Applicability of mechanical tests for biomass pellet characterisation for bioenergy applications

In this paper, the applicability of mechanical tests for biomass pellet characterisation was investigated. Pellet durability, quasi-static (low strain rate), and dynamic (high strain rate) mechanical tests were applied to mixed wood, eucalyptus, sunflower, miscanthus, and steam exploded and microwaved pellets, and compared to their Hardgrove Grindability Index (HGI), and milling energies for knife and ring-roller mills. The dynamic mechanical response of biomass pellets was obtained using a novel application of the Split Hopkinson pressure bar. Similar mechanical properties were obtained for all pellets, apart from steam-exploded pellets, which were significantly higher. The quasi-static rigidity (Young’s modulus) was highest in the axial orientation and lowest in flexure. The dynamic mechanical strength and rigidity were highest in the diametral orientation. Pellet strength was found to be greater at high strain rates. The diametral Young’s Modulus was virtually identical at low and high strain rates for eucalyptus, mixed wood, sunflower, and microwave pellets, while the axial Young’s Modulus was lower at high strain rates. Correlations were derived between the milling energy in knife and ring roller mills for pellet durability, and quasi-static and dynamic pellet strength. Pellet durability and diametral quasi-static strain was correlated with HGI. In summary, pellet durability and mechanical tests at low and high strain rates can provide an indication of how a pellet will break down in a mill

Improving the design of industrial microwave processing systems through prediction of the dielectric properties of complex multi-layered materials

Rigorous design of industrial microwave processing systems requires in-depth knowledge of the dielectric properties of the materials to be processed. These values are not easy to measure, particularly when a material is multi-layered containing multiple phases, when one phase has a much higher loss than the other and the application is based on selective heating. This paper demonstrates the ability of the Clausius-Mossotti (CM) model to predict the dielectric constant of multi-layered materials. Furthermore, mixing rules and graphical extrapolation techniques were used to further evidence our conclusions and to estimate the loss factor. The material used for this study was vermiculite, a layered alumina-silicate mineral containing up to 10 % of an interlayer hydrated phase. It was measured at different bulk densities at two distinct microwave frequencies, namely 934 and 2143 MHz. The CM model, based on the ionic polarisability of the bulk material, gives only a prediction of the dielectric constant for experimental data with a deviation of less than 5 % at microwave frequencies. The complex refractive index model (CRIM), Landau, Lifshitz and Loyenga (LLL), Goldschmidt, Böttcher and Bruggeman-Hanai model equations are then shown to give a strong estimation of both dielectric constant and loss factor of the solid material compared to that of the measured powder with a deviation of less than 1 %. Results obtained from this work provide a basis for the design of further electromagnetic processing systems for multi-layered materials consisting of both high loss and low loss components

Thermodynamic, pyrolytic, and kinetic investigation on the thermal decomposition of polyvinyl chloride in the presence of franklinite

Thermal co-treatment of Electric Arc Furnace Dust (EAFD) and polyvinyl chloride (PVC) may provide a viable route for reprocessing these hazardous materials within the circular economy. To develop and optimise a commercial treatment process, the complex mechanistic pathway resulting from the reaction of these two wastes must be understood. Franklinite (ZnFe2O4) is a major zinc containing phase in EAFD and to date, little work has been undertaken on the decomposition of PVC in its presence. Herein, we present a thermodynamic, pyrolytic, and kinetic study of PVC degradation in the presence of ZnFe2O4. It was found that, ZnFe2O4 decomposed to its associated halides. Additionally, the kinetics data confirmed the catalytic activity of ZnFe2O4, dropping the de-hydrochlorination onset temperature of PVC from 272 to 235 °C. The distribution of the activation energy with conversion suggests the presence of several competitive reactions each with a different energy barrier. In such a case, reaction channelling can take place leading to selective zinc chlorination.Moreover, since the reduction of Fe2O3 is slow at low temperatures, it is recommended to operate at a temperature as low as 235 °C which can promote the chlorination selectivity towards zinc leaving iron bearing compounds in their stable form (Fe2O3)

Benefits of dry comminution of biomass pellets in a knife mill

The potential benefits of dry comminution in a knife mill for a diverse range of biomass 6 pellets are explored. The impact of dry comminution on energy consumption, particle size and shape, 7 is examined as well as the link between milling and mechanical durability. Biomass pellet comminution 8 energy was significantly lower (19.3-32.5 kW h t-1 [fresh] and 17.8-23.2 kW h t-1 [dry]) than values 9 reported in literature for non-densified biomass in similar knife mills. The impact of drying was found 10 to vary by feedstock. Dry grinding reduced milling energy by 38% for mixed wood pellets, but only 2% 11 for steam exploded pellets. Particle size and shape, particle distribution dispersion, and distribution 12 shape parameters changes between fresh and dry milling were also material dependent. Von Rittinger 13 analysis showed that to maximise mill throughput, pellets should be composed of particles which can 14 pass through the screen and thus have a neutral size change. A strong correlation was found between 15 pellet durability and energy consumption for fresh biomass pellets. Dry grinding has the potential to 16 significantly reduce energy consumption without compromising the product particle size, as well as 17 enhancing product quality and optimising biomass pellet comminution and combustion

A thermo-kinetic investigation on the thermal degradation of polyvinyl chloride in the presence of magnetite and hematite

Electric arc furnace dust (EAFD) which is accumulated in large amounts world-wide contains hematite (Fe2O3) and significant quantities of magnetite (Fe3O4). Waste polyvinyl chloride (PVC) also poses a great environmental threat aside to accumulated EAFD. Both of these wastes have shown a great potential for their co-thermal treatment for metal extraction, thus minimising their environmental footprint. Herein, an investigation on the thermal degradation behaviour, reaction products, thermodynamics and the decomposition kinetics of PVC and its stoichiometric mixtures with Fe3O4 and Fe2O3 was conducted using non-isothermal thermogravimetric scans. The kinetic data suggests a significant increase in the average activation energy of PVC de-hydrochlorination from 122.6 ± 24.2 kJ/mol (pure PVC) to 177.0 ± 28.0 and 199.0 ± 77.0 kJ/mol when stoichiometric quantities of Fe3O4 and Fe2O3 were mixed with PVC. The inhibiting effect of both Fe3O4 and Fe2O3 on the degradation of PVC might be assigned to the capturing of emitted gaseous HCl which is known for its catalytic effect. This result suggests that EAFDs containing both Fe3O4 (in large amounts) and Fe2O3 can have an inhibiting effect on the de-hydrochlorination of PVC resulting in longer processing times or the requirement of higher processing temperatures for achieving reasonable reaction rates

Overcoming the caking phenomenon in olive mill wastes

The use of olive mill wastes (orujillo) within coal fired power stations in the UK has led to unexpected difficulties with material caking within the fuel handling plant. This study replicated orujillo caking on a laboratory scale using a planetary ball mill and explored the impact of mill parameters (speed, volume, and duration) on the caking phenomenon. The impact of orujillo composition was examined for 4 sections of fresh and dried orujillo (whole, pulp 0-850 µm, pulp 850-3350 µm, and cluster 3350 µm+) for set milling conditions. Caking was induced by heat generation within the mill and was most prevalent in the pulp section of orujillo. Caking was brought on by a glass transition step, which was measured to be around 97-98 °C for a moisture content of 6-7% in a differential scanning calorimeter (DSC). Caking was the result of the bulk moisture content (14-18%) being higher than the standard moisture content of orujillo (< 12%), and can be mitigated through drying. Thus the key to overcoming orujillo caking in fuel handling plants is through moisture content control. Additionally, as the caking issue is most prevalent in the pulp section, all fines below the required combustion particle size (typically < 1 mm) should be removed prior to comminution and sent directly to the burner. This would also reduce the comminution load by nearly 50%, increase the energy potential of the fuel, and remove the most problematic section of orujillo from the fuel handling plant

Microvawe pyrolysis of biomass: control of process parameters for high pyrolysis oil yields and enhanced oil quality

The oil yield and quality of pyrolysis oil from microwave heating of biomass was established by studying the behaviour of Larch in microwave processing. This is the first study in biomass pyrolysis to use a microwave processing technique and methodology that is fundamentally scalable, from which the basis of design for a continuous processing system can be derived to maximise oil yield and quality. It is shown systematically that sample size is a vital parameter that has been overlooked by previous work in this field. When sample size is controlled the liquid product yield is comparable to conventional pyrolysis, and can be achieved at an energy input of around 600 kWh/t. The quality of the liquid product is significantly improved compared to conventional pyrolysis processes, which results from the very rapid heating and quenching that can be achieved with microwave processing. The yields of Levoglucosan and phenolic compounds were found to be an order of magnitude higher in microwave pyrolysis when compared with conventional fast pyrolysis. Geometry is a key consideration for the development of a process at scale, and the opportunities and challenges for scale-up are discussed within this paper

Thermal analysis on the pyrolysis of tetrabromobisphenol A (TBBPA) and Electric Arc Furnace Dust mixtures

The pyrolysis of Tetrabromobisphenol A (TBBPA) mixed with Electric Arc Furnace Dust (EAFD) was studied using thermogravimetric analysis (TGA) and theoretically analysed using thermodynamic equilibrium calculations. Mixtures of both materials with varying TBBPA loads (1:1, and 1:3) were prepared and pyrolyzed in a nitrogen atmosphere under dynamic heating conditions at heating rates of 5 and 10 ⁰C/min. The mixtures degraded through several steps including decomposition of TBBPA yielding mainly HBr, bromination of metal oxides, followed by their evaporation in the sequence of CuBr3, ZnBr2, PbBr2, FeBr2, MnBr2, KBr, NaBr, CaBr2 and MgBr2, and finally reduction of the remaining metal oxides by the char formed from decomposition of TBBPA. Thermodynamic calculations suggest the possibility of selective bromination of zinc and lead followed by their evaporation leaving iron in its oxide form, while the char formed may serve as a reduction agent for iron oxides into metallic iron. However, at higher TBBPA volumes, iron bromide forms, which can be also evaporated at a temperature higher than those of ZnBr2 and PbBr2. Results from this work provide practical insight into selective recovery of valuable metals from EAFD while at the same time recycling the hazardous bromine content in TBBPA

Chlorine Fixing Ability of Electric Arc Furnace Dust During the Thermal Degradation of Polyvinyl Chloride under Oxidative Conditions

Electric arc furnace dust (EAFD) and polyvinyl chloride (PVC) are two hazardous wastes that are accumulated world-wide at an alarming rate. Utilising these two wastes simultaneously towards a sustainable recycling loop can greatly mitigate their environmental impact. Herein, EAFD was studied as a potential emission fixator of evolved gaseous HCl generated from the thermal decomposition of PVC under different operational conditions: EAFD-PVC mass ratio, solid reactants geometry, O2 partial pressure, holding temperature, holding time and heating rate. The highest chlorine fixation percentage was calculated to be 78.9% and was obtained at an EAFD-PVC mass ratio of 1:1 (thin disks geometry), while the rest escaped in the form of HCl/Cl2. No significant variation was observed on the percentage of fixed chlorine when the thermal treatment was performed using different geometries: long cylinder, thin disks, and powder forms with a maximum difference in fixation of only 5.6% between extremities. Increasing O2 partial pressure positively affected the chlorine fixation percentage increasing it from 39.9 to 48.4% at 0 and 21 kPa partial pressures, respectively. Increasing both the holding temperature and holding time under oxidative conditions negatively affected the percentage of fixed chlorine due to oxidation of formed FeCl2 back to Fe2O3. The heating rate did not show any significant effect on the amount of fixed HCl, suggesting that the speed of chlorination reactions can be identical to or faster than the decomposition rate of PVC. Overall, EAFD is believed to be an excellent candidate for capturing HCl contained in PVC upon thermal degradation

Microwave digestion of gibbsite and bauxite in sodium hydroxide

It was hypothesized that bauxite digestion may be improved by using microwave heating as it has been shown in literature that some material processes have improved efficiency. To test this hypothesis, a set of digestion experiments were conducted using gibbsite, one of the major minerals in bauxite. Gibbsite was digested at various temperatures (50, 75, and 95 °C) in either 1 M or 6 M sodium hydroxide solutions for 30 min using either a convection oven or a 2.45 GHz microwave applicator. Results show that microwave heating provided an increase of 5–7% in the digestion after 30 min and required around 1/10th the time to heat the solutions compared to conventional heating. Electromagnetic simulations show that preferential heating occurs at the solution surface creating a temperature gradient within the solution. Although vigorous stirring of the solution was used to minimize the temperature gradient, it could still be responsible for the observed difference in digestion. Digestion of bauxite itself yielded similar results to the gibbsite