The increased demand of fossil fuel along with the depletion of economical crude oil resources, environmental challenges such as the accumulation of CO2 and other greenhouse gases in the atmosphere and the reduction of the dependence on imported oil are some of the motivations for the huge interest in biofuels. Biobutanol produced from ABE fermentation has been considered to be a good partial replacement for fossil fuels. However, challenges such as the need for inexpensive feed-stocks, improved fermentation performance to achieve higher final butanol concentration and higher yield, an efficient method for solvent recovery, and water recycle are the main obstacles to make the production of this alcohol economically viable. Pervaporation, a membrane-based process, is considered to be an attractive separation method to remove butanol from ABE fermentation broth. Among the membranes used for butanol separation, PDMS membranes showed reasonable performance such as good permeability, and appropriate selectivity for butanol separation by pervaporation. However, PDMS membranes need to be improved in terms of performance to be applicable in large scale butanol production plants. In this study, activated carbon nanoparticles have been embedded into the matrix of the PDMS membrane to improve its separation performance and, in particular, the permeation flux and butanol selectivity. Result showed that the presence of nanoparticles improves the PDMS membrane performance up to a certain particle loading. Moreover, it was shown that the operating conditions have a major impact on the pervaporation membrane separation process. The best membrane for pervaporation separation of butanol from binary aqueous solutions was obtained for a 6 wt% particle concentration where the total permeation flux and butanol selectivity increased by 42.6% and 51.9%, respectively, compared to neat PDMS membranes. Moreover, the best performance for the separation of butanol from ABE model solutions was achieved for an 8 wt% nanoparticle loading. Both the selectivity for butanol and the total permeation flux more than doubled in comparison to neat PDMS membranes prepared in this study. Moreover, in order to compare the PDMS/AC mixed matrix membrane performance for pervaporation separation of butanol from binary and ABE model solutions with PDMS membranes available on the market, experiments were also performed with a commercial PDMS membrane. Result of butanol separation from ABE model solutions showed that mixed matrix membranes with 8 wt% nanoparticles loading had a higher permeation flux than that of the commercial membranes. It was clearly shown that the presence of activated carbon nanoparticles in the matrix of the PDMS would be beneficial for the pervaporation separation of butanol from ABE fermentation broths. To better comprehend how the presence of activated carbon nanoparticles in the polymeric membranes enhance the performance of the membranes, a series of numerical simulations were performed. A finite difference model was developed to simulate the mass transfer of permeating components through mixed matrix membranes by pervaporation for a wide range of relative permeability, nanoparticle loading, particle shape, particle size and different filler adsorption isotherms. Finally, an investigation has been performed to optimize the butanol pervaporation separation process from ABE fermentation broth at an industrial scale.

Liquid biofuels produced from biomass have the potential to partly replace gasoline. One of the most promising biofuels is butanol which is produced in acetone-butanol-ethanol (ABE) fermentation. The ABE fermentation is characterized by its low butanol concentration in the final fermentation broth. In this research, the simulation of three in situ recovery methods, namely, vacuum fermentation, gas stripping and pervaporation, were performed in order to increase the efficiency of the continuous ABE fermentation by decreasing the effect of butanol toxicity. The non-integrated and integrated butanol production systems were simulated and optimized based on a number of objectives such as maximizing the butanol productivity, butanol concentration, and butanol yield. In the optimization of complex industrial processes, where objectives are often conflicting, there exist numerous potentially-optimal solutions which are best obtained using multi-objective optimization (MOO). In this investigation, MOO was used to generate a set of alternative solutions, known as the Pareto domain. The Pareto domain allows to view very clearly the trade-offs existing between the various objective functions. In general, an increase in the butanol productivity resulted in a decrease of butanol yield and sugar conversion. To find the best solution within the Pareto domain, a ranking algorithm (Net Flow Method) was used to rank the solutions based on a set of relative weights and three preference thresholds. Comparing the best optimal solutions in each case study, it was clearly shown that integrating a recovery method with the ABE fermentation significantly increases the overall butanol concentration, butanol productivity, and sugar conversion, whereas butanol yield being microorganism-dependent, remains relatively constant.

Diplomová práce se zabývá studiem signální dráhy produkce butanolu bakterií rodu Clostridium. V první části pojednává o modelování signálních drah pomocí metod systémové biologie. Navazuje popisem zisku dat pro tvorbu a úpravu modelů signálních drah s hlavním zaměřením na techniky pro zjištění genové exprese, produkce a fenotypu. Třetí sekcí je získání základního modelu signální dráhy zapojené do produkce butanolu u solventogenních klostridií. Posledním bodem a zároveň hlavním cílem je vytvoření dynamického modelu signální dráhy produkce butanolu kmene Clostridium beijerinckii NRRL B-598, jeho vyhodnocení pomocí statické a dynamické analýzy a srovnání s biologickými daty.

In this study, pervaporation, a membrane-based process was studied for in-situ separation of butanol. This technique has a great potential due to its high selectivity, low energy requirement and high efficiency. The primary objective was to improve the performance of the Polydimethylsiloxane (PDMS) membrane for the pervaporation separation and the recovery of butanol by adding nanoparticles into its matrix to make mixed matrix membrane (MMM). These nanoparticles included zinc-based Metal Organic Frameworks (MOFs) and zinc oxide. Different particle sizes of zeolitic imidazolate framework (ZIF-8) were synthesized. The separation performance of MMMs incorporating different sizes of ZIF-8 nanoparticles was compared to the performance of mixed matrix membranes incorporating zinc oxide as well as pure PDMS membrane. Different characteristics of ZIF-8 and their impact on the performance of the host membrane were discussed. Result showed that the presence of nanoparticles improves the PDMS membrane performance up to a certain particle loading. Moreover, it was shown that the particle size and interfacial bond between polymer and particles have a major impact on the pervaporation membrane separation process. The best membrane for pervaporation separation of butanol from binary aqueous solutions was obtained for the 8 wt% small-size ZIF-8/PDMS MMM where the total permeation flux and butanol selectivity were increased by 350% and 6%, respectively, compared to neat PDMS membranes. In addition to the MOFs, nanotubes are considered emerging nanostructured materials for use in membrane separation applications due to their high molecular diffusivity and unique geometry. Recent progress has also been made on the modification of nanotube surface functionality, and the fabrication of nanotube mixed matrix membranes as well as the ability to align them in MMMs. Since numerous types of nanotubes are available and the process of producing well-aligned nanotube MMMs is very challenging, a theoretical model using finite difference method (FD) was used to gain a deeper understanding on the effect of nanotubes on the separation performance of mixed matrix membranes. A series of numerical simulations were performed and the effects of various structural parameters, including the tubular filler volume fraction, orientation, length-to-diameter aspect ratio, and permeability ratio, were assessed. The results showed that the relative permeability is enhanced by vertically-aligned nanotubes and further increased with an increase of the permeability ratio, filler volume fraction and the length-to-diameter aspect ratio. In addition, comparing the simulation results with existing analytical models for the prediction of the relative permeability acknowledges a need to develop a new correlation that would provide more accurate predictions of the relative permeability of MMMs with embedded nanotube fillers.

京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第18332号 / 農博第2057号 / 新制||農||1023(附属図書館) / 学位論文||H26||N4839(農学部図書室) / 31190 / 京都大学大学院農学研究科応用生命科学専攻 / (主査)教授 植田 充美, 教授 渡邊 隆司, 教授 梅澤 俊明 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

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The separation of four or more components traditionally requires the use of three or more distillation columns. Due to the associated high costs, process intensification techniques have been studied. Semicontinuous separation is one method that allows multiple separations using one column integrated with middle vessels. This thesis aims to develop a new semicontinuous separation process that can separate a mixture with four or more components into high purity products with one column and two or more middle vessels. It is an extension of the conventional ternary semicontinuous process, which has been repeatedly shown to be profitable at intermediate throughputs when compared to continuous systems. The semicontinuous process operates in a forced cycle, with three operating modes that ensure separation objectives are met. The performance of the proposed quaternary semicontinuous separation is analyzed through rigorous dynamic simulations over a range of production capacities. To determine the feasibility, operability, and applicability to non-ideal mixtures, three case studies were considered: 1. Equimolar mixture of alkanes (n-hexane; n-heptane; n-octane; n-nonane). 2. Equimolar mixture of aromatics (benzene; toluene; ethyl-benzene; and o-xylene). 3. Non-ideal mixture of mixed-alcohols (methanol, ethanol, and water; propanol; isobutanol; pentanol and hexanol) The extendibility of the quaternary semicontinuous separation process, referred to as quintenary semicontinuous separation, is then evaluated on a five-component alkane mixture (n-hexane; n-heptane; n-octane; n-nonane; n-decane), via three case studies: 1. Equimolar mixture 2. Non-equimolar mixture, rich in light and heavy components. 3. Non-equimolar mixture, rich in intermediate components. The results for both the quaternary and quintenary semicontinuous processes indicate that this new technique is successful at achieving separation objectives while staying within safe operating limits. Comparison of both equimolar mixtures of alkanes for quaternary and quintenary semicontinuous processes with continuous systems indicates that the proposed system is profitable for intermediate flow rates. / Thesis / Master of Applied Science (MASc) / Traditionally, several large distillation columns (that can be hundreds of feet tall) are required to split a mixture of liquid chemicals into its individual components. Distillation is the separation of mixtures due to differences in boiling points. When the mixture is heated, the vapour phase will contain the components with lower boiling points, which can be separated once the vapour phase is cooled and condensed. The main goal of this research is to create a new system that can carry out the same separation, but using complex techniques that require only one column and a few extra storage tanks that are much cheaper and smaller than a distillation column. Different liquid mixtures were used to show how well the new process is able to separate the liquid into its individual components, while remaining in safe operating limits.

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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.