Measurement of key compositional parameters in two species of energy grass by Fourier transform infrared spectroscopy

Two energy grass species, switch grass, a North American tuft grass, and reed canary grass, a European native, are likely to be important sources of biomass in Western Europe for the production of biorenewable energy. Matching chemical composition to conversion efficiency is a primary goal for improvement programmes and for determining the quality of biomass feed-stocks prior to use and there is a need for methods which allow cost effective characterisation of chemical composition at high rates of sample through-put. In this paper we demonstrate that nitrogen content and alkali index, parameters greatly influencing thermal conversion efficiency, can be accurately predicted in dried samples of these species grown under a range of agronomic conditions by partial least square regression of Fourier transform infrared spectra (R2 values for plots of predicted vs. measured values of 0.938 and 0.937, respectively). We also discuss the prediction of carbon and ash content in these samples and the application of infrared based predictive methods for the breeding improvement of energy grasses.

Intermediate pyrolysis:a sustainable biomass-to-energy concept-biothermal valorisation of biomass (BtVB) process

Wastewater treatment coupled with energy crop cultivation provides an attractive source of cheap feedstock. This study reviews an advanced, closed-loop bioenergy conversion process [biothermal valorisation of biomass (BtVB)], in which pyroformer is coupled to a gasifier. BtVB process was developed at European Bioenergy Research Institute (EBRI), Aston University, UK and demonstrates an improved method for thermal conversion of ash-rich biomass.

Studies on the thermal decomposition behaviour, kinetics and electrical conductivity of the non-isothermal decomposition of pyridine mono carboxylic acids and some of their transition metal complexes

The thesis is divided into four chapters. They are: introduction, experimental, results and discussion about the free ligands and results and discussion about the complexes. The First Chapter, the introductory chapter, is a general introduction to the study of solid state reactions. The Second Chapter is devoted to the materials and experimental methods that have been used for carrying out tile experiments. TIle Third Chapter is concerned with the characterisations of free ligands (Picolinic acid, nicotinic acid, and isonicotinic acid) by using elemental analysis, IR spectra, X-ray diffraction, and mass spectra. Additionally, the thermal behaviour of free ligands in air has been studied by means of thermogravimetry (TG), derivative thermogravimetry (DTG), and differential scanning calorimetry (DSC) measurements. The behaviour of thermal decomposition of the three free ligands was not identical Finally, a computer program has been used for kinetic evaluation of non-isothermal differential scanning calorimetry data according to a composite and single heating rate methods in comparison with the methods due to Ozawa and Kissinger methods. The most probable reaction mechanism for the free ligands was the Avrami-Erofeev equation (A) that described the solid-state nucleation-growth mechanism. The activation parameters of the decomposition reaction for free ligands were calculated and the results of different methods of data analysis were compared and discussed. The Fourth Chapter, the final chapter, deals with the preparation of cobalt, nickel, and copper with mono-pyridine carboxylic acids in aqueous solution. The prepared complexes have been characterised by analyses, IR spectra, X-ray diffraction, magnetic moments, and electronic spectra. The stoichiometry of these compounds was ML2x(H20), (where M = metal ion, L = organic ligand and x = water molecule). The environments of cobalt, nickel, and copper nicotinates and the environments of cobalt and nickel picolinates were octahedral, whereas the environment of copper picolinate [Cu(PA)2] was tetragonal. However, the environments of cobalt, nickel, and copper isonicotinates were polymeric octahedral structures. The morphological changes that occurred throughout the decomposition were followed by SEM observation. TG, DTG, and DSC measurements have studied the thermal behaviour of the prepared complexes in air. During the degradation processes of the hydrated complexes, the crystallisation water molecules were lost in one or two steps. This was also followed by loss of organic ligands and the metal oxides remained. Comparison between the DTG temperatures of the first and second steps of the dehydration suggested that the water of crystallisation was more strongly bonded with anion in Ni(II) complexes than in the complexes of Co(II) and Cu(II). The intermediate products of decomposition were not identified. The most probable reaction mechanism for the prepared complexes was also Avrami-Erofeev equation (A) characteristic of solid-state nucleation-growth mechanism. The tempemture dependence of conductivity using direct current was determined for cobalt, nickel, Cl.nd copper isonicotinates. An activation energy (ΔΕ), the activation energy (ΔΕ ) were calculated.The ternperature and frequency dependence of conductivity, the frequency dependence of dielectric constant, and the dielectric loss for nickel isonicotinate were determined by using altemating current. The value of s paralneter and the value of'density of state [N(Ef)] were calculated. Keyword Thermal decomposition, kinetic, electrical conduclion, pyridine rnono~ carboxylic acid, cOlnplex, transition metal compJex.

An evaluation of thermal plasmas in pyrometallurgy

The development of reliable, high powered plasma generators has resulted in many plasma processes being proposed as alternatives to existing pyrometallurgical technologies. This work evaluates the advantages and disadvantages of plasma systems by reviewing plasma generators, their integration with reactors and the process economics. Many plasma systems were shown to be technically and economically superior to existing technologies, but some of the plasma system advantages quoted in the literature were found to be impractical because of other system constraints. Process applications were limited by the power inputs available from plasma generators compared to AC electric furnaces. A series of trials were conducted where chromite and steelplant baghouse dusts were smelted in the Tetronics' 2.0 MW transferred arc/open bath reactor to confirm the operating characteristics of the plasma system and its economics. Chromite smelting was technical superior to submerged arc furnace technology, but the economics were unfavourable because of the limited power available from the water-cooled plasma torch and the high electrical energy consumption. A DC graphite electrode plasma furnace using preheated and prereduced chromite concentrates will compete economically with the submerged arc furnace. Ni, Cr and Mo were economically recovered from high alloy content steelplant dusts for recycling. Five Electric Arc Furnace dusts were smelted to produce a non-toxic residue and recover the contained zinc to an enriched zinc oxide product for recycling. It should be possible to condense the zinc vapour directly in a zinc splash condenser to increase the value of the product. Because of the limited power available from plasma generators, plasma processes will be most suitable for treating high and medium value materials such as Au, Pt, Mo, Ni, Ti, V, Cr etc at small production rates, heating metals in tundishes and ladles and remelting superalloy scrap. The treatment of environmentally hazardous waste materials is a particularly interesting application because of the additional financial incentives. Non-transferred arc plasma generators will be used for air and gas preheating in blast furnaces to reduce metallurgical coke consumptions.

Drying processess in the United Kingdom:assessment of industrial energy utilisation and efficiency of drying systems and the modelling of drying characters using neural networks (BL)

Drying is an important unit operation in process industry. Results have suggested that the energy used for drying has increased from 12% in 1978 to 18% of the total energy used in 1990. A literature survey of previous studies regarding overall drying energy consumption has demonstrated that there is little continuity of methods and energy trends could not be established. In the ceramics, timber and paper industrial sectors specific energy consumption and energy trends have been investigated by auditing drying equipment. Ceramic products examined have included tableware, tiles, sanitaryware, electrical ceramics, plasterboard, refractories, bricks and abrasives. Data from industry has shown that drying energy has not varied significantly in the ceramics sector over the last decade, representing about 31% of the total energy consumed. Information from the timber industry has established that radical changes have occurred over the last 20 years, both in terms of equipment and energy utilisation. The energy efficiency of hardwood drying has improved by 15% since the 1970s, although no significant savings have been realised for softwood. A survey estimating the energy efficiency and operating characteristics of 192 paper dryer sections has been conducted. Drying energy was found to increase to nearly 60% of the total energy used in the early 1980s, but has fallen over the last decade, representing 23% of the total in 1993. These results have demonstrated that effective energy saving measures, such as improved pressing and heat recovery, have been successfully implemented since the 1970s. Artificial neural networks have successfully been applied to model process characteristics of microwave and convective drying of paper coated gypsum cove. Parameters modelled have included product moisture loss, core gypsum temperature and quality factors relating to paper burning and bubbling defects. Evaluation of thermal and dielectric properties have highlighted gypsum's heat sensitive characteristics in convective and electromagnetic regimes. Modelling experimental data has shown that the networks were capable of simulating drying process characteristics to a high degree of accuracy. Product weight and temperature were predicted to within 0.5% and 5C of the target data respectively. Furthermore, it was demonstrated that the underlying properties of the data could be predicted through a high level of input noise.

Which is the best solar thermal collection technology for electricity generation in north-west India? Evaluation of options using the analytical hierarchy process

This study of concentrating solar thermal power generation sets out to evaluate the main existing collection technologies using the framework of the Analytical Hierarchy Process (AHP). It encompasses parabolic troughs, heliostat fields, linear Fresnel reflectors, parabolic dishes, compound parabolic concentrators and linear Fresnel lenses. These technologies are compared based on technical, economic and environmental criteria. Within these three categories, numerous sub-criteria are identified; similarly sub-alternatives are considered for each technology. A literature review, thermodynamic calculations and an expert workshop have been used to arrive at quantitative and qualitative assessments. The methodology is applied principally to a case study in Gujarat in north-west India, though case studies based on the Sahara Desert, Southern Spain and California are included for comparison. A sensitivity analysis is carried out for Gujarat. The study concludes that the linear Fresnel lens with a secondary compound parabolic collector, or the parabolic dish reflector, is the preferred technology for north-west India.

Design of a novel solar thermal collector using a multi-criteria decision-making methodology

Three novel solar thermal collector concepts derived from the Linear Fresnel Reflector (LFR) are developed and evaluated through a multi-criteria decision-making methodology, comprising the following techniques: Quality Function Deployment (QFD), the Analytical Hierarchy Process (AHP) and the Pugh selection matrix. Criteria are specified by technical and customer requirements gathered from Gujarat, India. The concepts are compared to a standard LFR for reference, and as a result, a novel 'Elevation Linear Fresnel Reflector' (ELFR) concept using elevating mirrors is selected. A detailed version of this concept is proposed and compared against two standard LFR configurations, one using constant and the other using variable horizontal mirror spacing. Annual performance is analysed for a typical meteorological year. Financial assessment is made through the construction of a prototype. The novel LFR has an annual optical efficiency of 49% and increases exergy by 13-23%. Operational hours above a target temperature of 300 C are increased by 9-24%. A 17% reduction in land usage is also achievable. However, the ELFR suffers from additional complexity and a 16-28% increase in capital cost. It is concluded that this novel design is particularly promising for industrial applications and locations with restricted land availability or high land costs. The decision analysis methodology adopted is considered to have a wider potential for applications in the fields of renewable energy and sustainable design. © 2013 Elsevier Ltd. All rights reserved.

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.

Solar thermal collectors for use in hybrid solar-biomass power plants in India

This thesis examined solar thermal collectors for use in alternative hybrid solar-biomass power plant applications in Gujarat, India. Following a preliminary review, the cost-effective selection and design of the solar thermal field were identified as critical factors underlying the success of hybrid plants. Consequently, the existing solar thermal technologies were reviewed and ranked for use in India by means of a multi-criteria decision-making method, the Analytical Hierarchy Process (AHP). Informed by the outcome of the AHP, the thesis went on to pursue the Linear Fresnel Reflector (LFR), the design of which was optimised with the help of ray-tracing. To further enhance collector performance, LFR concepts incorporating novel mirror spacing and drive mechanisms were evaluated. Subsequently, a new variant, termed the Elevation Linear Fresnel Reflector (ELFR) was designed, constructed and tested at Aston University, UK, therefore allowing theoretical models for the performance of a solar thermal field to be verified. Based on the resulting characteristics of the LFR, and data gathered for the other hybrid system components, models of hybrid LFR- and ELFR-biomass power plants were developed and analysed in TRNSYS®. The techno-economic and environmental consequences of varying the size of the solar field in relation to the total plant capacity were modelled for a series of case studies to evaluate different applications: tri-generation (electricity, ice and heat), electricity-only generation, and process heat. The case studies also encompassed varying site locations, capacities, operational conditions and financial situations. In the case of a hybrid tri-generation plant in Gujarat, it was recommended to use an LFR solar thermal field of 14,000 m2 aperture with a 3 tonne biomass boiler, generating 815 MWh per annum of electricity for nearby villages and 12,450 tonnes of ice per annum for local fisheries and food industries. However, at the expense of a 0.3 ¢/kWh increase in levelised energy costs, the ELFR increased saving of biomass (100 t/a) and land (9 ha/a). For solar thermal applications in areas with high land cost, the ELFR reduced levelised energy costs. It was determined that off-grid hybrid plants for tri-generation were the most feasible application in India. Whereas biomass-only plants were found to be more economically viable, it was concluded that hybrid systems will soon become cost competitive and can considerably improve current energy security and biomass supply chain issues in India.

Pyrolysis of contaminated energy crops and the characterisation of the gained biochar

The simultaneous use of willow as a vegetation filter and an energy crop can respond both to the increasing energy demand and to the problem of the soil and water contamination. Its characteristics guarantee that the resources are used economically. As a vegetation filter, willow uptakes organic and inorganic contaminants. As a fast growing energy crop it meets the requirements of rural areas without the exploitation of existing forestry. The aim of the research was to gather knowledge on the thermal behaviour of willow, uptaking contaminants and then used as an energy crop. For this reason pyrolysis experiments were performed in two different scales. In analytical scale metal-contaminated wood was investigated and bench scale pyrolysis experiments were performed with nitrogen-enriched willow, originated from a wastewater treatment plant. Results of the pyrolysis showed that 51-81 % of the wastewater derived nitrogen of willow was captured in the char product. Char had low surface area (1.4 to 5.4 m2/g), low bulk density (0.15–0.18 g/cm3), high pH values (7.8–9.4) and high water-holding capacity (1.8 to 4.3 cm3/g) while the bioavailability of char nutrients was low. Links were also established between the pyrolysis temperature and the product properties for maximising the biochar provided benefits for soil applications. Results also showed that the metal binding capacity of wood varied from one metal ion to another, char yield increased and levoglucosan yield decreased in their presence. While char yield was mainly affected by the concentration of the metal ions, levoglucosan yield was more dependent on the type of the ionic species. Combustion experiments were also carried out with metal-enriched char. The burnout temperatures, estimated ignition indices and the conversion indicate that the metal ions type and not the amount were the determining factors during the combustion. Results presented in the Thesis provide better understanding on the thermal behaviour of nitrogen-enriched and metal contaminated biomass which is crucial to design effective pyrolysis units and combustors. These findings are relevant for pyrolysis experiments, where the goal is to yield char for energetic or soil applications.

Hydrogen-terminated detonation nanodiamond:impedance spectroscopy and thermal stability studies

In this paper, we investigated the effect of hydrogen termination on the electrical properties and impedance spectra of detonation nanodiamond. The impedance spectra revealed that the hydrogen-termination process increases the electrical conductivity by four orders of magnitude at room temperature. An equivalent circuit has been proposed to correlate with the conduction mechanism. Arrhenius plot showed that there were two different activation energy levels located at 0.089 eV and 0.63 eV between 50 °C and 400 °C. The possible physical mechanism corresponding to these activation energy levels has been discussed. Hydrogen-terminated detonation nanodiamond has been further annealed at different temperatures prior to FTIR and XPS measurements in order to understand their thermal stability. The results demonstrated that the surface oxidization occurred between 100 °C and 150 °C. However, the C-H bonds could partially survive when the temperature reaches 400 °C in air. © 2013 American Institute of Physics.

Thermal processing of miscanthus, sugarcane bagasse, sugarcane trash and their acid hydrolysis residues

The research presented in this thesis was developed as part of DIBANET, an EC funded project aiming to develop an energetically self-sustainable process for the production of diesel miscible biofuels (i.e. ethyl levulinate) via acid hydrolysis of selected biomass feedstocks. Three thermal conversion technologies, pyrolysis, gasification and combustion, were evaluated in the present work with the aim of recovering the energy stored in the acid hydrolysis solid residue (AHR). Mainly consisting of lignin and humins, the AHR can contain up to 80% of the energy in the original feedstock. Pyrolysis of AHR proved unsatisfactory, so attention focussed on gasification and combustion with the aim of producing heat and/or power to supply the energy demanded by the ethyl levulinate production process. A thermal processing rig consisting on a Laminar Entrained Flow Reactor (LEFR) equipped with solid and liquid collection and online gas analysis systems was designed and built to explore pyrolysis, gasification and air-blown combustion of AHR. Maximum liquid yield for pyrolysis of AHR was 30wt% with volatile conversion of 80%. Gas yield for AHR gasification was 78wt%, with 8wt% tar yields and conversion of volatiles close to 100%. 90wt% of the AHR was transformed into gas by combustion, with volatile conversions above 90%. 5volO2%-95vol%N2 gasification resulted in a nitrogen diluted, low heating value gas (2MJ/m3). Steam and oxygen-blown gasification of AHR were additionally investigated in a batch gasifier at KTH in Sweden. Steam promoted the formation of hydrogen (25vol%) and methane (14vol%) improving the gas heating value to 10MJ/m3, below the typical for steam gasification due to equipment limitations. Arrhenius kinetic parameters were calculated using data collected with the LEFR to provide reaction rate information for process design and optimisation. Activation energy (EA) and pre-exponential factor (ko in s-1) for pyrolysis (EA=80kJ/mol, lnko=14), gasification (EA=69kJ/mol, lnko=13) and combustion (EA=42kJ/mol, lnko=8) were calculated after linearly fitting the data using the random pore model. Kinetic parameters for pyrolysis and combustion were also determined by dynamic thermogravimetric analysis (TGA), including studies of the original biomass feedstocks for comparison. Results obtained by differential and integral isoconversional methods for activation energy determination were compared. Activation energy calculated by the Vyazovkin method was 103-204kJ/mol for pyrolysis of untreated feedstocks and 185-387kJ/mol for AHRs. Combustion activation energy was 138-163kJ/mol for biomass and 119-158 for AHRs. The non-linear least squares method was used to determine reaction model and pre-exponential factor. Pyrolysis and combustion of biomass were best modelled by a combination of third order reaction and 3 dimensional diffusion models, while AHR decomposed following the third order reaction for pyrolysis and the 3 dimensional diffusion for combustion.

Spectral characteristics and thermal evolution of long-period gratings in photonic crystal fibers fabricated with a near-IR radiation femtosecond laser using point-by-point inscription

The spectral properties of long-period gratings (LPGs) fabricated in photonic crystal fibers using femtosecond laser pulses by the point-by-point technique, without oil-immersion of the fiber, are investigated in detail. Postfabrication spectral monitoring at room temperature showed significant long-term instability of the gratings and stable spectra only after 600 h. The stabilized spectral properties of the gratings improved with increasing annealing temperature. The observed changes in resonant wavelength, optical strength, and grating birefringence were correlated to the laser inscription energy and were further used to study the mechanism of femtosecond inscription. Furthermore, the femtosecond-laser inscribed LPGs were compared to electric-arc fabricated LPGs. Comparison of experimental results with theoretical models of LPGs and laser propagation during inscription indicate that the major processes responsible for the index change are permanent compaction and thermally induced strain, the latter can be significantly changed through annealing. © 2011 Optical Society of America.

Thermal stability of sewage sludge pyrolysis oil

The stability of the oil phase obtained from intermediate pyrolysis process was used for this investigation. The analysis was based on standard methods of determining kinematic viscosity, gas - chromatography / mass - spectrometry for compositional changes, FT-IR for functional group, Karl Fischer titration for water content and bomb calorimeter for higher heaating values. The methods were used to determine changes that occurred during ageing. The temperatures used for thermal testing were 60 °C and 80 °C for the periods of 72 and 168 h. Methanol and biodiesel were used as solvents for the analysis. The bio-oil samples contained 10 % methanol, 10 % Biodiesel, 20 % Biodiesel and unstabilised pyrolysis oil. The tests carried out at 80 °C showed drastic changes compared to those at 60 °C. The bio-oil samples containing 20 % biodiesel proved to be more stable than those with 10 % methanol. The unstabilised pyrolysis oil showed the greatest changes in viscosity, composition change and highest increase in water content. The measurement of kinematic viscosity and gas chromatograph mass spectrometry were found to be more reliable for predicting the ageing process.

Thermography-based virtual MPPT scheme for improving PV energy efficiency under partial shading conditions

This paper proposes a new thermography-based maximum power point tracking (MPPT) scheme to address photovoltaic (PV) partial shading faults. Solar power generation utilizes a large number of PV cells connected in series and in parallel in an array, and that are physically distributed across a large field. When a PV module is faulted or partial shading occurs, the PV system sees a nonuniform distribution of generated electrical power and thermal profile, and the generation of multiple maximum power points (MPPs). If left untreated, this reduces the overall power generation and severe faults may propagate, resulting in damage to the system. In this paper, a thermal camera is employed for fault detection and a new MPPT scheme is developed to alter the operating point to match an optimized MPP. Extensive data mining is conducted on the images from the thermal camera in order to locate global MPPs. Based on this, a virtual MPPT is set out to find the global MPP. This can reduce MPPT time and be used to calculate the MPP reference voltage. Finally, the proposed methodology is experimentally implemented and validated by tests on a 600-W PV array.