Pyrolysis and combustion of municipal solid wastes:evaluation of synergistic effects using TGA-MS

A thermogravimetric methodology was developed to investigate and semi-quantify the extent of synergistic effects during pyrolysis and combustion of municipal solid waste (MSW). Results from TGA-MS were used to compare the pyrolysis and combustion characteristics of single municipal solid waste components (polyvinyl chloride (PVC), polypropylene (PP), polystyrene (PS), branches (BR), leaves (LV), grass (GR), packaging paper (PK), hygienic paper (HP) and cardboard (CB)) and a mixture (MX) of PP, BR and CB. Samples were heated under dynamic conditions at 20°C/min from 25°C to 1000°C with the continuous record of their main evolved fragments. Synergistic effects were evaluated by comparing experimental and calculated weight losses and relative areas of MS peaks. Pyrolysis of the mixture happened in two stages, with the release of H2, CH4, H2O, CO and CO2 between 200 and 415°C and the release of CH4, CxHy, CO and CO2 between 415 and 525°C. Negative synergistic effect in the 1st stage was attributed to the presence of PP where the release of hydrocarbons and CO2 from BR and CB was inhibited, whereas positive synergistic effects were observed during the 2nd degradation stage. In a second part of the study, synergistic effects were related to the dependency of the effective activation energy (Eα) versus the conversion (α). Higher Eαs were obtained for MX during its 1st stage of pyrolysis and lower Eαs for the 2nd stage when compared to the individual components. On the other hand, mostly positive synergistic effects were observed during the combustion of the same mixture, for which lower Eαs were recorded.

Design and implementation of graphical user interfaces for complex simulations

The development of increasingly powerful computers, which has enabled the use of windowing software, has also opened the way for the computer study, via simulation, of very complex physical systems. In this study, the main issues related to the implementation of interactive simulations of complex systems are identified and discussed. Most existing simulators are closed in the sense that there is no access to the source code and, even if it were available, adaptation to interaction with other systems would require extensive code re-writing. This work aims to increase the flexibility of such software by developing a set of object-oriented simulation classes, which can be extended, by subclassing, at any level, i.e., at the problem domain, presentation or interaction levels. A strategy, which involves the use of an object-oriented framework, concurrent execution of several simulation modules, use of a networked windowing system and the re-use of existing software written in procedural languages, is proposed. A prototype tool which combines these techniques has been implemented and is presented. It allows the on-line definition of the configuration of the physical system and generates the appropriate graphical user interface. Simulation routines have been developed for the chemical recovery cycle of a paper pulp mill. The application, by creation of new classes, of the prototype to the interactive simulation of this physical system is described. Besides providing visual feedback, the resulting graphical user interface greatly simplifies the interaction with this set of simulation modules. This study shows that considerable benefits can be obtained by application of computer science concepts to the engineering domain, by helping domain experts to tailor interactive tools to suit their needs.

Effect of aspect ratio on thermal convection in open and closed systems

Internally heated fluids are found across the nuclear fuel cycle. In certain situations the motion of the fluid is driven by the decay heat (i.e. corium melt pools in severe accidents, the shutdown of liquid metal reactors, molten salt and the passive control of light water reactors) as well as normal operation (i.e. intermediate waste storage and generation IV reactor designs). This can in the long-term affect reactor vessel integrity or lead to localized hot spots and accumulation of solid wastes that may prompt local increases in activity. Two approaches to the modeling of internally heated convection are presented here. These are based on numerical analysis using codes developed in-house and simulations using widely available computational fluid dynamics solvers. Open and closed fluid layers at around the transition between conduction and convection of various aspect ratios are considered. We determine optimum domain aspect ratio (1:7:7 up to 1:24:24 for open systems and 5:5:1, 1:10:10 and 1:20:20 for closed systems), mesh resolutions and turbulence models required to accurately and efficiently capture the convection structures that evolve when perturbing the conductive state of the fluid layer. Note that the open and closed fluid layers we study here are bounded by a conducting surface over an insulating surface. Conclusions will be drawn on the influence of the periodic boundary conditions on the flow patterns observed. We have also examined the stability of the nonlinear solutions that we found with the aim of identifying the bifurcation sequence of these solutions en route to turbulence.

Weak form equation–based finite-element modeling of viscoelastic asphalt mixtures

The objective of this study is to demonstrate using weak form partial differential equation (PDE) method for a finite-element (FE) modeling of a new constitutive relation without the need of user subroutine programming. The viscoelastic asphalt mixtures were modeled by the weak form PDE-based FE method as the examples in the paper. A solid-like generalized Maxwell model was used to represent the deforming mechanism of a viscoelastic material, the constitutive relations of which were derived and implemented in the weak form PDE module of Comsol Multiphysics, a commercial FE program. The weak form PDE modeling of viscoelasticity was verified by comparing Comsol and Abaqus simulations, which employed the same loading configurations and material property inputs in virtual laboratory test simulations. Both produced identical results in terms of axial and radial strain responses. The weak form PDE modeling of viscoelasticity was further validated by comparing the weak form PDE predictions with real laboratory test results of six types of asphalt mixtures with two air void contents and three aging periods. The viscoelastic material properties such as the coefficients of a Prony series model for the relaxation modulus were obtained by converting from the master curves of dynamic modulus and phase angle. Strain responses of compressive creep tests at three temperatures and cyclic load tests were predicted using the weak form PDE modeling and found to be comparable with the measurements of the real laboratory tests. It was demonstrated that the weak form PDE-based FE modeling can serve as an efficient method to implement new constitutive models and can free engineers from user subroutine programming.

Supercritical water gasification of RDF and its components over RuO2/γ-Al2O3 catalyst:new insights into RuO2 catalytic reaction mechanisms

Five samples including a composite refuse derived fuel (RDF) and four combustible components of municipal solid wastes (MSW) have been reacted under supercritical water conditions in a batch reactor. The reactions have been carried out at 450 °C for 60 min reaction time, with or without 20 wt% RuO2/gamma-alumina catalyst. The reactivities of the samples depended on their compositions; with the plastic-rich samples, RDF and mixed waste plastics (MWP), giving similar product yields and compositions, while the biogenic samples including mixed waste wood (MWW) and textile waste (TXT) also gave similar reaction products. The use of the heterogeneous ruthenium-based catalyst gave carbon gasification efficiencies (CGE) of up to 99 wt%, which was up by at least 83% compared to the non-catalytic tests. In the presence of RuO2 catalyst, methane, hydrogen and carbon dioxide became the dominant gas products for all five samples. The higher heating values (HHV) of the gas products increased at least two-fold in the presence of the catalyst compared to non-catalytic tests. Results show that the ruthenium-based catalyst was active in feedstock steam reforming, methanation and possible direct hydrogenolysis of C-C bonds. This work provides new insights into the catalytic mechanisms of RuO2 during SCWG of carbonaceous materials, along with the possibility of producing high yields of methane from MSW fractions.

Sustainable energy from paper industry wastes

Secondary fibre paper mills are significant users of both heat and electricity which is mainly derived from the combustion of fossil fuels. The cost of producing this energy is increasing year upon year. These mills are also significant producers of fibrous sludge and reject waste material which can contain high amounts of useful energy. Currently the majority of these waste fractions are disposed of by landfill, land-spread or incineration using natural gas. These disposal methods not only present environmental problems but are also very costly. The focus of this work was to utilise the waste fractions produced at secondary fibre paper mills for the on-site production of combined heat and power (CHP) using advanced thermal conversion methods (gasification and pyrolysis), well suited to relatively small scales of throughput. The heat and power can either be used on-site or exported. The first stage of the work was the development of methods to condition selected paper industry wastes to enable thermal conversion. This stage required detailed characterisation of the waste streams in terms of proximate and ultimate analysis and heat content. Suitable methods to dry and condition the wastes in preparation for thermal conversion were also explored. Through trials at pilot scale with both fixed bed downdraft gasification and intermediate pyrolysis systems, the energy recovered from selected wastes and waste blends in the form of product gas and pyrolysis products was quantified. The optimal process routes were selected based on the experimental results, and implementation studies were carried out at the selected candidate mills. The studies consider the pre-processing of the wastes, thermal conversion, and full integration of the energy products. The final stage of work was an economic analysis to quantify economic gain, return on investment and environmental benefits from the proposed processes.

Fixed bed downdraft gasification of paper industry wastes

The two main wastes generated from secondary fibre paper mills are rejects (composed mainly of plastics and fibres) and de-inking sludge, both of which are evolved from the pulping process during paper manufacture. The current practice for the disposal of these wastes is either by land-spreading or land-filling. This work explores the gasification of blends of pre-conditioned rejects and de-inking sludge pellets with mixed wood chips in an Imbert type fixed bed downdraft gasifier with a maximum feeding capacity of 10kg/h. The producer gases evolved would generate combined heat and power (CHP) in an internal combustion engine. The results show that as much as 80wt.% of a brown paper mill's rejects (consisting of 20wt.% mixed plastics and 80wt.% paper fibres) could be successfully gasified in a blend with 20wt.% mixed wood chips. The producer gas composition was 16.24% H, 23.34% CO, 12.71% CO 5.21% CH and 42.49% N (v/v%) with a higher heating value of 7.3MJ/Nm. After the removal of tar and water condensate the producer gas was of sufficient calorific value and flow rate to power a 10kWe gas engine. Some blends using rejects from other mill types were not successful, and the limiting factor was usually the agglomeration of plastics present within the fuel.

Green preparation of tuneable carbon-silica composite materials from wastes

Bio-oil has successfully been utilized to prepare carbon-silica composites (CSCs) from mesoporous silicas, such as SBA-15, MCM-41, KIT-6 and MMSBA frameworks. These CSCs comprise a thin film of carbon dispersed over the silica matrix and exhibit porosity similar to the parent silica. The surface properties of the resulting materials can be simply tuned by the variation of preparation temperatures leading to a continuum of functionalities ranging from polar hydroxyl rich surfaces to carbonaceous aromatic surfaces, as reflected in solid state NMR, XPS and DRIFT analysis. N2 porosimetry, TEM and SEM images demonstrate that the composites still possess similar ordered mesostructures to the parent silica sample. The modification mechanism is also proposed: silica samples are impregnated with bio-oils (generated from the pyrolysis of waste paper) until the pores are filled, followed by the carbonization at a series of temperatures. Increasing temperature leads to the formation of a carbonaceous layer over the silica surface. The complex mixture of compounds within the bio-oil (including those molecules containing alcohols, aliphatics, carbonyls and aromatics) gives rise to the functionality of the CSCs.

An analysis of the effectiveness of a behavioural based safety intervention in a UK paper mill

This research examines a behavioural based safety (BBS) intervention within a paper mill in the South East of England. Further to this intervention two other mills are examined for the purposes of comparison — one an established BBS programme and the other an improving safety management system through management ownership. BBS programmes have become popular within the UK, but most of the research about their efficacy is carried out by the BBS providers themselves. This thesis aims to evaluate a BBS intervention from a standpoint which is not commercially biased in favour of BBS schemes. The aim of a BBS scheme is to either change personnel behaviours or attitudes, which in turn will positively affect the organisation's safety culture. The research framework involved a qualitative methodology in order to examine the effects of the intervention on the paper mill's safety culture. The techniques used were questionnaires and semi structured interviews, in addition to observation and discussions which were possible because of the author's position as participant observer. The results demonstrated a failure to improve any aspect of the mill's safety culture, which worsened following the BBS intervention. Issues such as trust, morale, communication and support of management showed significant signs of negative workforce response. The paper mill where the safety management system approach was utilised demonstrated a significantly improved safety culture and achieved site ownership from middle managers and supervisors. Research has demonstrated that a solid foundation is required prior to successfully implementing a BBS programme. For a programme to work there must be middle management support in addition to senior management commitment. If a trade union actively distances itself from BBS, it is also unlikely to be effective. This thesis proposes that BBS observation programmes are not suitable for the papermaking industry, particularly when staffing levels are low due to challenging economic conditions. Observers are not available when there are high hazard situations and this suggests that BBS implementation is not the correct intervention for the paper industry.

The ecology of paper mill by-product and its evaluation as a casing medium in the culture of Agaricus bisporus (Lange) Pilat

Effluent from pulp and paper production at the Kemsley mill of Bowaters U.K. Paper Company Limited passes through two treatment stages before its discharge into the Swale estuary. Suspended material removed during treatment is deposited on wasteground as a thin sludge. The solids it contains are mainly wood components lost during pulp production, whilst it also has a high salt content, derived from chemicals used in pulping processes. After deposition the sludge undergoes an ageing process during which it dries out and its salt content is reduced. This ageing can be reproduced and accelerated by improved drainage under controlled conditions. The paper mill sludge was investigated as a casing medium in the culture of Agaricus bisporus (Lange) Pilat, the cultivated mushroom. It was unsuitable up to one year from deposition due largely to the inhibitory effect of its salt content on fruiting. Material eighteen months or more in age gave yields comparable to standard peat casing. Before use as a casing the material must be shredded to a satisfactory structure, neutralised with chalk, and pasteurised to eliminate organisms harmful to the crop. The prepared medium has a high water holding capacity and a structure resilient to management procedures, important requirements of a good casing. A passive movement of salts from the compost to the casing was shown to occur during culture, capable of enhancing the natural decline in cropping if sufficiently great. The ions chloride, potassium, sodium and sulphate were shown to be responsible, their damaging effects being due to high conductivity created in the casing. Studies of elements available during culture suggested phosphate availability in the compost could limit crop potential, whilst iron released by mycelium of A.bisporus in the casing may be utilised by associated micro-organisms.

Computer interpretation of engineering drawings as solid models

Much of the geometrical data relating to engineering components and assemblies is stored in the form of orthographic views, either on paper or computer files. For various engineering applications, however, it is necessary to describe objects in formal geometric modelling terms. The work reported in this thesis is concerned with the development and implementation of concepts and algorithms for the automatic interpretation of orthographic views as solid models. The various rules and conventions associated with engineering drawings are reviewed and several geometric modelling representations are briefly examined. A review of existing techniques for the automatic, and semi-automatic, interpretation of engineering drawings as solid models is given. A new theoretical approach is then presented and discussed. The author shows how the implementation of such an approach for uniform thickness objects may be extended to more general objects by introducing the concept of `approximation models'. Means by which the quality of the transformations is monitored, are also described. Detailed descriptions of the interpretation algorithms and the software package that were developed for this project are given. The process is then illustrated by a number of practical examples. Finally, the thesis concludes that, using the techniques developed, a substantial percentage of drawings of engineering components could be converted into geometric models with a specific degree of accuracy. This degree is indicative of the suitability of the model for a particular application. Further work on important details is required before a commercially acceptable package is produced.

The development of a solid waste management strategy

This research is concerned with the application of operational research techniques in the development of a long- term waste management policy by an English waste disposal authority. The main aspects which have been considered are the estimation of future waste production and the assessment of the effects of proposed systems. Only household and commercial wastes have been dealt with in detail, though suggestions are made for the extension of the effect assessment to cover industrial and other wastes. Similarly, the only effects considered in detail have been costs, but possible extensions are discussed. An important feature of the study is that it was conducted in close collaboration with a waste disposal authority, and so pays more attention to the actual needs of the authority than is usual in such research. A critical examination of previous waste forecasting work leads to the use of simple trend extrapolation methods, with some consideration of seasonal effects. The possibility of relating waste production to other social and economic indicators is discussed. It is concluded that, at present, large uncertainties in predictions are inevitable; waste management systems must therefore be designed to cope with this uncertainty. Linear programming is used to assess the overall costs of proposals. Two alternative linear programming formulations of this problem are used and discussed. The first is a straightforward approach, which has been .implemented as an interactive computer program. The second is more sophisticated and represents the behaviour of incineration plants more realistically. Careful attention is paid to the choice of appropriate data and the interpretation of the results. Recommendations are made on methods for immediate use, on the choice of data to be collected for future plans, and on the most useful lines for further research and development.

A legal perspective of integrated surface mining, solid waste landfill reclamation and land conservation

In the area of international environmental law this thesis proposes the formulation of one-step planning and permitting regulation for the integrated utilisation of new surface mines as depositories for municipal solid waste. Additionally, the utilisation of abandoned and currently operated surface mines is proposed as solid waste landfills as an integral step in their reclamation. Existing laws, litigation and issues in the United Kingdom, the U.S. and Canada are discussed because of their common legal system, language and heritage. The critical shortage of approved space for disposal of solid waste has caused an urgent and growing problem for both the waste disposal industry and society. Surface mining can serve three important environmental and societal functions inuring to the health and welfare of the public: (1) providing basic minerals for goods and construction; (20 sequentially, to provide critically needed, safe burial sites for society's wastes, and (3) to conserve land by dual purpose use and to restore derelict land to beneficial surface use. Currently, the first two functions are treated environmentally, and in regulation, as two different siting problems, yet they both are earth-disturbing and excavating industries requiring surface restoration. The processes are largely duplicative and should be combined for better efficiency, less earth disturbance, conservation of land, and for fuller and better reclamation of completed surface mines returning the surfaces to greater utility than present mined land reclamation procedures. While both industries are viewed by a developed society and its communities as "bad neighbours", they remain essential and critical for mankind's existence and welfare. The study offers successful examples of the integrated process in each country. The study argues that most non-fuel surface mine openings, if not already safe, can economically, through present containment technology, be made environmentally safe for use as solid waste landfills. Simultaneously, the procedure safeguards and monitors protection of ground and surface waters from landfill contamination.

Evaluation of options for energy recovery from municipal solid waste in India using the hierarchical analytical network process

In this paper a Hierarchical Analytical Network Process (HANP) model is demonstrated for evaluating alternative technologies for generating electricity from MSW in India. The technological alternatives and evaluation criteria for the HANP study are characterised by reviewing the literature and consulting experts in the field of waste management. Technologies reviewed in the context of India include landfill, anaerobic digestion, incineration, pelletisation and gasification. To investigate the sensitivity of the result, we examine variations in expert opinions and carry out an Analytical Hierarchy Process (AHP) analysis for comparison. We find that anaerobic digestion is the preferred technology for generating electricity from MSW in India. Gasification is indicated as the preferred technology in an AHP model due to the exclusion of criteria dependencies and in an HANP analysis when placing a high priority on net output and retention time. We conclude that HANP successfully provides a structured framework for recommending which technologies to pursue in India, and the adoption of such tools is critical at a time when key investments in infrastructure are being made. Therefore the presented methodology is thought to have a wider potential for investors, policy makers, researchers and plant developers in India and elsewhere. © 2013 Elsevier Ltd. All rights reserved.

New solid bases for biodiesel synthesis

Biodiesel is a promising non-toxic and biodegradable renewable fuel, synthesized by the homogeneous base-catalyzed transesterification of vegetable oils or animal fats with methanol or ethanol. Removal of the base, typically Na or K alkoxide, after reaction is a major problem since aqueous quenching results in stable emulsions and saponification. The use of a solid base catalyst offers several process advantages including the elimination of a quenching step (and associated basic water waste) to isolate the products, and the opportunity to operate in a continuous process. The synthesis and characterization of a series of Li-doped CaO and Mg-Al hydrotalcite solid base catalysts were presented and their physicochemical properties were correlated with their activity in biodiesel synthesis. Both catalysts were effective solid bases for the transesterification of triglycerides to the methyl ester, with catalyst activity related to the electronic properties of Li and Mg dopants. This is an abstract of a paper presented at the 230th ACS National Meeting (Washington, DC 8/28/2005-9/1/2005).