Hydrothermal technologies for the production of fuels and chemicals from biomass

Biomass and non-food crop residues are seen as relatively low cost and abundant renewable sources capable of making a large contribution to the world’s future energy and chemicals supply. Signifi cant quantities of ethanol are currently produced from biomass via biochemical processes, but thermochemical conversion processes offer greater potential to utilize the entire biomass source to produce a range of products. This chapter will review thermochemical gasifi cation and pyrolysis methods with a focus on hydrothermal liquefaction processes. Hydrothermal liquefaction is the most energetically advantageous thermochemical biomass conversion process. If the target is to produce sustainable liquid fuels and chemicals and reduce the impact of global warming as a result of carbon dioxide, nitrous oxide, and methane emissions (i.e., protect the natural environment), the use of “green” solvents, biocatalysts and heterogeneous catalysts must be the main R&D initiatives. As the biocrude produced from hydrothermal liquefaction is a complex mixture which is relatively viscous, corrosive, and unstable to oxidation (due to the presence of water and oxygenated compounds), additional upgrading processes are required to produce suitable biofuels and chemicals.

ATR-FTIR measurement of biomass components in phosphonium ionic liquids

Qualitative and quantitative measurements of biomass components dissolved in the phosphonium ionic liquids (ILs), trihexyltetradecylphosphonium chloride ([P66614]Cl) and tributylmethylphosphonium methylsulphate ([P4441]MeSO 4), are obtained using attenuated total reflectance-FTIR. Absorption bands related to cellulose, hemicelluloses, and lignin dissolution monitored in situ in biomass-IL mixtures indicate lignin dissolution in both ILs and some holocellulose dissolution in the hydrophilic [P4441]MeSO 4. The kinetics of lignin dissolution reported here indicate that while dissolution in the hydrophobic IL [P66614]Cl appears to follow an accepted mechanism of acid catalyzed -aryl ether cleavage, dissolution in the hydrophilic IL [P4441]MeSO 4 does not appear to follow this mechanism and may not be followed by condensation reactions (initiated by reactive ketones). The measurement of lignin dissolution in phosphonium ILs based on absorbance at 1510 cm 1 has demonstrated utility. When coupled with the gravimetric Klason lignin method, ATR-FTIR study of reaction mixtures can lead to a better understanding of the delignification process. © 2012 Copyright Taylor and Francis Group, LLC.

Gravy

To many aspiring writer/directors of feature film breaking into the industry may be perceived as an insurmountable obstacle. In contemplating my own attempt to venture into the world of feature filmmaking I have reasoned that a formulated strategy could be of benefit. As the film industry is largely concerned with economics I decided that writing a relatively low-cost feature film may improve my chances of being allowed directorship by a credible producer. As a result I have decided to write a modest feature film set in a single interior shooting location in an attempt to minimise production costs, therefore also attempting to reduce the perceived risk in hiring the writer as debut director. As a practice-led researcher, the primary focus of this research is to create a screenplay in response to my greater directorial aspirations and to explore the nature in which the said strategic decision to write a single-location film impacts on not only the craft of cinematic writing but also the creative process itself, as it pertains to the project at hand. The result is a comedy script titled Gravy, which is set in a single apartment and strives to maintain a fast comedic pace whilst employing a range of character and plot devices in conjunction with creative decisions that help to sustain cinematic interest within the confines of the apartment. In addition to the screenplay artifact, the exegesis also includes a section that reflects on the writing process in the form of personal accounts, decisions, problems and solutions as well as examination of other author’s works.

Dynamic covalent chemistry on surfaces employing highly reactive cyclopentadienyl moieties

Silicon substrates coated with a bromide-terminated silane are transformed into highly reactive, cyclopentadiene covered analogues. These surfaces undergo rapid cycloaddition reactions with various dienophile-capped polymers. Mild heating of the substrates causes the retro-Diels-Alder reaction to occur, thus reforming the reactive cyclopentadiene surface, generating an efficiently switchable surface.

Photoclickable surfaces for profluorescent covalent polymer coatings

The nitrile imine-mediated tetrazole-ene cycloaddition reaction (NITEC) is introduced as a powerful and versatile conjugation tool to covalently ligate macromolecules onto variable (bio)surfaces. The NITEC approach is initiated by UV irradiation and proceeds rapidly at ambient temperature yielding a highly fluorescent linkage. Initially, the formation of block copolymers by the NITEC methodology is studied to evidence its efficacy as a macromolecular conjugation tool. The grafting of polymers onto inorganic (silicon) and bioorganic (cellulose) surfaces is subsequently carried out employing the optimized reaction conditions obtained from the macromolecular ligation experiments and evidenced by surface characterization techniques, including X-ray photoelectron spectroscopy and FT-IR microscopy. In addition, the patterned immobilization of variable polymer chains onto profluorescent cellulose is achieved through a simple masking process during the irradiation. Photoinduced nitrile imine-alkene 1,3-dipolar cycloaddition (NITEC) is employed to covalently bind well-defined polymers onto silicon oxide or cellulose. A diaryl tetrazole-functionalized molecule is grafted via silanization or amidification, respectively. Under UV light, a reactive nitrile imine rapidly forms and reacts with maleimide-functionalized polymers yielding a fluorescent linkage. Via a masking method, polymeric fluorescent patterns are achieved.

(Ultra)fast catalyst-free macromolecular conjugation in aqueous environment at ambient temperature

Tailor-made water-soluble macromolecules, including a glycopolymer, obtained by living/controlled RAFT-mediated polymerization are demonstrated to react in water with diene-functionalized poly(ethylene glycol)s without pre- or post-functionalization steps or the need for a catalyst at ambient temperature. As previously observed in organic solvents, hetero-Diels-Alder (HDA) conjugations reached quantitative conversion within minutes when cyclopentadienyl moieties were involved. However, while catalysts and elevated temperatures were previously necessary for open-chain diene conjugation, additive-free HDA cycloadditions occur in water within a few hours at ambient temperature. Experimental evidence for efficient conjugations is provided via unambiguous ESI-MS, UV/vis, NMR, and SEC data.

Chaos and creativity of play : designing emotional engagement in public spaces

How do we create strong urban narratives? How do we create affection for our cities? Play, an essential part of any species' biological existence and development, can often be perceived as chaotic and derogatory to social and spatial order. Play is also often perceived as a creative force which generates social and spatial value. This paper looks at the design approaches to both chaotic and creative perceptions of publics at play in urban space. Commonly, Urban and Architectural Design constitutes reactive management of perceived chaos, which derogatorily effects our sensory and emotional engagement with space. Alternatively, Urban and Architectural Design can appeal to the creativity of play, by encouraging unsolicited novelty that is vital to strong experiential narratives in the city and iterating environments that encourage the emergence of physical, emotional and cultural invention. These perceptions of chaos and creativity affect the design methodology of professional practice. Tested through the exciting vehicle of Parkour as urban narrative, the constraints and opportunities of both approaches are presented.

Persistent digital hyperthermia over a 48 h period does not induce laminitis in horses

Persistent digital hyperthermia, presumably due to vasodilation, occurs during the developmental and acute stages of insulin-induced laminitis. The objectives of this study were to determine if persistent digital hyperthermia is the principal pathogenic mechanism responsible for the development of laminitis. The potent vasodilator, ATP-MgCl 2 was infused continuously into the distal phalanx of the left forefoot of six Standardbred racehorses for 48h via intra-osseous infusion to promote persistent digital hyperthermia. The right forefoot was infused with saline solution and acted as an internal control. Clinical signs of lameness at the walk were not detected at 0h, 24h or 48h post-infusion. Mean±SE hoof wall temperatures of the left forefoot (29.4±0.25°C) were higher (P<0.05) than those on the right (27.5±0.38°C). Serum insulin (15.0±2.89μIU/mL) and blood glucose (5.4±0.22mM) concentrations remained unchanged during the experiment. Histopathological evidence of laminitis was not detected in any horse. The results demonstrated that digital vasodilation up to 30 °C for a period of 48. h does not trigger laminitis in the absence of hyperinsulinaemia. Thus, although digital hyperthermia may play a role in the pathogenesis of laminitis, it is not the sole mechanism involved.

Continuous intravenous infusion of glucose induces endogenous hyperinsulinaemia and lamellar histopathology in Standardbred horses

Endocrinopathic laminitis is frequently associated with hyperinsulinaemia but the role of glucose in the pathogenesis of the disease has not been fully investigated. This study aimed to determine the endogenous insulin response to a quantity of glucose equivalent to that administered during a laminitis-inducing, euglycaemic, hyperinsulinaemic clamp, over 48. h in insulin-sensitive Standardbred racehorses. In addition, the study investigated whether glucose infusion, in the absence of exogenous insulin administration, would result in the development of clinical and histopathological evidence of laminitis. Glucose (50% dextrose) was infused intravenously at a rate of 0.68 mL/kg/h for 48. h in treated horses (n = 4) and control horses (n = 3) received a balanced electrolyte solution (0.68 mL/kg/h). Lamellar histology was examined at the conclusion of the experiment. Horses in the treatment group were insulin sensitive (M value 0.039 ± 0.0012. mmol/kg/min and M-to-I ratio (100×) 0.014 ± 0.002) as determined by an approximated hyperglycaemic clamp. Treated horses developed glycosuria, hyperglycaemia (10.7 ± 0.78. mmol/L) and hyperinsulinaemia (208 ± 26.1. μIU/mL), whereas control horses did not. None of the horses became lame as a consequence of the experiment but all of the treated horses developed histopathological evidence of laminitis in at least one foot. Combined with earlier studies, the results showed that laminitis may be induced by either insulin alone or a combination of insulin and glucose, but that it is unlikely to be due to a glucose overload mechanism. Based on the histopathological data, the potential threshold for insulin toxicity (i.e. laminitis) in horses may be at or below a serum concentration of ∼200. μIU/mL.

Use of hierarchical cluster analysis to assess the representativeness of a baseline groundwater quality monitoring network: comparison of New Zealand’s national and regional groundwater monitoring programs

Baseline monitoring of groundwater quality aims to characterize the ambient condition of the resource and identify spatial or temporal trends. Sites comprising any baseline monitoring network must be selected to provide a representative perspective of groundwater quality across the aquifer(s) of interest. Hierarchical cluster analysis (HCA) has been used as a means of assessing the representativeness of a groundwater quality monitoring network, using example datasets from New Zealand. HCA allows New Zealand's national and regional monitoring networks to be compared in terms of the number of water-quality categories identified in each network, the hydrochemistry at the centroids of these water-quality categories, the proportions of monitoring sites assigned to each water-quality category, and the range of concentrations for each analyte within each water-quality category. Through the HCA approach, the National Groundwater Monitoring Programme (117 sites) is shown to provide a highly representative perspective of groundwater quality across New Zealand, relative to the amalgamated regional monitoring networks operated by 15 different regional authorities (680 sites have sufficient data for inclusion in HCA). This methodology can be applied to evaluate the representativeness of any subset of monitoring sites taken from a larger network.

Submarine pyroclastic deposits formed during the 20th May 2006 dome collapse of the Soufrière Hills Volcano, Montserrat

The 20th May 2006 lava dome collapse of the Soufrière Hills Volcano, Montserrat, had a total non-dense rock equivalent (non-DRE) collapse volume of approximately 115 × 10 6 m 3. The majority of this volume was deposited into the ocean. The collapse was rapid, 85% of the mobilized volume being removed in just 35 min, giving peak pyroclastic flow flux of 66 × 10 3 m 3 s -1. Channel and levee facies on the submarine flanks of the volcano and formation of a thick, steep-sided ridge, suggest that the largest and most dense blocks were transported proximally as a high concentration granular flow. Of the submerged volume, 30% was deposited from the base of this granular flow, forming a linear, high-relief ridge that extends 7 km from shore. The remaining 70% of the submerged volume comprises the finer grain sizes, which were transported at least 40 km by turbidity currents on gradients of <2°. At several localities, the May 2006 distal turbidity currents ran up 200 m of topography and eroded up to 20 cm of underlying substrate. Multiple turbidites are preserved, representing current reflection from the graben margins and deflection around topography. The high energy of the May 2006 collapse resulted in longer submarine run out than the larger (210 × 10 6 m 3) Soufrière Hills dome collapse in July 2003.

Entrepreneurship education in non-business schools : best practice for Australian contexts of knowledge and innovation communities (Final Report)

In the current era of global economic instability, business and industry have already identified a widening gap between graduate skills and employability. An important element of this is the lack of entrepreneurial skills in graduates. This Teaching Fellowship investigated two sides of a story about entrepreneurial skills and their teaching. Senior players in the innovation commercialisation industry, a high profile entrepreneurial sector, were surveyed to gauge their needs and experiences of graduates they employ. International contexts of entrepreneurship education were investigated to explore how their teaching programs impart the skills of entrepreneurship. Such knowledge is an essential for the design of education programs that can deliver the entrepreneurial skills deemed important by industry for future sustainability. Two programs of entrepreneurship education are being implemented at QUT that draw on the best practice exemplars investigated during this Fellowship. The QUT Innovation Space (QIS) focuses on capturing the innovation and creativity of students, staff and others. The QIS is a physical and virtual meeting and networking space; a connected community enhancing the engagement of participants. The Q_Hatchery is still embryonic; but it is intended to be an innovation community that brings together nascent entrepreneurial businesses to collaborate, train and support each other. There is a niche between concept product and business incubator where an experiential learning environment for otherwise isolated ‘garage-at-home’ businesses could improve success rates. The QIS and the Q_Hatchery serve as living research laboratories to trial the concepts emerging from the skills survey. The survey of skills requirements of the innovation commercialisation industry has produced a large and high quality data set still being explored. Work experience as an employability factor has already emerged as an industry requirement that provides employee maturity. Exploratory factor analysis of the skills topics surveyed has led to a process-based conceptual model for teaching and learning higher-order entrepreneurial skills. Two foundational skills domains (Knowledge, Awareness) are proposed as prerequisites which allow individuals with a suite of early stage entrepreneurial and behavioural skills (Pre-leadership) to further leverage their careers into a leadership role in industry with development of skills around higher order elements of entrepreneurship, management in new business ventures and progressing winning technologies to market. The next stage of the analysis is to test the proposed model through structured equation modelling. Another factor that emerged quickly from the survey analysis broadens the generic concept of team skills currently voiced in Australian policy documents discussing the employability agenda. While there was recognition of the role of sharing, creating and using knowledge in a team-based interdisciplinary context, the adoption and adaptation of behaviours and attitudes of other team members of different disciplinary backgrounds (interprofessionalism) featured as an issue. Most undergraduates are taught and undertake teamwork in silos and, thus, seldom experience a true real-world interdisciplinary environment. Enhancing the entrepreneurial capacity of Australian industry is essential for the economic health of the country and can only be achieved by addressing the lack of entrepreneurial skills in graduates from the higher education system. This Fellowship has attempted to address this deficiency by identifying the skills requirements and providing frameworks for their teaching.