Since the beginning of farming, and even before, humans have been actively modifying our environment in order to harvest biomass. With the ‘Great Acceleration’ of the industrial age, the global system of biomass harvest for food production has become a major driver of Earth system processes, and caused multi-dimensional sustainability issues which must be addressed in order to meet continued increases in demand for food and other biomass. In addition, bioenergy generation, with the subsequent storage of some or all of the carbon content of the feedstock (known as bioenergy with carbon storage or BECS), is now seen as an important tool for rebalancing the carbon cycle. This thesis has used a biomass flows modelling approach to examine possible trajectories for the socio-ecological metabolism of humanity, with a focus on fluxes of carbon contained in biomass. This approach connects social and economic drivers of biomass harvest with physical Earth systems processes such as the global carbon cycle. Meeting growing food demand in the years 2000-2050 is likely to be a significant challenge in its own right, necessitating the harvest of over 30% of terrestrial biomass. This can only be done without significant damage to natural ecosystems if large increases in efficiency and intensity of food production are achieved, or diets are altered. The production of livestock products is shown to be a major cause of inefficiency in biomass harvest, and changes to livestock demand or production are particularly powerful in ensuring a less damaging relationship with Earth system processes. If increases in efficiency are achieved, it may be possible to grow dedicated bioenergy crops, which, combined with the biomass available in waste and residue streams can be used to generate significant carbon dioxide removal (CDR) fluxes via BECS. Following this strategy it is possible to have a non-trivial effect on atmospheric CO2 concentration by 2050. Increasing the intensity of biomass harvest, particularly when low intensity pasture is replaced with intense bioenergy cropping, also has significant implications for ecological energy flows, and the potential trade-off between protecting biodiversity and growing bioenergy crops to mitigate climate change is also discussed. This body of work presents several interesting areas of potential conflict in different drivers of biomass harvest, and suggestions are made for ways in which to develop the approach in order to explore them.

Chemical absorption and desorption processes are two fundamental operations in the process industry. Due to the rate-controlled nature of these processes, classical equilibrium stage models are usually inadequate for describing the behaviour of chemical absorption and desorption processes. A more effective modelling method is the non-equilibrium rate-based approach, which considers the effects of the various driving forces across the vapour-liquid interface. In this thesis, a new non-equilibrium rate-based model for chemical absorption and desorption is developed and applied to the hot potassium carbonate process CO₂ Removal Trains at the Santos Moomba Processing Facility. The rate-based process models incorporate rigorous thermodynamic and mass transfer relations for the system and detailed hydrodynamic calculations for the column internals. The enhancement factor approach was used to represent the effects of the chemical reactions. The non-equilibrium rate-based CO₂ Removal Train process models were implemented in the Aspen Custom Modeler® simulation environment, which enabled rigorous thermodynamic and physical property calculations via the Aspen Properties® software. Literature data were used to determine the parameters for the Aspen Properties® property models and to develop empirical correlations when the default Aspen Properties® models were inadequate. Preliminary simulations indicated the need for adjustments to the absorber column models, and a sensitivity analysis identified the effective interfacial area as a suitable model parameter for adjustment. Following the application of adjustment factors to the absorber column models, the CO₂ Removal Train process models were successfully validated against steady-state plant data. The success of the Aspen Custom Modeler® process models demonstrated the suitability of the non-equilibrium rate-based approach for modelling the hot potassium carbonate process. Unfortunately, the hot potassium carbonate process could not be modelled as such in HYSYS®, Santos’s preferred simulation environment, due to the absence of electrolyte components and property models and the limitations of the HYSYS® column operations in accommodating chemical reactions and non-equilibrium column behaviour. While importation of the Aspen Custom Modeler® process models into HYSYS® was possible, it was considered impractical due to the significant associated computation time. To overcome this problem, a novel approach involving the HYSYS® column stage efficiencies and hypothetical HYSYS® components was developed. Stage efficiency correlations, relating various operating parameters to the column performance, were derived from parametric studies performed in Aspen Custom Modeler®. Preliminary simulations indicated that the efficiency correlations were only necessary for the absorber columns; the regenerator columns were adequately represented by the default equilibrium stage models. Hypothetical components were created for the hot potassium carbonate system and the standard Peng-Robinson property package model in HYSYS® was modified to include tabular physical property models to accommodate the hot potassium carbonate system. Relevant model parameters were determined from literature data. As for the Aspen Custom Modeler® process models, the HYSYS® CO₂ Removal Train process models were successfully validated against steady-state plant data. To demonstrate a potential application of the HYSYS® process models, dynamic simulations of the two most dissimilarly configured trains, CO₂ Removal Trains #1 and #7, were performed. Simple first-order plus dead time (FOPDT) process transfer function models, relating the key process variables, were derived to develop a diagonal control structure for each CO₂ Removal Train. The FOPDT model is the standard process engineering approximation to higher order systems, and it effectively described most of the process response curves for the two CO₂ Removal Trains. Although a few response curves were distinctly underdamped, the quality of the validating data for the CO₂ Removal Trains did not justify the use of more complex models than the FOPDT model. While diagonal control structures are a well established form of control for multivariable systems, their application to the hot potassium carbonate process has not been documented in literature. Using a number of controllability analysis methods, the two CO₂ Removal Trains were found to share the same optimal diagonal control structure, which suggested that the identified control scheme was independent of the CO₂ Removal Train configurations. The optimal diagonal control structure was tested in dynamic simulations using the MATLAB® numerical computing environment and was found to provide effective control. This finding confirmed the results of the controllability analyses and demonstrated how the HYSYS® process model could be used to facilitate the development of a control strategy for the Moomba CO₂ Removal Trains. In conclusion, this work addressed the development of a new non-equilibrium rate-based model for the hot potassium carbonate process and its application to the Moomba CO₂ Removal Trains. Further work is recommended to extend the model validity over a wider range of operating conditions and to expand the dynamic HYSYS® simulations to incorporate the diagonal control structures and/or more complex control schemes. / http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1350259 / Thesis (Ph.D.) - University of Adelaide, School of Chemical Engineering, 2009

Chemical absorption and desorption processes are two fundamental operations in the process industry. Due to the rate-controlled nature of these processes, classical equilibrium stage models are usually inadequate for describing the behaviour of chemical absorption and desorption processes. A more effective modelling method is the non-equilibrium rate-based approach, which considers the effects of the various driving forces across the vapour-liquid interface. In this thesis, a new non-equilibrium rate-based model for chemical absorption and desorption is developed and applied to the hot potassium carbonate process CO₂ Removal Trains at the Santos Moomba Processing Facility. The rate-based process models incorporate rigorous thermodynamic and mass transfer relations for the system and detailed hydrodynamic calculations for the column internals. The enhancement factor approach was used to represent the effects of the chemical reactions. The non-equilibrium rate-based CO₂ Removal Train process models were implemented in the Aspen Custom Modeler® simulation environment, which enabled rigorous thermodynamic and physical property calculations via the Aspen Properties® software. Literature data were used to determine the parameters for the Aspen Properties® property models and to develop empirical correlations when the default Aspen Properties® models were inadequate. Preliminary simulations indicated the need for adjustments to the absorber column models, and a sensitivity analysis identified the effective interfacial area as a suitable model parameter for adjustment. Following the application of adjustment factors to the absorber column models, the CO₂ Removal Train process models were successfully validated against steady-state plant data. The success of the Aspen Custom Modeler® process models demonstrated the suitability of the non-equilibrium rate-based approach for modelling the hot potassium carbonate process. Unfortunately, the hot potassium carbonate process could not be modelled as such in HYSYS®, Santos’s preferred simulation environment, due to the absence of electrolyte components and property models and the limitations of the HYSYS® column operations in accommodating chemical reactions and non-equilibrium column behaviour. While importation of the Aspen Custom Modeler® process models into HYSYS® was possible, it was considered impractical due to the significant associated computation time. To overcome this problem, a novel approach involving the HYSYS® column stage efficiencies and hypothetical HYSYS® components was developed. Stage efficiency correlations, relating various operating parameters to the column performance, were derived from parametric studies performed in Aspen Custom Modeler®. Preliminary simulations indicated that the efficiency correlations were only necessary for the absorber columns; the regenerator columns were adequately represented by the default equilibrium stage models. Hypothetical components were created for the hot potassium carbonate system and the standard Peng-Robinson property package model in HYSYS® was modified to include tabular physical property models to accommodate the hot potassium carbonate system. Relevant model parameters were determined from literature data. As for the Aspen Custom Modeler® process models, the HYSYS® CO₂ Removal Train process models were successfully validated against steady-state plant data. To demonstrate a potential application of the HYSYS® process models, dynamic simulations of the two most dissimilarly configured trains, CO₂ Removal Trains #1 and #7, were performed. Simple first-order plus dead time (FOPDT) process transfer function models, relating the key process variables, were derived to develop a diagonal control structure for each CO₂ Removal Train. The FOPDT model is the standard process engineering approximation to higher order systems, and it effectively described most of the process response curves for the two CO₂ Removal Trains. Although a few response curves were distinctly underdamped, the quality of the validating data for the CO₂ Removal Trains did not justify the use of more complex models than the FOPDT model. While diagonal control structures are a well established form of control for multivariable systems, their application to the hot potassium carbonate process has not been documented in literature. Using a number of controllability analysis methods, the two CO₂ Removal Trains were found to share the same optimal diagonal control structure, which suggested that the identified control scheme was independent of the CO₂ Removal Train configurations. The optimal diagonal control structure was tested in dynamic simulations using the MATLAB® numerical computing environment and was found to provide effective control. This finding confirmed the results of the controllability analyses and demonstrated how the HYSYS® process model could be used to facilitate the development of a control strategy for the Moomba CO₂ Removal Trains. In conclusion, this work addressed the development of a new non-equilibrium rate-based model for the hot potassium carbonate process and its application to the Moomba CO₂ Removal Trains. Further work is recommended to extend the model validity over a wider range of operating conditions and to expand the dynamic HYSYS® simulations to incorporate the diagonal control structures and/or more complex control schemes. / http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1350259 / Thesis (Ph.D.) - University of Adelaide, School of Chemical Engineering, 2009

No description available.

No description available.

Cross-linked poly(ethylene oxide) (XLPEO) based on poly(ethylene glycol) diacrylate (PEGDA) is an amorphous rubbery material with potential applications for carbon dioxide removal from mixtures with light gases such as methane, hydrogen, oxygen and nitrogen. Changing the polymer network structure of XLPEO through copolymerization has previously been shown to influence gas transport properties, which correlated with fractional free volume according to the Cohen-Turnbull model. This project explores strategic modifications of the cross-linked polymer structure and their effect on the chemical, physical and gas transport properties with an aim to develop rational, molecular-based design rules for tailoring separation performance. Experimental results from calorimetric and dynamic thermal analysis studies are presented, along with pure gas permeability and solubility obtained at 35°C. Incorporation of dangling side chains by copolymerization of PEGDA with methoxy-terminated poly(ethylene glycol) methyl ether acrylate, n=8 (PEGMEA) was previously shown to be effective in increasing fractional free volume of XLPEO through the opening of local free volume elements, which in turn increased CO₂ permeability. Through a comparative study ofshort chain analogs to these co-monomers, incorporation of an ethoxy-terminated co-monomer was shown to be more effective than a comparable methoxy-terminated co-monomer in increasing gas permeability. For instance, copolymerization of PEGDA with 71 wt% ethoxy-terminated diethylene glycol ethyl ether acrylate increased CO₂ permeability from 110 barrer to 320 barrer. Gas permeability increase was not observed when hydroxy or phenoxy-terminated pendants were introduced, which was attributed to reduction in chain mobility due to increased inter-chain chemical interactions or steric restrictions, respectively. Based on these results, incorporation of a co-monomer containing a bulky non-polar terminal group, tris-(trimethylsiloxy)silyl, was examined in order to further increase gas permeability. Addition of 80 wt% TRIS-A co-monomer increased CO₂ permeability of cross-linked PEGDA to 800 barrer. However, the resulting changes in chemical character of the copolymer reduced CO₂/light gas selectivity, even as gas permeability increased. The effect of incorporating a bulky, stiff functional group in the cross-linker chain was studied using cross-linked bisphenol-A ethoxylate diacrylate, which showed 40% increase in permeability compared to cross-linked PEGDA. This study affirmed the importance of polymer chain interaction, in addition to free volume, in determining the gas transport properties of the polymer. / text

abstract: Research confirms that climate change is primarily due to the influx of greenhouse gases from the anthropogenic burning of fossil fuels for energy. Carbon dioxide (CO2) is the dominant greenhouse gas contributing to climate change. Although research also confirms that negative emission technologies (NETs) are necessary to stay within 1.5-2°C of global warming, this dissertation proposes that the climate change problem has been ineffectively communicated to suggest that CO2 emissions reduction is the only solution to climate change. Chapter 1 explains that current United States (US) policies focus heavily on reducing CO2 emissions, but ignore the concentrations of previous CO2 emissions accumulating in the atmosphere. Through political, technological, and ethical lenses, this dissertation evaluates whether the management process of CO2 emissions and concentrations in the US today can effectively combat climate change. Chapter 2 discusses the historical management of US air pollution, why CO2 is regulated as an air pollutant, and how the current political framing of climate change as an air pollution problem promotes the use of market-based solutions to reduce emissions but ignores CO2 concentrations. Chapter 3 argues for the need to reframe climate change solutions to include reducing CO2 concentrations along with emissions. It presents the scientific reasoning and technological needs for reducing CO2 concentrations, why direct air capture (DAC) is the most effective NET to do so, and existing regulatory systems that can inform future CO2 removal policy. Chapter 4 explores whether Responsible Innovation (RI), a framework that includes society in the innovation process of emerging technologies, is effective for the ethical research and deployment of DAC; reveals the need for increased DAC governance strategies, and suggests how RI can be expanded to allow continued research of controversial emerging technologies in case of a climate change emergency. Overall, this dissertation argues that climate change must be reframed as a two-part problem: preventing new CO2 emissions and reducing concentrations, which demands increased investment in DAC research, development, and deployment. However, without a national or global governance strategy for DAC, it will remain difficult to include CO2 concentration reduction as an essential piece to the climate change solution. / Dissertation/Thesis / Doctoral Dissertation Civil, Environmental and Sustainable Engineering 2020

No description available.

Der anhaltende Anstieg der anthropogenen Treibhausgasemissionen führt zu einer erheblichen Verschärfung des Klimawandels und bedroht damit zunehmend die Integrität der Biosphäre und Gesellschaften weltweit. Negative Emissions-Technologien (NETs) wie die Pyrogene Kohlenstoffbindung und -speicherung (PyCCS) bieten potenzielle Lösungsansätze zur Minderung dieser Bedrohung. Diese Dissertation umfasst drei Studien, in denen das Vegetationsmodell LPJmL angewendet wird, um die globalen biogeochemischen Potenziale von PyCCS unter verschiedenen Implementierungsszenarien zu analysieren und die damit verbundenen Landnutzungsdynamiken zu evaluieren, die zu den kritischsten Zielkonflikten gehören. Zunächst zeigt die erste Studie mithilfe einer bedarfsorientierten Analyse, dass die Speicherung von Pflanzenkohle im Boden das Potenzial aufweist, NE von einem Umfang zu liefern, der laut klima-ökonomischen Szenarien zur Begrenzung der globalen Klimaerwärmung auf 1,5°C erforderlich wäre, was als besonders schwer vereinbar mit Naturschutz identifiziert wird. Die zweite Studie untersucht darauffolgend einen PyCCS-Ansatz, der den Landnutzungsdruck reduziert, indem Ackerflächen für PyCCS freigegeben werden, während die Kalorienversorgung auf den verbleibenden Anbauflächen durch Ertragssteigerungen mittels Pflanzenkohlezuführung aufrechterhalten wird. Dieser Ansatz könnte NE aus Bioenergie mit CO2-Abscheidung und -Speicherung—eine wichtige NET in ökonomischen Mitigationsszenarien—ersetzen und Flächen freigeben, die alternativ die Kalorienproduktion oder Naturschutzflächen fördern könnten. Im Rahmen der dritten Studie baut die Dissertation das Verständnis über das Potenzial von LCN-PyCCS als Instrument zur Klimastabilisierung durch die zusätzliche Darstellung der sich verbreitenden Praxis der Pflanzenkohle-basierten Düngung und Sensitivitätsanalysen der angenommenen Pyrolyseparameter und Bewirtschaftungsintensitäten weiter aus. / The ongoing rise in anthropogenic greenhouse gas emissions is significantly exacerbating climate change, which poses an increasing threat to the integrity of the biosphere and societies worldwide. Negative emission technologies (NETs) like Pyrogenic carbon capture and storage (PyCCS) offer potential mitigation solutions. This dissertation comprises three studies that apply the Dynamic Global Vegetation Model LPJmL to estimate global biogeochemical potentials of PyCCS under different deployment scenarios and evaluate the associated land use dynamics, which are among the most critical potential trade-offs. The first study is a demand-driven analysis aiming to achieve NEs projected to be required for limiting global warming to 1.5°C by PyCCS deployment. It finds that that biochar application has the potential to deliver these NEs — yet only under significant land use expansion, posing a significant threat to areas identified as particularly relevant for conservation. Subsequently, a novel approach to PyCCS deployment was assessed that reduces land pressure by releasing cropland to PyCCS feedstock production while maintaining calorie supply through biochar-mediated yield increases on remaining cropland. Based on this allocation scheme and LPJmL-computed biomass yields, a sequestration potential of 0.44–2.62 Gt CO2 yr−1 was quantified alongside calculating the potential benefits of replacing NE from BECCS (bioenergy with carbon capture and storage — a prominent NET in stabilization scenarios of climate economics) with PyCCS for nature restoration and calorie production. The understanding of the potential for LCN-PyCCS as a strategy for climate stabilization was further expanded by the representation of the emerging practice of biochar-based fertilization (i.e., biochar applied as mixtures with fertilizer at lower rates than the previously evaluated soil amendment) and sensitivity analyses of assumed pyrolysis parameters and management intensities in the third study.

Conversion of natural gas and other light hydrocarbons via steam reforming is currently the major process for hydrogen production. However, conventional hydrogen production technologies are not cost effective and therefore, cost is the biggest impediment to use hydrogen in fuel cell applications. In order to optimize and overcome cost problems in hydrogen production, sorption and membrane enhanced reaction processes are the two novel technologies for in situ operation of reforming and removal of carbon dioxide. Adsorption of carbon dioxide onto activated hydrotalcite and activated soda, obtained from either trona or NaHCO3, had been studied using a stainless steel packed bed tubular reactor as a function of temperature. Adsorption of CO2 in the presence and absence of steam onto activated hydrotalcite was conducted in the temperature range of 400-527 oC, whereas sorption studies with activated soda were performed for 80 to 152 oC in the presence of steam. Also, two-parameter deactivation model was developed to justify the experimental data and predictions of the breakthrough curves by deactivation model indicated a good agreement with the experimental results. In order to obtain physical properties of the sorbents, untreated and calcined sorbents were characterized by using TGA, B.E.T (N2 adsorption), and Hg porosimetry techniques. When hydrotalcite was used as the sorbent, total adsorption capacity of the material reduced from 1.18 mol/kg to 0.66 mol/kg as the temperature was increased from 400 oC to 527 oC. On the other hand, activated soda exhibited a total adsorption capacity 1.15 to 0.68 mol/kg for a temperature change from 80 to 152 oC. For high temperature removal of CO2, hydrotalcite and its promoted forms (using K2CO3 or Na2CO3) are pretty good sorbents to be used in single step hydrogen production processes, such as SERP. On the other hand, activated soda could also be used for CO2 abatement of the effluent gas from the reformer only when the temperature is lowered enough to obtain efficient adsorption capacity within the multi-bed adsorbers.