and high specific strength properties of cellulose nanofibres and microfibrils have made them very attractive in nano-biocomposite science. Treatment of natural fibers with suitable enzymes or fungus has been found to substantially alleviate the high energy requirement associated with the isolation of cellulose nanofibers via high shear refining and subsequent cryocrushing. This article briefly describes a novel enzymatic fiber pretreatment developed to facilitate the isolation of cellulose nanofibres and explores the effect of pre-refining of fibers on the effectiveness of bio-treatment. Soft wood Kraft pulp was pre-sheared to different degree and treated with a genetically modified fungus isolated from fungus infected Dutch elm tree. Cellulose nanofibres were isolated from these treated fibers by high shear refining. The percentage yield of nanofibres from pre-refined fibers in the less than 50 nm range showed a substantial increase and at the same time the number of revolutions required during the high shear refining to attain a comparable level of nanofibres isolation decreased. This observation may be attributed to the better fiber internal accessibility of the enzymes due to loosening up of the fibers and increased number of fiber ends as a result of pre-refining.     

Investigation of hydrocyclones for the separation of shredded fridge plastics

The recycling of fridges produces a mixed plastic product of limited value. In order to maximise its value, the separation of the individual polymers that include high impact polystyrene (HIPS), acrylonitrile butadiene styrene (ABS), polyvinyl chloride (PVC) and polyethylene (PE) must take place. The effectiveness of a hydrocyclone system for the separation of these plastics, using both water and calcium chloride solutions, has been investigated. In addition a qualitative procedure for the determination of the HIPS content of a mixed ABS/HIPS product, by selective dissolution in R-limonene, has been developed. It was found that the effective density of separation depended on the particle size and aspect ratio. As the particle size and aspect ratio decreased, the separation became more efficient and the offset between separation density and hydrocyclone medium density decreased. This suggests that, for efficient density separation, closely sized, fine plastic fractions are required. Using these criteria, it was found that the removal of high density plastic such as PVC was readily achieved using a hydrocyclone. A partial separation of HIPS from ABS was found to be possible, taking advantage of a small density difference, using a hydrocyclone medium density of 1035kgm(-3).