The Utilisation of biomass as a fuel for chemical looping combustion

Development of a commercially viable carbon capture and sequestration (CCS) technology for fossil fuel power generation is vital if the anticipated effects of global warning are to be avoided. Chemical-looping combustion (CLC) is an indirect combustion process that utilises a regenerable solid oxygen sorbent (oxygen carrier, OC), typically a metal oxide, to transfer oxygen from the combustion air to the fuel such that direct contact between air and fuel is avoided. CLC is a variant on an oxy-fuel carbon capture system that offers the potential for a much lower energy penalty as CO2 separation is achieved intrinsically such that additional energy-intensive gas separation steps are avoided. Our research focuses on the development and optimisation of OCs for CLC systems using biomass and biomass derived fuels. The development of a CLC process utilising biomass is of particular interest as it has the potential to result in negative CO2 emissions i.e. a net removal of CO2 from the atmosphere. Thermochemical conversion of biomass typically results in the formation of significant quantities of refractory tar compounds which are difficult to combust and can lead to reduced fuel conversion efficiencies. Decomposition of the tars on the surface of the OC can result in severe coking and temporary deactivation. Coking of the OC also limits the overall CO2 capture efficiency of the process as regeneration of the OC in air produces CO2 which cannot be captured. This thesis documents the progress made towards the development of a robust laboratory based system for testing the effects of biomass tars on the long term performance of a chemical-looping combustion process. The work completed in this thesis can be divided into two main areas: the first involved developing optimised fabrication strategies for the production of inexpensive iron-based oxygen carrier particles of high reactivity and robust physical characteristics that could be used in CLC systems utilising biomass as the fuel. The second research focus involved the development of a reactor and analysis protocol for studying the interactions between biomass pyrolysis tars and the cheap, synthetic iron-based oxygen carrier materials. A range of pure iron oxide and iron oxide supported with 40 wt.% Al2O3 oxygen carrier materials were prepared via simple scalable fabrication techniques based on wet granulation for use in CLC systems utilising biomass or gasified biomass as a fuel. The oxygen carrier particles were subjected to rigorous testing using a range of analytical methods to assess their physical and chemical properties and suitability for use in large-scale systems. The effect of fabrication method and alumina precursor material used for producing the supported iron oxide materials were found to have a considerable effect on the physical characteristics and reactivity of the oxygen carrier material. The reduction kinetics (the rate limiting step in the CLC of gaseous fuels) of the different OC materials prepared in this work were assessed using a thermogravimetric analyser (TGA). A simple particle model based on the concept of effectiveness factor was applied to determine the intrinsic kinetic information. Preparation of the Al2O3 supported iron oxide oxygen carrier material using a Al(OH)3 alumina precursor gave the most porous oxygen carrier material with the highest surface area. This oxygen carrier was also the most reactive particularly at temperatures above 973 K and demonstrated very good thermal stability at temperatures up to 1173 K. The activation energy of the oxygen carrier was found to increase from 73 kJ mol-1 for the temperature range 823-1073 K to 123 kJ mol-1 at temperatures of 1073-1173 K. The increase in the activation energy was attributed to further conversion of Fe3O4 to FeAl2O4 which was more pronounced at the higher temperature range. Here we propose that the formation of FeAl2O4 was beneficial, acting to enhance the thermal stability, reactivity and oxygen transfer capacity of the iron oxide based oxygen carrier material. A new 500W laboratory-scale, two-stage fixed-bed reactor for simulating CLC with ex situ solid fuel gasification has been designed and constructed. Preliminary studies of the interactions between OC materials consisting of pure iron oxide and 60 wt.% Fe2O3 iron oxide supported on Al2O3 and a gas stream produced from the pyrolysis of biomass to emulate a fuel gas containing large quantities of tars were carried out. The presence of both OC materials at 973 K was found to significantly reduce the amount of biomass tars by up to 71 wt.% in the case of the 60 wt.% Fe2O3/40 wt.% Al2O3 OC material compared with analogous experiments in which the biomass tars were exposed to an inert bed of sand. Exposing the pyrolysis vapours to the oxygen carriers in their oxidised form favoured the production of CO2. The production of CO was favoured when the oxygen carriers were in their reduced forms. Both oxygen carrier materials were affected by carbon deposition. Carbon deposition was removed in the subsequent oxidation phase with no obvious deleterious effects on the reactivity of the oxygen carrier materials after exposure to the pyrolysis gases and vapours.Open Acces

Hydrogen production by sorption enhanced steam reforming (SESR) of biomass in a fluidised-bed reactor using combined multifunctional particles

The performance of combined CO2-sorbent/catalyst particles for sorption enhanced steam reforming (SESR), prepared via a simple mechanical mixing protocol, was studied using a spout-fluidised bed reactor capable of continuous solid fuel (biomass) feeding. The influence of particle size (300–500 and 710–1000 µm), CaO loading (60–100 wt %), Ni-loading (10–40 wt %) and presence of dicalcium silicate support (22.6 wt %) on SESR process performance were investigated. The combined particles were characterised by their density, porosity and CO2 carrying capacity with the analysis by thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET), Barrett-Joyner-Halenda (BJH) and mercury intrusion porosimetry (MIP). All experiments were conducted with continuous oak biomass feeding at a rate of 0.9 g/min ± 10%, and the reactor was operated at 660 ± 5 °C, 1 atm and 20 ± 2 vol % steam which corresponds to a steam-to-carbon ratio of 1.2:1. Unsupported combined particles containing 21.0 wt % Ni and 79 wt % CaO were the best performing sorbent/catalyst particle screened in this study, when accounting for the cost of Ni and the improvement in H2 produced by high Ni content particles. SESR tests with these combined particles produced 61 mmol H2/gbiomass (122 g H2/kgbiomass) at a purity of 61 vol %. Significant coke formation within the feeding tube and on the surfaces of the particles was observed which was attributed to the low steam to carbon ratio utilised

The utilisation of post-activation performance enhancement to enhance jump performance during training and sporting competition

Post-activation performance enhancement (PAPE) may be used to enhance jump performance. The review recommends PAPE can be subcategorised into two groups: Training PAPE and Performance PAPE. Training PAPE methods can be incorporated for training purposes where more select equipment, time, and space is available. Performance PAPE can be utilised to enhance competition performance in which limited, or no equipment, is required and can be easily performed before an event. This review highlighted that isoinertial methods are commonly employed for both performance and Training PAPE; however, plyometric training appears a more favourable form of Performance PAPE. Furthermore, accentuated eccentric loading could be coupled with plyometric training to achieve the highest PAPE response, but further work is required

The Acute Effects of Weighted Vest Protocols on 20-Metre Sprint Performance in Youth Soccer Players

This investigation examined the effects of a warm-up containing weighted vest (WV) sprints on subsequent 20-metre sprint time relative to a control (C) condition in youth soccer players (n=12, mean ± SD age 16 ± 0.60 years, height 175.17 ± 5.92 cm and body mass 61.85 ± 5.88 kg). The main experimental trials consisted of three WV conditions at 10, 20 and 30% of body mass (WV10, WV20 and WV30) and C. Participants were required to complete one 20-metre sprint with each of WV conditions or without additional mass as part of C prior to a 20-metre sprint at 4-, 8- and 12-minutes. A two-way repeated measures ANOVA revealed no significant difference between any of the conditions and rest periods (p = >0.05). The between condition effect sizes for 20-metre sprint times were moderate at 4- and 12-minutes post WV10 (d = -0.86 and -1.15, respectively) and 12-minutes post WV20 (d = -0.84) and WV30 (d = -0.80). Moderate effect sizes were also observed at 4-minutes post WV10 (d = -1.04) and WV20 (d = -0.67) for 10-metre sprint times. These findings demonstrate that WV loading has no significant effect on 20-metre sprint time in youth soccer players. However, there is an opportunity for S&C coaches to implement WV warm-ups of no more than 30% body mass to improve 20-metre sprint times

A Novel Form of Chondrocyte Stress is Triggered by a COMP Mutation Causing Pseudoachondroplasia

Pseudoachondroplasia (PSACH) results from mutations in cartilage oligomeric matrix protein (COMP) and the p.D469del mutation within the type III repeats of COMP accounts for approximately 30% of PSACH. To determine disease mechanisms of PSACH in vivo, we introduced the Comp D469del mutation into the mouse genome. Mutant animals were normal at birth but grew slower than their wild-type littermates and developed short-limb dwarfism. In the growth plates of mutant mice chondrocyte columns were reduced in number and poorly organized, while mutant COMP was retained within the endoplasmic reticulum (ER) of cells. Chondrocyte proliferation was reduced and apoptosis was both increased and spatially dysregulated. Previous studies on COMP mutations have shown mutant COMP is co-localized with chaperone proteins, and we have reported an unfolded protein response (UPR) in mouse models of PSACH-MED (multiple epiphyseal dysplasia) harboring mutations in Comp (T585M) and Matn3, Comp etc (V194D). However, we found no evidence of UPR in this mouse model of PSACH. In contrast, microarray analysis identified expression changes in groups of genes implicated in oxidative stress, cell cycle regulation, and apoptosis, which is consistent with the chondrocyte pathology. Overall, these data suggest that a novel form of chondrocyte stress triggered by the expression of mutant COMP is central to the pathogenesis of PSACH. Hum Mutat 33:218–231, 2012. © 2011 Wiley Periodicals, Inc

Building for the Future: A Systematic Review of the Effects of Eccentric Resistance Training on Measures of Physical Performance in Youth Athletes

Background: Eccentric resistance training is recognised as an effective stimulus for enhancing measures of muscular strength and power in adult populations; however, its value in youth athletes is currently not well understood. Objective: The aim of this systematic review was to critically appraise the effects of eccentric resistance training on measures of physical performance (i.e. muscular strength, jump, sprint and change of direction) in youth athletes 18 years of age and under. Methods: Original journal articles published between 1950 and June 2022 were retrieved from electronic search engines of PubMed, SPORTDiscus and Google Scholar’s advanced search option. Full journal articles investigating the acute and chronic effects of eccentric resistance training on measures of physical performance in youth athletes (i.e. a person 18 years of age or under who competes in sport) were included. The methodological quality and bias of each study were assessed prior to data extraction using a modified Downs and Black checklist. Results: The search yielded 749 studies, of which 436 were duplicates. Three-hundred studies were excluded based upon title and abstract review and a further 5 studies were removed following the modified Downs and Black checklist. An additional 14 studies were identified during backward screening. Accordingly, 22 studies were included in our systematic review. The Nordic hamstring exercise and flywheel inertial training were the most frequently used eccentric resistance training methods in youth athletes. Improvements in physical performance following the Nordic hamstring exercise are dependent upon an increase in the breakpoint angle, rather than training volume (sets and repetitions), and are further elevated with the addition of hip extension exercises or high-speed running. A minimum of 3 familiarisation trials is necessary to elicit meaningful adaptations following flywheel inertial training. Furthermore, an emphasis should be placed upon decelerating the rotating flywheel during the final one to two thirds of the eccentric phase, rather than gradually throughout the entire eccentric phase. Conclusions: The findings of this systematic review support the inclusion of eccentric resistance training in youth athletes to improve measures of muscular strength, jump, sprint and change of direction performance. The current eccentric resistance training methods are predominantly limited to the Nordic hamstring exercise and flywheel inertial training; however, the efficacy of accentuated eccentric loading to improve jump performance warrants attention in future investigations

Development and Reliability of Countermovement Jump Performance in Youth Athletes at Pre-, Circa- and Post-Peak Height Velocity

The purpose of this study was to establish the intrasession reliability of various outcome, propulsion and braking phase countermovement jump (CMJ) variables and to compare the mean differences in youth athletes at different stages of maturity. Thirty male participants, aged 10-16 years, were grouped as either pre-, circa- or post-peak height velocity (PHV) according to their percentage of predicted adult height. All participants performed 3 CMJ trials on a force plate, sampling at 1000 Hz. A one-way ANOVA identified statistically significant differences between maturity groups for all CMJ variables (P<0.05) excluding propulsion peak rate of force development (RFD), braking peak velocity and countermovement depth. Post-hoc analysis revealed that the significant differences in CMJ variables were between the pre- to post- and circa- to post-PHV groups (P <0.05), with moderate to very large effect sizes. Relative and absolute reliability improved with maturity as the post-PHV group demonstrated superior reliability scores (ICC = 0.627-0.984; CV% = 3.25-21.55) compared to circa- (ICC = 0.570-0.998; CV% = 1.82-20.05) and pre-PHV groups (ICC= 0.851-0.988; CV% = 2.16-14.12). In summary, these results suggest that the biggest differences in CMJ performance are observed between preto post- and circa- to post-PHV, and that careful consideration is warranted when selecting variables in youth athletes at pre- and circa-PHV, given the lower reliability scores observed

Dispersible microporous di-block co-polymer Nanoparticles via polymerisation-induced self-assembly

Microporous materials are predominantly formed as insoluble powders which means that they can be difficult to process. Here we report a new class of solvent-dispersible porous polymers synthesised by reversible addition-fragmentation chain transfer mediated polymerisation-induced self-assembly (RAFT-mediated PISA), formed from a PEG macro-CTA polymerised with divinylbenzene and fumaronitrile. The particles have a dual morphology consisting of smaller spheres of 24-29 nm aggregated into larger particles of 204 - 262 nm. Gas sorption analysis showed the particles to have BET surface areas of 274 to 409 m2/g with internal pore sizes centred around 1.8 nm and further larger pores arising from the sphere packing of the aggregates. The particles were found to be photoluminescent (emission λmax = 326 nm) when exposed to UV light which could be quenched by the addition of nitroaromatic compounds. For example, 99% if the emission was quenched in the presence of 38 ppm of picric acid