O aumento da conscientização ecológica, observado nos últimos anos, levou às indústrias investirem em alguns sistemas de produção tecnologicamente menos impactantes ao meio ambiente, como é o caso das biorrefinarias. No setor de celulose e papel as indústrias podem ser consideradas como biorrefinarias pois produzem bioenergia e bioprodutos a partir da utilização da biomassa, tais como energia elétrica e polpa celulósica. No processo de polpação kraft, obtém-se o licor negro o qual contém compostos orgânicos e inorgânicos provenientes da matéria prima e dos reagentes químicos e aditivos utilizados no processo. Com isso, o licor negro contém além da lignina dissolvida da madeira, alguns subprodutos formados em reações específicas e que podem ser recuperados, destacando-se entre esses o metanol, o qual pode chegar a compor 1% do licor negro. O metanol celulósico extraído na etapa de tratamento de condensado contaminado contém diversos compostos noviços ao meio ambiente e por este motivo o metanol celulósico é utilizado como combustível, sendo incinerado para geração de energia e para redução dos contaminantes a formas menos nocivas ao meio ambiente. Assim, obter o metanol celulósico significa purificá-lo para que possa ser aplicado para outros fins mais nobre, como por exemplo, aplicado como reagente nas indústrias químicas. Com isso, o presente estudo teve por objetivo avaliar o potencial de operação de uma unidade de recuperação e de purificação de metanol celulósico acoplado a uma moderna unidade de produção de polpa celulósica. Para isso, foram realizadas visitas técnicas à unidade industrial e efetuada uma ampla revisão bibliográfica do processo de evaporação de licor negro e de formação dos compostos presentes no metanol celulósico de forma a definir as condições e métodos de modelagem e simulação mais apropriados para o desenvolvimento desta dissertação. O estudo foi divido em duas etapas, sendo que a primeira consistiu na utilização do simulador comercial WinGEMS® para construção de um modelo computacional de uma unidade de evaporação de licor negro, o qual mostrou-se adequado para a determinada aplicação através de validações comparativas entre os resultados da simulação com valores reais de operação. Na sequência, desenvolveu-se um modelo computacional para o planejamento de uma unidade de obtenção e purificação de metanol celulósico via software Aspen Plus® sendo acoplado ao modelo anterior. Em síntese, a metodologia aplicada mostrou-se satisfatória para o presente estudo sendo possível simular com propriedade uma unidade de evaporação de licor negro e avaliar o impacto industrial de se acoplar uma unidade de purificação de metanol celulósico a indústria celulósica, no que tange a dimensionamentos de equipamentos, quantificação dos insumos e eficiência de purificação de metanol celulósico. / The increase in ecological awareness observed in recent years has led industries to invest in some production systems technologically less harmful to the environment, such as biorefineries. The industries form the pulp and paper sector, can be considered as biorefineries because they produce bioenergy and bioproducts from the use of biomassa, such as electric power and cellulosic pulp. In the kraft pulping process, the black liquor is obtained, wich contains organic and inorganic compounds from the raw material and from the chemicals reagents and additives used in the process. Black liquor contains, in addition to the dissolved lignin of the wood, some by-products formed in specific reactions and that can be recovered, among them methanol, which can make up 1% of the black liquor. The cellulosic methanol extracted in the treatment stage of contaminated condensate contains several compounds that are harmful to the environment and for this reason the cellulosic methanol is used as fuel, being incinerated for energy generation and for the reduction of contaminants to forms less harmful to the environment. Thus, obtaining the cellulosic methanol means purifying it so that it can be applied to other, more noble purposes, for example, as a reagent in the chemical industry. The aim of this study was to evaluate the potential of a cellulosic methanol recovery and purification unit coupled to a modern cellulosic pulp production unit. Technical visits were made to the industrial unit and a vast bibliographical review of the process of evaporation of black liquor and formation of the compounds present in the cellulosic methanol was carried out in order to define the conditions and the most appropriate modeling and simulation methods for the development of this dissertation. The study was divided in two stages, the first one consisted of the use of the WinGEMS® commercial simulator to construct a computational model of a black liquor evaporation unit, which proved to be suitable for the given application through comparative validations between simulation results with actual operating values. In the sequence, a computational model was developed for the planning of a cellulosic methanol purification and purification unit using Aspen Plus® software being coupled to the previous model. In summary, the applied methodology proved to be satisfactory for the present study, being it possible to properly simulate a black liquor evaporation unit and to evaluate the industrial impact of coupling a cellulosic methanol purification unit to the cellulosic industry, in terms of equipment design, input quantification and cellulosic methanol purification.

No description available.

No description available.

Face à l’enjeu de la transition énergétique, l’utilisation de la biomasse végétale ligno-cellulosique pour produire des énergies et matériaux ‘bio-sourcés’, est l’une des alternatives au pétrole ciblées. Le sorgho (Sorghum bicolor) est à ce titre de plus en plus étudié. Sa diversité génétique est une richesse considérable pour concevoir des variétés à forte production de biomasse de tige, de composition biochimique adaptée à divers usages et adaptées à des agroenvironnements limités en eau. Cette thèse s’inscrit dans deux projets d’amélioration variétale du sorgho biomasse, Biomass For the Future (ANR) et BioSorg (Agropolis-Cariplo). Son objectif est de comprendre les traits phénotypiques, de nature morphologique, biochimique, histologique, et leurs interactions, expliquant à l’échelle de l’organe (entrenœud) la production de biomasse de tige du sorgho, sa variabilité génotypique et en réponse à l’environnement climatique notamment hydrique. Pour cela une approche combinant expérimentations et modélisation écophysiologique a été adoptée.Trois saisons d’expérimentation ont été organisées au champ (plateforme DIAPHEN, Mauguio, France), afin de comparer des génotypes sous condition irriguée et déficitaire en eau durant la phase d’allongement des tiges. Deux hybrides de sorgho biomasse ont été étudiés (2013-2014) pour mettre en évidence les traits contribuant à la régulation par la disponibilité en eau de l’accumulation de la biomasse de tige. Une dynamique de développement commune à tous les entrenœuds d’un génotype a été mise en évidence pour les traits histochimiques étudiés ; les entrenœuds d’âge différent sur la tige d’une même plante peuvent donc être utilisés pour le phénotypage de cette dynamique. Ainsi, les traits fixés progressivement durant le développement de l’entrenœud s’avèrent les plus sensibles au déficit hydrique. La quantité de biomasse de tige produite a été réduite par le déficit hydrique et sa composition biochimique modifiée. Ceci s’explique par une réduction du nombre d’entrenœuds allongés, de leur longueur et teneur en ligno-cellulose, mais une augmentation de leur teneur en sucre soluble. Les entrenœuds développés après ré-irrigation ont montré une récupération remarquable à l’inverse des entrenœuds développés durant la période de stress. Ainsi, à la récolte, l’effet du déficit hydrique sur la production de la biomasse de tige était très atténué. Ces mêmes traits ont été étudiés sur 8 génotypes de morphologie et biochimie de tige contrastées (2014-2015). Les résultats ont montré une forte variabilité génotypique de sensibilité au déficit hydrique et de capacité de récupération. Les traits de croissance et histochimie de l’entrenœud ont montré des réponses au statut hydrique partiellement corrélées. La faible corrélation entre traits biochimiques et histologiques suggère que la variabilité de la qualité de tige entre génotypes et environnements s’explique au niveau tissulaire. La stabilité de la production de biomasse de tige est donc contrôlée par ces traits de façon complexe et fonction du pattern de disponibilité en eau.Ces résultats ont été utilisés pour adapter et tester la capacité du modèle écophysiologique Ecomeristem à capturer les traits expliquant la variabilité des phénotypes de sorgho biomasse sous conditions hydriques non limitantes. La validation du modèle s’est avérée satisfaisante avec quelques limites dans sa capacité à capturer les cinétiques de vie des talles et, de fait, la répartition de la biomasse entre talles. L’analyse de sensibilité du modèle a montré que les génotypes simulés produisant le plus de biomasse de tige résultent de combinaisons de traits différentes en fonction de la densité de peuplement. Le trade-off entre propension au tallage et à accumuler plus de biomasse au niveau de l’entrenœud individuel s’avère déterminante. La balance entre ces traits devrait être davantage considérée dans la démarche de phénotypage et d’idéotypage et sous des environnements contrastés. / In the context of the energy transition, the use of ligno-cellulosic biomass for producing ‘bio-sourced’ energy and product is one of the major alternatives to oil. Sorghum bicolor is with this respect more and more studied, particularly for water limited cropping environments. Its genetic diversity is a huge opportunity for creating varieties with a high production of stem biomass, with a biochemical composition adapted to diverse end-uses and for water-limited environments. This PhD thesis takes place in the context of two projects dedicated to biomass sorghum improvement: Biomass For the Future (ANR) and BioSorg (Fondation Agropolis-Cariplo). Its objective is to understand the morphological and histochemical traits and their interactions, underlying at organ (internode) level, stem biomass production in sorghum, its genotypic variability and its plasticity in response to climatic environment, in particular water availability. For this purpose, an approach combining field experiments and eco-physiological modeling was adopted. Three experimental seasons were organized in the field (DIAPHEN platform, Mauguio, France), in order to compare genotypes under contrasted water situations (irrigated, water deficit during stem elongation). Two biomass sorghum hybrids were studied (2013-2014) to point out the traits contributing to the regulation by water availability of stem biomass accumulation. First, a common dynamics of internode development for a given genotype was highlighted for studied histochemical traits. This result will enable to use all internodes of different ages on a given plant to set up such a dynamic in a phenotyping context. Accordingly, the traits set up progressively along internode development were those with the highest drought sensitivity. Stem biomass production was reduced by drought and its biochemical composition modified. This could be explained by a reduced number of expanded internodes with a reduced length and ligno-cellulosic content. A contrario, their soluble sugar content was increased. The internodes developed after re-watering observed a remarkable recovery whereas those developed under stress did not recover. At final harvest, water deficit effect on stem biomass production was thus strongly attenuated. The same traits were studied on 8 genotypes more contrasted for stem morphology and biochemistry (2014-2015). The results confirmed those on two hybrids and showed a high genotypic variability for drought sensitivity and recovery capacity. The response to water availability of traits related to internode or stem growth and to their biochemical composition was only partially correlated. The weak correlation between biochemical and histological traits suggests that the vartiability of stem biomass quality among genotypes and environments is explained at tissue level. The stability of stem biomass production is thus a highly complex process involving trade-off among morphological and histochemical traits that may differ depending on drought pattern, targeted end-use and cycle duration.These results were used for adapting and testing the ecophysiological model Ecomeristem in its capacity to capture the traits underlying phenotypic variability in biomass sorghum, in a first time under non-limiting water conditions. Model validation was satisfying but pointed out remaining limitation in the way the model captures tillering and accordingly biomass partitioning among them. A sensitivity analysis was performed showing that the simulated genotypes with the highest stem biomass production resulted from variable trait combinations (model parameters) depending on plant density in the field. The trade-off between tillering propensity and the capacity to accumulate biomass in the individual internode was particularly influencing and the balance between these traits should be further considered in a phenotyping and ideotyping context, with respect to fluctuating environmental conditions.

Interest in renewable energy and governmental mandates has motivated land managers to consider cellulosic feedstocks for bioenergy. I investigated plant community response to a system including switchgrass (Panicum virgatum) as a feedstock intercropped with loblolly pine (Pinus taeda). I estimated plant species evenness, richness, and diversity and biomass production, with emphasis on white-tailed deer (Odocoileus virginianus) forages. I detected 225 species in 2,220 1-m2 quadrats, and 7,495 biomass samples (96.4 kg dry weight) from 960 quadrats. Intercropping reduced plant species diversity, total non-pine tree biomass, and biomass of deer forages during switchgrass establishment. These effects were no longer apparent at treatment level two years after switchgrass establishment, except that deer browse and total deer forage biomass remained less in intercropped interbeds. Intercropping in managed pines may temporarily effect plant communities but further studies are needed to examine longer term effects and to quantify effects on nutritional carrying capacity for deer.

The use of biofuels in the United States has increased dramatically in the last few years. The largest source of feedstock for ethanol to date has been corn. However, corn is also a vitally important food crop and is used commonly as feed for cattle and other livestock. To prevent further diversion of an important food crop to production of ethanol, there is great interest in developing commercial-scale technologies to make ethanol from non-food crops, or other suitable plant material. This is commonly referred to as biomass. A review is made of lignocellulosic sources being considered as feedstocks to produce ethanol. Current technologies for pretreatment and hydrolysis of the biomass material are examined and discussed. Production data and cost estimates are culled from the literature, and used to assist in development of mathematical models for evaluation of production ramp-up profiles, and cost estimation. These mathematical models are useful as a planning tool, and provide a methodology to estimate monthly production output and costs for labor, capital, operations and maintenance, feedstock, raw materials, and total cost. Existing credits for ethanol production are also considered and modeled. The production output in liters is modeled as a negative exponential growth curve, with a rate coefficient providing the ability to evaluate slower, or faster, growth in production output and its corresponding effect on monthly cost. The capital and labor costs per unit of product are determined by dividing the monthly debt service and labor costs by that month’s production value. The remaining cost components change at a constant rate in the simulation case studies. This methodology is used to calculate production levels and costs as a function of time for a 25 million gallon per year capacity cellulosic ethanol plant. The parameters of interest are calculated in MATLAB with a deterministic, continuous system simulation model. Simulation results for high, medium, and low cost case studies are included. Assumptions for the model and for each case study are included and some comparisons are made to cost estimates in the literature. iv While the cost per unit of product decreases and production output increases over time, some reasonable cost values are obtained by the end of the second year for both the low and medium cost case studies. By the end of Year 2, total costs for those case studies are $0.48 per liter and $0.88 per liter, respectively. These cost estimates are well within the reported range of values from the reviewed literature sources. Differing assumptions for calculations made by different sources make a direct cost comparison with the outputs of this modeling methodology extremely difficult. Proposals for reducing costs are introduced. Limitations and shortcomings of the research activity are discussed, along with recommendations for potential future work in improving the simulation model and model verification activities. In summary, the author was not able to find evidence—within the public domain—of any similar modeling and simulation methodology that uses a deterministic, continuous simulation model to evaluate production and costs as a function of time. This methodology is also unique in highlighting the important effect of production ramp-up on monthly costs for capital (debt service) and labor. The resultant simulation model can be used for planning purposes and provides an independent, unbiased estimate of cost as a function of time.

The research described here encompasses several different aspects of lithium ion battery operation including deep eutectic electrolytes, manganese trapping evaluation, silicon monoxide anodes, and in-situ NMR development under both static and spinning conditions. Individually, the results of these investigations as contained within the corresponding chapters contribute valuable insight. Collectively, they represent a snapshot into the numerous different ways in which nuclear magnetic resonance spectroscopy is applicable to lithium ion battery characterization. For instance, the deep eutectic electrolytes thus studied were amenable to diffusion coefficient characterization via the 1H, 7Li and 19F nuclei. This provided dynamical information on the anion, cation and neutral component and lent itself well towards parameterization of molecular dynamics simulations. The results thus obtained were useful in describing this relatively understudied class of electrolytes. Another example is that of the evaluation of manganese trapping. In this context 7Li NMR measurements were used to investigate the competitive inhibition of manganese trapping in crown ethers by lithium. Candidate crown ethers were thus evaluated for their ability to trap Mn2+ and Mn3+ in a lithium rich environment. Given the detrimental effects that manganese dissolution from cathode materials has on cycle life performance, the NMR enabled assessment of the appropriate chelating agents had identifiable importance. Additionally described was the progress made with silicon monoxide anodes supported on cellulosic substrates. The high active material loadings achieved, while also intriguing from a performance perspective, enabled 29Si MAS-NMR and 7Li static in-situ NMR measurements. For the in-situ measurements in particular, a novel cell design was constructed to utilize the advantages of a cellulosic substrate in this context. This has also enabled preliminary work on a spinning in-situ design. / Thesis / Doctor of Philosophy (PhD)

No description available.

In order to meet the energy needs of a growing world in a sustainable manner, new high efficiency, carbon-neutral fuels and chemical feedstocks are required. An emerging approach that shows promise for high efficiency production of renewable fuels and chemicals is the use of purified enzymes combined in one pot to catalyze complex conversions: synthetic pathway biotransformations (SyPaB). An exemplary technology in this burgeoning field is the production of hydrogen from biomass sugars. Lignocellulosic biomass, which includes agricultural residues, energy crops, and industrial waste streams, is an ideal substrate for SyPaB conversion, as it is abundant and cheap, second only to untaxed coal on a $/energy content basis. But the structure of biomass is highly recalcitrant, making high-yield biological conversion difficult to achieve. In order to increase susceptibility to enzymatic digestion, thermochemical pretreatments are applied, with the goals of removing of lignin, the simplest example being soaking in aqueous ammonia (SAA); hemicellulose removal, most often using dilute acid (DA); and increasing cellulose accessibility by cellulose solvent-based pretreatments, such as cellulose solvent- and organic solvent-based lignocellulose fractionation (COSLIF). In a comparison of the lignin removal (SAA) and accessibility increase (COSLIF) approaches, we found that certain levels of lignin removal (~15%) were important, but further lignin removal was less effective at achieving digestibility gains than increasing cellulose accessibility. Pretreated biomass forms an excellent substrate for SyPaB hydrogen generation, due to low cost and high sugar content. Following experiments demonstrating the high yield conversion of sucrose to hydrogen (97%) and SyPaB generation of hydrogen at a rate commensurate with the best biological rates achieved, 157 mmol/L/h. SyPaB was combined with enzymatic hydrolysis to enable the direct conversion of cellulosic biomass, including untreated, DA, and COSLIF corn stover. In addition, an updated kinetic model of the system was used to rationally increase the maximum hydrogen production rate by 70% while minimizing total enzyme loading and without increasing substrate concentration. Together, these results demonstrate the high level of engineering control in cell-free systems, which can enable conversion of a variety of substrates to hydrogen at the highest possible yield and rates as high as any biohydrogen production method. / Ph. D.

The incentives and policies spearheaded by the U.S. government have created abundant opportunities for renewable fuel production and commercialization. Bio-butanol is a very promising renewable fuel for the future transportation market. Many efforts have been made to improve its production process, but seldom has bio-butanol research discussed the integration and optimization of a cellulosic bio-butanol supply chain network. This study focused on the development of a physical supply chain network and the optimization of a green supply chain network for cellulosic bio-butanol. To develop the physical supply chain network, the production process, material flow, physical supply chain participants, and supply chain logistics activities of cellulosic bio-butanol were identified by conducting an onsite visit and survey of current bio-fuel stakeholders. To optimize the green supply chain network for cellulosic bio-butanol, the life cycle analysis was integrated into a multi-objective linear programming model. With the objectives of maximizing the economic profits and minimizing the greenhouse gas emissions, the proposed model can optimize the location and size of a bio-butanol production plant. The mathematical model was applied to a case study in the state of Missouri, and solved the tradeoff between the feedstock and market availabilities of sorghum stem bio-butanol. The results of this research can be used to support the decision making process at the strategic, tactical, and operational levels of cellulosic bio-butanol commercialization and cellulosic bio-butanol supply chain optimization. The results of this research can also be used as an introductory guideline for beginners who are interested in cellulosic bio-butanol commercialization and supply chain design. / Ph. D. / Renewable energy is one of the most effective tools to fight the threats of climate change, global warming, food price rising, and energy dependence. Cellulosic bio-butanol, a renewable alcohol-based biofuel, is a very promising energy candidate to support the fight for these threats. Due to its low water miscibility, similar energy content and octane number with gasoline, blending ability with gasoline in any proportions, and its directly utilization in gasoline engine, cellulosic bio-butanol is a potential candidate to replace gasoline. Unlike bioethanol, which only relies its fuel distribution on railway and tanker trucks, bio-butanol is compatible with not only railway and tanker trucks but also current pipeline based fuel distribution infrastructures. In order to increase the competitively of this promising energy candidate, the cellulosic bio-butanol is worth to be commercialized. An important step for the commercialization of cellulosic bio-butanol is the network design of its supply chain. In this research, the supply chain network of cellulosic bio-butanol was constructed and optimized. The supply chain network of cellulosic bio-butanol was constructed by identifying the three important aspects of a supply chain network structure: structure dimension, participants in supply chain, and supply chain business process links. A) The structure dimension was identified by understanding the production process of bio-butanol. A case study was used to study the production process of cellulosic bio-butanol. B) The supply chain business process links were identified by conducting a survey on the logistics activities in bio-butanol supply chain. C) The participants of cellulosic bio-butanol supply chain were identified by identifying the physical infrastructure of cellulosic bio-butanol supply chain. The results of the literature review, case study and survey were analyzed to identify the physical infrastructure and the participants in the supply chain. It was found out that the supply chain network structure of cellulosic bio-butanol includes 4 tiers of horizontal structure: suppliers, producers, distributors, and customers. The suppliers refer to the local farmers and feedstock aggregators. The producers are the cellulosic bio-butanol production plants. The distributors are the fuel logistics companies and fuel distributors. The customers are the fuel companies. The cellulosic bio-butanol producers use contracts to connect with biomass suppliers, fuel distributors, and bio-butanol customers. Based on the proposed network structure of cellulosic bio-butanol supply chain, the optimization of the green cellulosic bio-butanol supply chain network was conducted. A multi-objective linear integer programming model was developed to design the green cellulosic bio-butanol supply chain network. Life cycle analysis (LCA) and net present value techniques were used in the proposed model to formulate the environmental and economic objective function. With the objectives of maximizing the economic profits while minimizing the greenhouse gas (GHG) emissions, the proposed model can optimize the location and the size of bio-butanol production plant. The model was applied using data from the state of Missouri (MO). The results showed that the optimal location of cellulosic bio-butanol production plant is in the southeastern region of MO. And the production size of bio-butanol production plant is based on the tradeoff between the economic and environmental objectives. The lower GHG emissions results in a smaller size of production plant.