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BACKGROUND: Ethanol production through fermentation of gas mixtures containing CO, CO2 and H2 has just started operating at commercial scale. However, quantitative schemes for understanding and predicting productivities, yields, mass transfer rates, gas flow profiles and detailed energy requirements have been lacking in literature; such are invaluable tools for process improvements and better systems design. The present study describes the construction of a hybrid model for simulating ethanol production inside a 700 m3 bubble column bioreactor fed with gas of two possible compositions, i.e., pure CO and a 3:1 mixture of H2 and CO2. RESULTS: Estimations made using the thermodynamics-based black-box model of microbial reactions on substrate threshold concentrations, biomass yields, as well as CO and H2 maximum specific uptake rates agreed reasonably well with data and observations reported in literature. According to the bioreactor simulation, there is a strong dependency of process performance on mass transfer rates. When mass transfer coefficients were estimated using a model developed from oxygen transfer to water, ethanol productivity reached 5.1 g L-1 h-1; when the H2/CO2 mixture is fed to the bioreactor, productivity of CO fermentation was 19% lower. Gas utilization reached 23 and 17% for H2/CO2 and CO fermentations, respectively. If mass transfer coefficients were 100% higher than those estimated, ethanol productivity and gas utilization may reach 9.4 g L-1 h-1 and 38% when feeding the H2/CO2 mixture at the same process conditions. The largest energetic requirements for a complete manufacturing plant were identified for gas compression and ethanol distillation, being higher for CO fermentation due to the production of CO2. CONCLUSIONS: The thermodynamics-based black-box model of microbial reactions may be used to quantitatively assess and consolidate the diversity of reported data on CO, CO2 and H2 threshold concentrations, biomass yields, maximum substrate uptake rates, and half-saturation constants for CO and H2 for syngas fermentations by acetogenic bacteria. The maximization of ethanol productivity in the bioreactor may come with a cost: low gas utilization. Exploiting the model flexibility, multi-objective optimizations of bioreactor performance might reveal how process conditions and configurations could be adjusted to guide further process development.

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The use of renewable jet fuels (RJFs) is an option for meeting the greenhouse gases (GHG) reduction targets of the aviation sector. Therefore, most of the studies have focused on climate change indicators, but other environmental impacts have been disregarded. In this paper, an attributional life cycle assessment is performed for ten RJF pathways in Brazil, considering the environmental trade-offs between climate change and seven other categories, i.e., fossil depletion, terrestrial acidification, eutrophication, human and environmental toxicity, and air quality-related categories, such as particulate matter and photochemical oxidant formation. The scope includes sugarcane and soybean for first-generation (1G) pathways and residual materials (wood and sugarcane residues, beef tallow, and used cooking oil-UCO) for second-generation (2G) pathways. Three certified technologies to produce RJF are considered: hydroprocessed esters and fatty acids (HEFA), alcohol-to-jet (ATJ), and Fischer-Tropsch (FT). Assuming the residual feedstocks as wastes or by-products, the 2G pathways are evaluated by two different approaches, in which the biomass sourcing processes are either accounted for or not. Results show that 1G pathways lead to significant GHG reductions compared to fossil kerosene from 55% (soybean/HEFA) to 65% (sugarcane/ATJ). However, the sugarcane-based pathway generated three-fold higher values than fossil kerosene for terrestrial acidification and air quality impacts, and seven-fold for eutrophication. In turn, soybean/HEFA caused five-fold higher levels of human toxicity. For 2G pathways, when the residual feedstock is assumed to be waste, the potential GHG emission reduction is over 74% with no relevant trade-offs. On the other hand, if the residual feedstocks are assumed as valuable by-products, tallow/HEFA becomes the worst option and pathways from sugarcane residues, even providing a GHG reduction of 67% to 94%, are related to higher impacts than soybean/HEFA for terrestrial acidification and air quality. FT pathways represent the lowest impacts for all categories within both approaches, followed by UCO/HEFA.

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In this chapter we aim to give an overview of the main societal and ethical issues that are currently voiced around industrial biotechnology. We will illustrate this with some recent cases, such as the development of synthetic artemisinin, synthetic vanillin and vegetable oil produced by engineered algae. We show that current societal and ethical issues in industrial biotechnology centre on the following five themes: sustainability, naturalness, innovation trajectories, risk management and economic justice. In each of these themes, clashing public opinions fuel the public debate on the acceptability of new industrial biotechnology. In some cases this has led to the failure of otherwise promising innovations. In the last part, we provide suggestions on how to deal with these ethical and societal aspects based on the approach of Responsible Research and Innovation (RRI).

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Syngas fermentation is one of the bets for the future sustainable biobased economies due to its potential as an intermediate step in the conversion of waste carbon to ethanol fuel and other chemicals. Integrated with gasification and suitable downstream processing, it may constitute an efficient and competitive route for the valorization of various waste materials, especially if systems engineering principles are employed targeting process optimization. In this study, a dynamic multi-response model is presented for syngas fermentation with acetogenic bacteria in a continuous stirred-tank reactor, accounting for gas-liquid mass transfer, substrate (CO, H2 ) uptake, biomass growth and death, acetic acid reassimilation, and product selectivity. The unknown parameters were estimated from literature data using the maximum likelihood principle with a multi-response nonlinear modeling framework and metaheuristic optimization, and model adequacy was verified with statistical analysis via generation of confidence intervals as well as parameter significance tests. The model was then used to study the effects of process conditions (gas composition, dilution rate, gas flow rates, and cell recycle) as well as the sensitivity of kinetic parameters, and multiobjective genetic algorithm was used to maximize ethanol productivity and CO conversion. It was observed that these two objectives were clearly conflicting when CO-rich gas was used, but increasing the content of H2 favored higher productivities while maintaining 100% CO conversion. The maximum productivity predicted with full conversion was 2 g·L-1 ·hr-1 with a feed gas composition of 54% CO and 46% H2 and a dilution rate of 0.06 hr-1 with roughly 90% of cell recycle.

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Selection of optimal technologies for novel biobased products and processes is a major challenge in process design, especially when are considered many alternatives available to transform materials into valuable products. Furthermore, such technological alternatives vary in their technical performances and cause different levels of economic and environmental impacts throughout their life cycles. Additionally, selection of optimal production pathways requires a shift from the traditional materials management practices to more sustainable practices. This contribution provides a method for optimizing multi-product network systems from a sustainability perspective by applying the GREENSCOPE framework as a sustainable objective function. A case study is presented in which the four GREENSCOPE target areas (i.e., efficiency, energy, economics, and environment) are evaluated by 21 preselected indicators as part of a multi-objective optimization problem of a biojet fuel production network. The biojet fuel production network evaluated in this study consists of four main elements: (1) feedstocks management, (2) conversion technologies, (3) co-products upgrading, and (4) auxiliary sections for in situ production of raw materials and utilities. For the sustainability objective function, the 21 indicators are analyzed considering multiple perspectives of stakeholders to study their influence on the decision-making process. It is, different sets of weighting factors are assigned to each of the four target areas. Hence, this sustainability evaluation from different stakeholders' perspectives allows identifying optimal networks, specific target areas with great potential for improvements, and processing steps with great influence in the entire network performance. As a result, diverse optimal network arrangements were obtained according to the multiple stakeholders' perspectives. This evidences that a win-win situation for all sustainability aspects considered can hardly be reached. Finally, this contribution demonstrated the applicability of the proposed methodology for sustainability evaluation, optimization, and decision-making in the context of a multi-product material facility by developing a multi-objective optimization model.

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An early stage assessment method is applied to the production of isobutanol from lignocellulosic biomass, and to three multiproduct portfolios from the conversion of isobutanol: Case 1: production of isobutyl acetate and glycerol tert-butyl ether (GTBE), Case 2: production of isobutyl acetate and ketones, and Case 3: production of isobutyl acetate alkanes. The method screens and compares each route with its equivalent petrochemical counterpart. The method is composed by different indicators involving economic and environmental aspects. Sensitivity analyses were carried out to account for variation in prices, weighting factors and distribution of isobutanol to isobutyl acetate (in multiproduct portfolios). Results show that bio-based isobutanol has advantages over fossil-based isobutanol. In multiproduct systems, case 1 performs better, followed by cases 2 and 3. Screening using economic or environmental aspects show to have a significant effect on the results, where bio-based systems tend to perform better when environmental aspects are included.

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This work investigates the potential for polyhydroxybutyrate (PHB) production from wastewater, from a techno-economic and an environmental perspective, examining scale-up opportunities and bottlenecks prior to commercialisation. Conceptual process design, economic, environmental impacts and sensitivity analysis are developed for one fermentation process and three downstream processing routes, based on alkali, surfactant-hypochlorite and solvent treatments. Environmentally and cost-wise, the alkali treatment is the most favourable with production costs of 1.40€/kg PHB, global warming potential of 2.4kgCO2-eq/kg PHB and non-renewable energy use of 106MJ/kg PHB. The solvent-based process yields the highest costs and environmental burdens: 1.95€/kg PHB, 4.30kgCO2-eq/kg PHB and 156MJ/kg PHB. The production of PHB from wastewater is identified as an interesting alternative to pure culture-polyhydroxyalkanoates production from sugars. However, these results are not yet competitive with those for the petrochemical counterparts. Additional performance improvements may be possible, through process integration and optimisation.

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In this work technical and economic analyses were performed to evaluate the glycerol transformation into Polyhydroxybutyrate using Bacillus megaterium. The production of PHB was compared using glycerol or glucose as substrates and similar yields were obtained. The total production costs for PHB generation with both substrates were estimated at an industrial scale. Compared to glucose, glycerol showed a 10% and 20% decrease in the PHB production costs using two different separation schemes respectively. Moreover, a 20% profit margin in the PHB sales price using glycerol as substrate resulted in a 166% valorization of crude glycerol. In this work, the feasibility of glycerol as feedstock for the production of PHB at laboratory (up to 60% PHB accumulation) and industrial (2.6US$/kgPHB) scales is demonstrated.

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The aim of this study is to present and apply a quick screening method and to identify the most promising bioethanol derivatives using an early-stage sustainability assessment method that compares a bioethanol-based conversion route to its respective petrochemical counterpart. The method combines, by means of a multi-criteria approach, quantitative and qualitative proxy indicators describing economic, environmental, health and safety and operational aspects. Of twelve derivatives considered, five were categorized as favorable (diethyl ether, 1,3-butadiene, ethyl acetate, propylene and ethylene), two as promising (acetaldehyde and ethylene oxide) and five as unfavorable derivatives (acetic acid, n-butanol, isobutylene, hydrogen and acetone) for an integrated biorefinery concept.

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Glycerol as a low-cost by-product of the biodiesel industry can be considered a renewable building block for biorefineries. In this work, the conversion of raw glycerol to nine added-value products obtained by chemical (syn-gas, acrolein, and 1,2-propanediol) or bio-chemical (ethanol, 1,3-propanediol, d-lactic acid, succinic acid, propionic acid, and poly-3-hydroxybutyrate) routes were considered. The technological schemes for these synthesis routes were designed, simulated, and economically assessed using Aspen Plus and Aspen Icarus Process Evaluator, respectively. The techno-economic potential of a glycerol-based biorefinery system for the production of fuels, chemicals, and plastics was analyzed using the commercial Commercial Sale Price/Production Cost ratio criteria, under different production scenarios. More income can be earned from 1,3-propanediol and 1,2-propanediol production, while less income would be obtained from hydrogen and succinic acid. This analysis may be useful mainly for biodiesel producers since several profitable alternatives are presented and discussed.

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Glycerol has become an ideal feedstock for producing fuels and chemicals. Here, five technological schemes for optically pure D: -lactic acid production from raw glycerol were designed, simulated, and economically assessed based on five fermentative scenarios using engineered Escherichia coli strains. Fermentative scenarios considered different qualities of glycerol (pure, 98 wt.%, and crude, 85 wt.%) with concentrations ranging from 20 to 60 g/l in the fermentation media, and two fermentation stages were also analyzed. Raw glycerol (60 wt.%) was considered as the feedstock feeding the production process in all cases; then a purification process of raw glycerol up to the required quality was required. Simulation processes were carried out using Aspen Plus, while economic assessments were performed using Aspen Icarus Process Evaluator. D: -Lactic acid recovery and purification processes were based on reactive extraction with tri-n-octylamine using dichloromethane as active extractant agent. The use of raw glycerol represents only between 2.4% and 7.8% of the total production costs. Also, the total production costs obtained of D: -lactic acid in all cases were lower than its sale price indicating that these processes are potentially profitable. Thus, the best configuration process requires the use of crude glycerol diluted at 40 g/l with total glycerol consumption and with D: -lactic acid recovering by reactive extraction. The lowest obtained total production cost was 1.015 US$/kg with a sale price/production cost ratio of 1.53.

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