This work seeks to compare various Acetone-Butanol-Ethanol (ABE) fermentation extraction chemicals on an economic and environmental basis. The chemicals considered are: decane, a decane/oleyl alcohol blend, decanol, a decanol/oleyl alcohol blend, 2-ethyl-hexanol, hexanol, mesitylene, and oleyl alcohol. To facilitate comparison a pure-distillation base case was also considered. The aforementioned extractants are a mix of both toxic and non-toxic extractants. Non-toxic extractants can be used directly in fermentation reactors, improving overall fermentation yield by removal of toxic butanol. The extractants were modelled in Aspen Plus V8.8 and separation trains were designed to take advantage of extractant properties. The separation section of the plant was then integrated with upstream and downstream units to determine the Minimum Butanol Selling Prices (MBSP) for second generation extractive ABE fermentation. Upstream processes include biomass (switchgrass) solids processing, biomass pre-treatment/saccharification and fermentation while downstream processes include utility generation and wastewater treatment. The cost of CO2 equivalent emissions avoided (CCA) was used as a metric to compare environmental impact of each process as compared to gasoline. The economic best and environmental best extractant is shown to be 2-ethyl-hexanol with a MBSP of $1.58/L and a CCA of $471.57/tonne CO2 equivalent emissions avoided. Wastewater treatment, which is often ignored in other works, was found to makeup over 30% of total installed capital cost for all extractants. / Thesis / Master of Applied Science (MASc)

Grape pomace (GP) is one of the most abundant and underutilized fruit-derived wastes. GP is generated during winemaking, occupying over 60% of the total solid winery wastes. GP may cause serious environmental problems if it is not properly handled. On the other hand, it is rich in valuable compounds that are worthy of recovery. Although research has been working on GP upgrading, the utilizations are limited to producing a single product (e.g., grape seeds oil or polyphenol powders), which leads to large volumes of secondary wastes left. Therefore, the goal of this study is to develop an integrated process for the comprehensive utilization of GP by the production of multiple value-added products and evaluate its economic feasibility at a commercial scale. First, the chemical composition of different industrial GPs was analyzed to lay the foundation for the process design. Based on the analyzed chemical composition, an integrated process was developed to produce grape oil, polyphenols, and biofuels from GP. In this process, GP was extracted by hexane to produce oil, followed by aqueous ethanol solution extraction to obtain polyphenols. The solid residue rich in structural carbohydrates was then pretreated by alkali to partially remove lignin and enzymatically hydrolyzed to produce monomer sugars. The produced sugars were used as feedstock to produce acetone, butanol and ethanol (ABE) through anaerobic fermentation. Under the optimized conditions, the process was able to produce 71.9 g crude oil, 322.8 g crude polyphenols (equivalent to 72.6 g gallic acid), and 20.7 g ABE from 1 kg dry GP. Besides the valuable products, the process co-generated a large amount (50% of input GP biomass) of secondary waste, which is rich in lignin. Therefore, we further converted the secondary waste to biochars and evaluated their potential application in water purification by removing lead (Pb) from contaminated water. Based on the results, the produced biochar showed a high Pb adsorption ability (134 mg/g), with 66.5% of lead removal achieved within the first 30 min. Experimental and modeling results indicated that both physisorption and chemisorption mechanisms were involved in the Pb adsorption of the biochar. Finally, techno-economic analysis was conducted to evaluate the economic feasibility of the integrated processing of GP into oil, polyphenols, and biochar at an industrial scale. The results showed that compared with generating of single product or dual products, the integrated process aiming to produce multiple products had the best economic performance with the net present value (NPV), internal rate of return (IRR), and payback period of $135.0 million, 47.5%, and 1.8 years, respectively. Sensitivity analysis showed that plant capacity and polyphenol selling price had major impacts on process economics. Therefore, a suggestion for implementing this integrated process is to invest more in the polyphenol production and purification process to generate high-quality polyphenols with a high selling price and running the plant with a large capacity. Overall, we explored a novel integrated process that aims to produce multiple value-added products to increase the economic gain for the wine industry, and at the same time, potentially reduce the environmental burdens caused by GP disposal. / Doctor of Philosophy / During wine making, a large amount of solid waste is generated, and the major one is called grape pomace (GP). GP is mainly consisted of grape skins, seeds, and some stems. Normally, GP is discarded as waste; however, if it is not handled properly, GP may cause serious damages to the environment such as contaminating soil and stream water. On the other hand, GP has valuable compounds that could be recovered for other applications. Previous researchers used GP to produce a single product, which still leads to a large amount of components not used. Therefore, the aim of the current study is to design a process to comprehensively utilize GP to produce multiple value-added products. The developed process can produce grape seed oil, polyphenols, and biofuels from GP. The solid residue generated from the designed process was further converted into biochar, which can be used as an excellent adsorbent to remove lead (Pb) from contaminated water. Based on the economic model results, the developed process to convert GP into grape seed oil, polyphenols, and biochar could be a promising investment at an industrial scale. Generally speaking, various valuable products were obtained from low value GP waste, which could not only reduce the potential environmental problems caused by waste disposal, but also provide different value-added products for food, pharmacy, chemical, and energy industries.

La préoccupation de plus en plus importante ces dernières décennies, liée à l’épuisement des ressources pétrolières et au réchauffement climatique par les gaz à effet de serre a accentué l’intérêt du butanol comme carburant alternatif dans le secteur des transports grâce à ses propriétés adaptées pour le moteur à allumage par compression. Cependant, le faible rendement des procédés de production et de séparation empêche encore sa commercialisation en tant que carburant. C’est pourquoi le mélange de fermentation intermédiaire de la production de butanol, Acétone-Butanol-Ethanol(ABE), est de plus en plus considéré comme un carburant alternatif potentiel en raison de ses propriétés similaires au butanol et de ses avantages quant à son cout énergétique pour sa fabrication.Dans ce cadre, ce travail a pour objectif d’étudier l’impact des propriétés de différents mélanges d’ABE et n-dodécane en comparaison avec des mélanges d’alcools (éthanol et butanol) sur le processus de pulvérisation et de combustion et ce,pour différentes proportions en volume allant de 20% à 50%. Pour cela, une nouvelle chambre de combustion appelée"New One Shot Engine ", a été réalisée et utilisée car les conditions haute pression et haute température de "Spray-A" (60bars, 800-900 K et 22,8 kg/m³) définies par le réseau Engine Combustion network (ECN) peuvent être atteintes. Autant les phases liquides et vapeur que de combustion ont été caractérisées grâce à l’utilisation des plusieurs techniques optiques (extinction, Schlieren, chimiluminescence d’OH*) dans des conditions non réactives (Azote pur) et réactives (avec15% d'oxygène). Ces résultats expérimentaux ont non seulement permis d’étudier l’impact en oxygène moléculaire et de fournir une nouvelle base de données fiables, mais aussi d’affirmer la possibilité d’utiliser jusque 20% d’ABE en volume dans des moteurs à allumage par compression, grâce à ses caractéristiques de pulvérisation et de combustion similaires au carburant Diesel conventionnel. / The growing concern in recent decades, linked to the depletion of oil resources and global warming by greenhouse gases has increased the interest of butanol as an alternative fuel in the transport sector. However, the low yield of production and separation processes still prevents its commercialization as a fuel. Therefore, the intermediate fermentation mixture of butanol production, Acetone-Butanol-Ethanol (ABE), is increasingly considered as a potential alternative fuel because of its similar properties to butanol and its advantages in terms of the energy and cost in the separation process.The context of this work aims to study the impact of fuel properties on the spray and combustion processes of ABE mixture and alcohol fuels, blended with the diesel surrogate fuel, n-dodecane, in different volume ratio from 20% to 50%. A new combustion chamber called "New One Shot Engine," was designed and developed to reach the high-pressure and high temperatureconditions of "Spray-A" (60 bar, 800-900 K and 22.8 kg/m³) defined by the Engine Combustion Network (ECN).The macroscopic spray and combustion parameters were characterized by using the several optical techniques (extinction,Schlieren, chemiluminescence of OH*) under non-reactive (pure Nitrogen) and reactive (15% of oxygen) conditions. These experimental results not only made it possible to study the molecular oxygen impact and provide a new accurate database,but also to affirm the possibility of using ABE up to 20% by volume in compression-ignition engines, as its spray and combustion characteristics similar to conventional diesel fuel.

Butanol production by four different Clostridium sp. strains was investigated using glucoseP2-medium supplemented with increasing concentrations of butyric acid, added as cosubstrate.Batch fermentations were carried out in serum bottles (freely-suspended cellcultures) and fibrous-bed bioreactor (FBB) with medium recirculation (immobilized cells).Butyric acid clearly revealed to inhibit cellular growth with all specific growth rates decliningupon the increase of butyrate concentrations. However, the presence of low and moderatelevels in the medium can readily enhance the ABE-fermentation and increase butanolproduction through a shift induction towards the solventogenic phase controlled by themedium pH. In all cases it was found that 4.0 g⋅l-1 is the optimal concentration of butyratethat maximizes the yields for all ABE-solvents and butanol productivities. The non-mutant C.acetobutylicum ATCC 824 was singled out as the most efficient butanol productive strainamong all bacteria tested (10.3 g⋅l-1 butanol versus 0.72 g⋅l-1 with and without 4.0 g⋅l-1butyrate, respectively) showing a productivity augment in the order of 0.078 g⋅l-1⋅h-1 (78.5%)and yields of 0.3 g⋅g-1 from substrate and 7.6 g⋅g-1 from biomass versus 0.072 g⋅g-1 and 0.41g⋅g-1 with and without the optimal butyrate concentration, respectively. This strain alsorevealed the best overall tolerance over increasing butyrate concentrations up to ∼6.0 g⋅l-1 andthe highest glucose uptake (65.5%) among all bacteria. Furthermore, the beneficial effects ofbutyric acid were also observed through the use of a fibrous bed-bioreactor when the mutatedstrains of C. beijerinckii ATCC 55025 and BA 101 were tested. The use of this immobilizedcell system effectively improved butanol production over the free system with butanol titersin the fermentation broth around 11.5 g⋅l-1 and 9.4 g⋅l-1 for the two bacteria, respectively,roughly doubling the values attained with the corresponding suspended cell cultures when themedia were supplemented with 4.0 g⋅l-1 of butyrate. All these results confirm theenhancement of butanol formation using either free or immobilized cell culturessupplemented with butyric acid concentrations up to 4.0 g⋅l-1 in the media.