T. Jankovic
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23 records found
1
This study advances the development of syngas fermentation by presenting the first industrial-scale process design for producing isopropanol (IPA) and acetone from steel mill off-gas, with a total production capacity of 46–50 ktonne per year. The process was rigorously developed in Aspen Plus, with a comprehensive techno-economic assessment and life-cycle analysis performed to evaluate the process performance. The developed process maximizes energy efficiency by utilizing the heat content of steel off-gas and implementing advanced heat pump systems. As a result, the process is thermally self-sufficient and can operate solely on renewable electricity. Efficient utilization of waste gases results in substantial reductions in global warming potential compared with petrochemical-based production (144–160% for IPA and 138–149% for acetone). The unit production cost of 0.58–0.74 $/kgIPA/Ac and potential profit margins of 49–65% testify to the cost-effectiveness of the developed process. These findings demonstrate the environmental and economic sustainability of syngas fermentation from steel mill off-gas, establishing it as a potentially viable alternative to conventional petrochemical processes. This technology may hold great potential in reducing environmental impacts and carbon emissions in industrial chemical production.
Carbon dioxide utilization is a key strategy for sustainable chemical production and climate change mitigation. Microbial electrosynthesis (MES) offers a promising approach to convert CO₂ into organic acids and multi‑carbon compounds, but its industrial application requires improved product recovery methods. In this study, we developed an integrated MES-sorption-distillation system for the recovery of pure hexanoic acid. Adsorption experiments identified conditions for C6-selective capture from C2–C6 carboxylate mixtures typically produced from MES. Subsequent desorption using CO₂ expanded methanol enriched hexanoic acid concentration by 13-fold compared to the aqueous feed, achieving 67 % recovery in a single pass, but 100 % overall, since recirculation of unrecovered carboxylates back to the MES reactor is proposed. This recirculation will enhance chain elongation, eliminate loss of unrecovered carboxylates, and reduce the need for external pH control during MES. Distillation of the desorbed mixture led to streams of pure products and reusable solvent, without losses. Notably, 87 % of the total energy demand for product formation is attributed to the MES stage, where electrical energy is directly supplied as electrons to drive microbial production. Thus, MES with the proposed recovery method enables pure hexanoic acid production with minimal losses of materials or energy and potentially allows the system to operate in a carbon-negative manner.
Fermentation can be used to obtain a wide variety of valuable high-boiling components. Among these components, microorganisms can produce aliphatic diols (e.g. propanediols, butanediols, etc.) in significant concentrations (e.g. 5–15 wt.%). Nonetheless, the high boiling points of these components, presence of microorganisms, and formation of by-products complicate recovery after fermentation. Hence, this perspective offers valuable insights into downstream processing options. A novel methodology was developed for recovering high-boiling components from dilute aqueous solutions, whereby both light and heavy impurities are present. The main steps in the proposed methodology are heat pump-assisted preconcentration and final purification in a dividing-wall column. These steps allow effective separation of high-purity product from water, light and heavy impurities. Furthermore, processes for recovery of 1,3-propanediol, 2,3-, 1,4- and 1,3-butanediol, designed according to the proposed methodology, were compared. Downstream processing performance is mainly determined by the product concentration in the fermentation broth, but is also influenced by the amount of impurities in the broth.
2-Phenylethanol (2-PE) and 2-phenylethyl acetate (2-PEAc) are valuable aroma compounds with growing market demands. As an alternative to conventional petrochemical production, more valuable natural forms of these chemicals can be obtained by biotransformation. Low product concentrations, resulting from significant product toxicity to microorganisms, and high boiling points of products complicate recovery process. In situ product recovery by liquid–liquid extraction can be used to increase bioprocess yield and productivity. However, the subsequent purification of 2-PE and 2-PEAc is challenging as a consequence of the multiple phases, high-boiling temperatures of main products, occurrence of remaining substrate and byproducts, and presence of microorganisms.
RESULTS
The main goal of this original work is to improve the competitiveness of the biotechnological production of 2-PE by using in silico methods to develop an advanced industrial process for the final purification after centrifugation. An adaptable dividing-wall column was designed to remove 2-PE with 2-PEAc from organic phase or to esterify 2-PE to pure 2-PEAc. The production flexibility of the developed process allows adjustability to market demand. Additionally, recovery of co-produced ethanol from aqueous phase can increase the economic and environmental performance of the developed process. As confirmed by detailed techno-economic analysis, the proposed processes can cost-effectively (total recovery costs of 0.64–0.72 US$/kg2-PE/2-PEAc) and energy-efficiently (primary energy requirements of 1.83–2.05 kWthh/kg2-PE/2-PEAc) recovery of 2-PE or 2-PEAc after biotransformation.
CONCLUSION
The developed process enhances economic and environmental viability of biotechnological 2-PE production by reducing costs and energy requirements, while ensuring flexibility to adapt to market demands. ...
2-Phenylethanol (2-PE) and 2-phenylethyl acetate (2-PEAc) are valuable aroma compounds with growing market demands. As an alternative to conventional petrochemical production, more valuable natural forms of these chemicals can be obtained by biotransformation. Low product concentrations, resulting from significant product toxicity to microorganisms, and high boiling points of products complicate recovery process. In situ product recovery by liquid–liquid extraction can be used to increase bioprocess yield and productivity. However, the subsequent purification of 2-PE and 2-PEAc is challenging as a consequence of the multiple phases, high-boiling temperatures of main products, occurrence of remaining substrate and byproducts, and presence of microorganisms.
RESULTS
The main goal of this original work is to improve the competitiveness of the biotechnological production of 2-PE by using in silico methods to develop an advanced industrial process for the final purification after centrifugation. An adaptable dividing-wall column was designed to remove 2-PE with 2-PEAc from organic phase or to esterify 2-PE to pure 2-PEAc. The production flexibility of the developed process allows adjustability to market demand. Additionally, recovery of co-produced ethanol from aqueous phase can increase the economic and environmental performance of the developed process. As confirmed by detailed techno-economic analysis, the proposed processes can cost-effectively (total recovery costs of 0.64–0.72 US$/kg2-PE/2-PEAc) and energy-efficiently (primary energy requirements of 1.83–2.05 kWthh/kg2-PE/2-PEAc) recovery of 2-PE or 2-PEAc after biotransformation.
CONCLUSION
The developed process enhances economic and environmental viability of biotechnological 2-PE production by reducing costs and energy requirements, while ensuring flexibility to adapt to market demands.
Process systems engineering is essential in developing competitive (bio)chemical processes, as it integrates process design and simulation in biotechnology. Hence, this thesis aims to advance industrial biotechnology by developing advanced, large-scale downstream processes for the recovery of fermentation products such as alcohols, diols, esters, carboxylic acids, and aromatic compounds. A systematic approach to downstream process development was undertaken through multiple case studies that were organized into chapters based on the characteristics of the primary product being recovered. Aspen Plus software was used as a computer aided process engineering tool for process design. Various process intensification techniques (e.g. dividing-wall column and reactive distillation), heat integration and heat pumping were studied to reduce energy requirements and decrease total process costs. The performance of the developed processes was assessed through economic analysis and the evaluation of key sustainability metrics, including energy requirements, greenhouse gas emissions, water consumption, water losses, and toxic materials and pollutants intensity.
Chapter 2 focuses on designing downstream processing strategies tailored for low-boiling alcohols produced through fermentation, including ethanol, isopropanol, isobutanol, and hexanol. Since these products are sufficiently volatile, the end-product inhibition can be mitigated by continuously removing the product from the broth using a distillation-based loop around the bioreactor. Heat pump-assisted vacuum distillation was demonstrated as an effective method for initial product recovery from the broth. Additionally, a novel pass-through distillation process was designed specifically for ethanol recovery. This innovative technique separates the evaporation and condensation parts of distillation by introducing an absorption-desorption loop between them. As a result, these operations can be conducted at different pressures, allowing the use of inexpensive cooling utilities while maintaining mild evaporation temperatures. Furthermore, a hybrid approach combining gas stripping with heat pump-assisted vacuum evaporation was developed for the recovery of isobutanol from fermentation broth. In all cases, the initial separation of the product from most of the broth under reduced pressure lowers the operational temperature, making it possible to reuse the remaining broth along with the microorganisms. This may improve fermentation performance by avoiding biomass loss, increasing substrate-to-product yield and reducing water requirements. Following this initial step, a preconcentration step using heat pump-assisted atmospheric distillation was carried out to remove most of the remaining water. The final purification method depended on the properties of the target product. Ethanol and isopropanol, which form homogeneous azeotropes with water, were purified using extractive distillation with ethylene glycol. In contrast, isobutanol and hexanol, which form heterogeneous azeotropes, were purified through a combination of simple distillation and liquid-liquid phase separation. Furthermore, a general methodology for recovering volatile alcohols from fermentation broths was developed and the performance of downstream processing was compared for the recovery of ethanol, isopropanol, isobutanol, and hexanol. Due to the higher hydrophobicity of longer-chain alcohols, their concentrations in the fermentation broth tend to be lower (e.g. 6.14 wt% for ethanol, 5.00 wt% for isopropanol, 1.61 wt% for isobutanol, and 0.24 wt% for hexanol). More dilute fermentation broths result in higher processing costs (0.08, 0.11, 0.16, and 0.53 $/kg, respectively) and increased energy requirements (0.96, 1.35, 2.02 and 3.07 kWthh/kg, respectively) of the downstream processing. Finally, it was concluded that the primary factor influencing downstream processing efficiency is the achievable product concentration in the fermentation broth, rather than the alcohol chain length.
Chapter 3 focuses on developing recovery processes for aliphatic diols that can be produced through fermentation, including 1,3-propanediol, 2,3-butanediol, 1,4-butanediol, and 1,3-butanediol. Due to their high boiling points, simple distillation is unsuitable for separating these compounds from the fermentation broth. Instead, initial separation steps are required to remove biomass, as well as large organic and inorganic molecules. These initial steps result in a clarified, desalted solution, which then undergoes further treatment through preconcentration and final purification. Since these final two steps contribute significantly to overall purification costs due to their high energy requirements, this research focuses on enhancing them to improve the efficiency of downstream processing for aliphatic diols. The preconcentration step was designed to remove most of water along with some light impurities using a heat pump-assisted vacuum distillation. The final purification step, which separates high-purity diol from residual light and heavy impurities, was effectively carried out in a dividing wall column. Furthermore, a general methodology for recovering high boiling components from dilute aqueous solutions was developed. Recovery processes for 1,3-propanediol, 2,3-butanediol, 1,4-butanediol, and 1,3-butanediol, designed according to this methodology, were compared. The performance of downstream processing was primarily determined by the product concentration in the fermentation broth, though the presence of impurities also played a significant role. Nonetheless, in all cases, the proposed methodology enabled the cost effective (total recovery costs of 0.29-0.70 $/kg) and energy-efficient (primary energy requirements of 1.35-2.01 kWthh/kg) recovery of valuable propanediol and butanediol from dilute aqueous solutions (7.0-10.0 wt%). Lastly, adaptable process design offers the possibility of using a single process configuration to produce various aliphatic diols depending on the market demand.
Chapter 4 discusses the development of recovery processes for various organic chemicals produced through different biotechnology-based processes, such as ethyl acetate, propionic acid, 2-phenylethanol, acetic acid, furfural, etc. While these processes differ due to the unique properties of each compound, they all rely on distillation as a primary recovery method. It was employed as the main separation technique to efficiently recover propionic, acetic, and succinic acids from dilute aqueous solutions. An adaptable dividing-wall column design was demonstrated to effectively recover propionic and acetic acids or perform esterification with methanol to recover methyl-propionate and methyl-acetate (total recovery costs of 0.40-0.47 $/kg). Distillation was also utilized as the primary technique in the recovery of ethyl acetate. Due to its high volatility, most of the ethyl acetate is separated in the fermenter off-gas. Consequently, product recovery was carried out from both the vapor and liquid phases, with an azeotropic dividing-wall column used effectively for final purification (total recovery costs of 0.61-1.09 $/kg). Furthermore, distillation-based downstream processing was effectively used for the solvent recovery and final purification of 2-phenylethanol after in-situ product recovery by liquid-liquid extraction. An adaptable azeotropic dividing-wall column was designed to recover high-purity 2-phenylethanol or perform esterification and recover 2-phenylethyl acetate (total recovery costs of 0.64-0.73 $/kg). Lastly, a sequence of distillation steps was developed to recover by-products (acetic acid, formic acid, furfural, 5-hydroxymethyl furfural) from the lignocellulosic biomass pretreatment process using liquid hot water (total recovery costs of 0.78 $/kg). This process could enhance the competitiveness of lignocellulosic biorefineries by enabling the valorization of additional products.
Furthermore, this thesis emphasizes the importance of advancing both upstream and downstream processes simultaneously to ensure the competitiveness and viability of entire bioprocesses. While the primary focus of this research is on recovery process development, it serves as an initial step toward achieving that broader goal. Chapter 5 highlights the significance of integrating upstream and downstream processes in bioprocess development. Isopropanol, along with acetone, and 2-phenylethanol, were selected as representative examples of low boiling and high-boiling biochemicals. Large-scale bioprocesses for their production were designed to showcase the practical application of integrated process design. Isopropanol and acetone were produced through gas fermentation, with different combinations of products (isopropanol and acetone together or separately) considered. Previously developed advanced recovery processes, including heat pump-assisted vacuum distillation, followed by heat pump-assisted atmospheric distillation and extractive distillation, were employed. Detailed techno-economic analysis and life cycle assessments demonstrated competitive economic performance (total production costs of 0.57-0.74 $/kg) and reduced environmental impacts compared to fossil fuel-based production (reduced global warming potential by 138-160%). 2-phenylethanol was produced de-novo through fermentation from glucose. Two different in-situ product recovery processes were compared: liquid-liquid extraction using oleyl alcohol and product adsorption. In both cases, distillation-based separations were used to effectively recover the solvent and obtain high-purity 2-phenylethanol. Additionally, a sensitivity analysis was conducted to examine the influence of 2-phenylethanol concentration on total production costs. This analysis revealed that minimal costs were achieved at a concentration of 1.5 g/L, with concentrations above 1 g/L not resulting in a significant reduction in costs due to increased fermentation costs. Regardless of the used in-situ recovery technique, the developed processes for producing 2-phenylethanol were found to be highly cost-effective (total production costs of 9.03-9.40 $/kg).
Summarizing, this thesis illustrates the significant impact that advancements in downstream processing can have on overall process performance. Specifically, it supports the development of novel advanced separation processes, based on process intensification principles, which have received relatively limited attention in industrial biotechnology. These innovations can play a decisive role in determining the feasibility of bioprocesses for industrial scale applications. Furthermore, the importance of incorporating downstream processing at the early stages of developing biotechnology-based processes is highlighted. The findings presented in this thesis have the potential to drive progress in industrial biotechnology and contribute to the successful commercialization of biotechnology-based products.
...
Process systems engineering is essential in developing competitive (bio)chemical processes, as it integrates process design and simulation in biotechnology. Hence, this thesis aims to advance industrial biotechnology by developing advanced, large-scale downstream processes for the recovery of fermentation products such as alcohols, diols, esters, carboxylic acids, and aromatic compounds. A systematic approach to downstream process development was undertaken through multiple case studies that were organized into chapters based on the characteristics of the primary product being recovered. Aspen Plus software was used as a computer aided process engineering tool for process design. Various process intensification techniques (e.g. dividing-wall column and reactive distillation), heat integration and heat pumping were studied to reduce energy requirements and decrease total process costs. The performance of the developed processes was assessed through economic analysis and the evaluation of key sustainability metrics, including energy requirements, greenhouse gas emissions, water consumption, water losses, and toxic materials and pollutants intensity.
Chapter 2 focuses on designing downstream processing strategies tailored for low-boiling alcohols produced through fermentation, including ethanol, isopropanol, isobutanol, and hexanol. Since these products are sufficiently volatile, the end-product inhibition can be mitigated by continuously removing the product from the broth using a distillation-based loop around the bioreactor. Heat pump-assisted vacuum distillation was demonstrated as an effective method for initial product recovery from the broth. Additionally, a novel pass-through distillation process was designed specifically for ethanol recovery. This innovative technique separates the evaporation and condensation parts of distillation by introducing an absorption-desorption loop between them. As a result, these operations can be conducted at different pressures, allowing the use of inexpensive cooling utilities while maintaining mild evaporation temperatures. Furthermore, a hybrid approach combining gas stripping with heat pump-assisted vacuum evaporation was developed for the recovery of isobutanol from fermentation broth. In all cases, the initial separation of the product from most of the broth under reduced pressure lowers the operational temperature, making it possible to reuse the remaining broth along with the microorganisms. This may improve fermentation performance by avoiding biomass loss, increasing substrate-to-product yield and reducing water requirements. Following this initial step, a preconcentration step using heat pump-assisted atmospheric distillation was carried out to remove most of the remaining water. The final purification method depended on the properties of the target product. Ethanol and isopropanol, which form homogeneous azeotropes with water, were purified using extractive distillation with ethylene glycol. In contrast, isobutanol and hexanol, which form heterogeneous azeotropes, were purified through a combination of simple distillation and liquid-liquid phase separation. Furthermore, a general methodology for recovering volatile alcohols from fermentation broths was developed and the performance of downstream processing was compared for the recovery of ethanol, isopropanol, isobutanol, and hexanol. Due to the higher hydrophobicity of longer-chain alcohols, their concentrations in the fermentation broth tend to be lower (e.g. 6.14 wt% for ethanol, 5.00 wt% for isopropanol, 1.61 wt% for isobutanol, and 0.24 wt% for hexanol). More dilute fermentation broths result in higher processing costs (0.08, 0.11, 0.16, and 0.53 $/kg, respectively) and increased energy requirements (0.96, 1.35, 2.02 and 3.07 kWthh/kg, respectively) of the downstream processing. Finally, it was concluded that the primary factor influencing downstream processing efficiency is the achievable product concentration in the fermentation broth, rather than the alcohol chain length.
Chapter 3 focuses on developing recovery processes for aliphatic diols that can be produced through fermentation, including 1,3-propanediol, 2,3-butanediol, 1,4-butanediol, and 1,3-butanediol. Due to their high boiling points, simple distillation is unsuitable for separating these compounds from the fermentation broth. Instead, initial separation steps are required to remove biomass, as well as large organic and inorganic molecules. These initial steps result in a clarified, desalted solution, which then undergoes further treatment through preconcentration and final purification. Since these final two steps contribute significantly to overall purification costs due to their high energy requirements, this research focuses on enhancing them to improve the efficiency of downstream processing for aliphatic diols. The preconcentration step was designed to remove most of water along with some light impurities using a heat pump-assisted vacuum distillation. The final purification step, which separates high-purity diol from residual light and heavy impurities, was effectively carried out in a dividing wall column. Furthermore, a general methodology for recovering high boiling components from dilute aqueous solutions was developed. Recovery processes for 1,3-propanediol, 2,3-butanediol, 1,4-butanediol, and 1,3-butanediol, designed according to this methodology, were compared. The performance of downstream processing was primarily determined by the product concentration in the fermentation broth, though the presence of impurities also played a significant role. Nonetheless, in all cases, the proposed methodology enabled the cost effective (total recovery costs of 0.29-0.70 $/kg) and energy-efficient (primary energy requirements of 1.35-2.01 kWthh/kg) recovery of valuable propanediol and butanediol from dilute aqueous solutions (7.0-10.0 wt%). Lastly, adaptable process design offers the possibility of using a single process configuration to produce various aliphatic diols depending on the market demand.
Chapter 4 discusses the development of recovery processes for various organic chemicals produced through different biotechnology-based processes, such as ethyl acetate, propionic acid, 2-phenylethanol, acetic acid, furfural, etc. While these processes differ due to the unique properties of each compound, they all rely on distillation as a primary recovery method. It was employed as the main separation technique to efficiently recover propionic, acetic, and succinic acids from dilute aqueous solutions. An adaptable dividing-wall column design was demonstrated to effectively recover propionic and acetic acids or perform esterification with methanol to recover methyl-propionate and methyl-acetate (total recovery costs of 0.40-0.47 $/kg). Distillation was also utilized as the primary technique in the recovery of ethyl acetate. Due to its high volatility, most of the ethyl acetate is separated in the fermenter off-gas. Consequently, product recovery was carried out from both the vapor and liquid phases, with an azeotropic dividing-wall column used effectively for final purification (total recovery costs of 0.61-1.09 $/kg). Furthermore, distillation-based downstream processing was effectively used for the solvent recovery and final purification of 2-phenylethanol after in-situ product recovery by liquid-liquid extraction. An adaptable azeotropic dividing-wall column was designed to recover high-purity 2-phenylethanol or perform esterification and recover 2-phenylethyl acetate (total recovery costs of 0.64-0.73 $/kg). Lastly, a sequence of distillation steps was developed to recover by-products (acetic acid, formic acid, furfural, 5-hydroxymethyl furfural) from the lignocellulosic biomass pretreatment process using liquid hot water (total recovery costs of 0.78 $/kg). This process could enhance the competitiveness of lignocellulosic biorefineries by enabling the valorization of additional products.
Furthermore, this thesis emphasizes the importance of advancing both upstream and downstream processes simultaneously to ensure the competitiveness and viability of entire bioprocesses. While the primary focus of this research is on recovery process development, it serves as an initial step toward achieving that broader goal. Chapter 5 highlights the significance of integrating upstream and downstream processes in bioprocess development. Isopropanol, along with acetone, and 2-phenylethanol, were selected as representative examples of low boiling and high-boiling biochemicals. Large-scale bioprocesses for their production were designed to showcase the practical application of integrated process design. Isopropanol and acetone were produced through gas fermentation, with different combinations of products (isopropanol and acetone together or separately) considered. Previously developed advanced recovery processes, including heat pump-assisted vacuum distillation, followed by heat pump-assisted atmospheric distillation and extractive distillation, were employed. Detailed techno-economic analysis and life cycle assessments demonstrated competitive economic performance (total production costs of 0.57-0.74 $/kg) and reduced environmental impacts compared to fossil fuel-based production (reduced global warming potential by 138-160%). 2-phenylethanol was produced de-novo through fermentation from glucose. Two different in-situ product recovery processes were compared: liquid-liquid extraction using oleyl alcohol and product adsorption. In both cases, distillation-based separations were used to effectively recover the solvent and obtain high-purity 2-phenylethanol. Additionally, a sensitivity analysis was conducted to examine the influence of 2-phenylethanol concentration on total production costs. This analysis revealed that minimal costs were achieved at a concentration of 1.5 g/L, with concentrations above 1 g/L not resulting in a significant reduction in costs due to increased fermentation costs. Regardless of the used in-situ recovery technique, the developed processes for producing 2-phenylethanol were found to be highly cost-effective (total production costs of 9.03-9.40 $/kg).
Summarizing, this thesis illustrates the significant impact that advancements in downstream processing can have on overall process performance. Specifically, it supports the development of novel advanced separation processes, based on process intensification principles, which have received relatively limited attention in industrial biotechnology. These innovations can play a decisive role in determining the feasibility of bioprocesses for industrial scale applications. Furthermore, the importance of incorporating downstream processing at the early stages of developing biotechnology-based processes is highlighted. The findings presented in this thesis have the potential to drive progress in industrial biotechnology and contribute to the successful commercialization of biotechnology-based products.
Sustainable Isopropanol, Acetone or Mixed Production from Steel Mill Offgas
Modelling and Assessment of Syngas Fermentation at Different Titers and Yields
BACKGROUND: 2-Phenylethanol (2PE) is a valuable aroma component that can be obtained through de-novo fermentation from glucose. However, its toxicity at very low concentrations (<2.5 g L−1) limits the fermentation titer, rate and yield. To address these limitations, in-situ product removal has been explored, leading to a recent scale-up to pilot scale. Nonetheless, an industrial scale has yet to be achieved. RESULTS: This original research pioneers conceptual development of two large-scale (2 ktonne2PE/y) production processes for 2PE via de-novo fermentation from glucose. Liquid–liquid extraction with oleyl alcohol and adsorption by hydrophobic resins followed by ethanol desorption, were alternatives considered for in-situ 2PE removal. For either design, solvent recovery and final purification were performed using advanced distillation techniques, including a heat pump-assisted distillation and a dividing-wall column. A fermentation titer of approximately 1.5 g2PE/Lbroth minimized production costs by achieving balance between upstream and downstream processing costs. This resulted in a cost-effective 2PE production for both designs of the recovery process (9.03–9.40 $/kg2PE). Sensitivity analysis revealed that glucose, oleyl alcohol, and ethanol costs strongly impact total production costs. CONCLUSION: This novel study provides a comprehensive and scalable process framework for the large-scale production of 2PE through de-novo fermentation. Integrating in-situ product removal and energy-efficient purification strategies, it marks a significant step forward in industrial biotechnology.
Green Industrial Scale Plant Design for Syngas Fermentation to Isopropyl Alcohol and Acetone
Economic and Environmental Sustainability Assessment
Ethyl acetate is a platform chemical conventionally obtained through fossil fuel routes, but more recently its production by fermentation from carbohydrates has been scaled up to a pilot scale. Yet, the complexity of downstream processing (low product concentrations in liquid broth and in off-gas, azeotrope formation, and the presence of microorganisms) may complicate industrial application. This original theoretical study is the first to develop advanced downstream processing, based on process intensification principles, for large-scale recovery (~10 kton/year) of ethyl acetate after fermentation. To minimize product losses, ethyl acetate is separated from both the liquid broth and off-gas. The final purification is performed in a highly integrated azeotropic dividing-wall column. The economic and sustainability analysis shows that using refrigeration for initial product separation from the gas phase is more cost-effective (~0.61 $/kg) and less energy-intensive (2.20–2.40 kWthh/kg) than compression combined with high-pressure condensation using chilled water (1.09 $/kg and 9.98 kWthh/kg).
Isobutanol is a highly attractive renewable alternative to conventional fossil fuels, with superior fuel properties as compared to ethanol and 1-butanol. Even though the isobutanol production by fermentation has significant potential, complex downstream processing is limiting the wide-spreading of this technology. Accordingly, this original research significantly contributes to the advancement in industrial biofuel production by developing two eco-efficient downstream processes for the industrial-scale recovery of isobutanol (production capacity 50 ktonneIBUT/y), from a highly dilute fermentation broth (>98 wt% water). Vacuum distillation and a novel hybrid combination of gas stripping and vacuum evaporation were coupled with atmospheric azeotropic distillation to recover over 99.9 % of isobutanol as a high-purity product (100 wt%). Advanced heat pumping and heat integration techniques were further implemented to allow the complete electrification of these recovery processes. Furthermore, implementation of these techniques significantly decreased total annual costs (0.131–0.161 $/kgIBUT), reduced energy requirements (0.488–0.807 kWeh/kgIBUT) and lowered CO2 emissions (0.303–0.449 kgCO2/kgIBUT), resulting in highly competitive purification processes. In addition to efficiently recovering isobutanol, the designed downstream processes provide the potential to enhance the fermentation process by recycling all present microorganisms and reducing water demand. Therefore, the results of this original research substantially contribute to the advancement in industrial biotechnology and the wide-spreading of biofuel production.
Isopropanol-butanol-ethanol (IBE) fermentation is a superior biofuel production technology as compared to acetone-butanol-ethanol (ABE) fermentation due to the better fuel properties of the obtained products. However, low product concentrations, thermodynamic constraints and the presence of microorganisms lead to complex downstream processing that limits the competitiveness of this biofuel production method. Thus, this original research proposes a novel thermally self-sufficient and eco-efficient downstream process for industrial-scale recovery after IBE fermentation (74 ktonne/y capacity), from a highly dilute broth (>97 wt% water). Gas stripping and heat pump-assisted vacuum evaporation were implemented to separate valuable products from most of the broth. Furthermore, an advanced highly integrated heat pump-assisted azeotropic dividing-wall column was designed to recover high-purity (99 wt%) butanol biofuel and isopropanol – ethanol fuel supplement (89 wt%). The proposed purification process recovers over 99 % of biofuel products in a cost-effective (0.130 $/kgIBE) and energy-efficient way (0.673 kWeh/kgIBE) while allowing full recycle of biomass and most of the separated water. Besides improving yield by continuously recovering the inhibitory products, fermentation can be further enhanced by avoiding biomass loss and reducing water requirements. Lastly, the implemented energy-saving techniques ensure complete electrification of the proposed IBE recovery process. Therefore, the original results of this research study significantly contribute to the development of sustainable biofuel production processes.
Distillation is the most used separation technology at industrial-scale, but using distillation in bio-based processes (e.g. fermentation processes to produce bioethanol) is quite challenging when mild temperatures are needed to keep the microbes alive. Vacuum distillation can be used to perform evaporation at low temperatures, but setting a low distillation pressure fixes also the condensation temperature to very low values that may require expensive refrigeration. Pass-through distillation (PTD) is an emerging hybrid separation technology that effectively combines distillation with absorption in a sorption-assisted distillation process that decouples the evaporation and condensation steps. This is achieved by inserting between the evaporation and condensation steps an absorption-desorption loop that passes through the component to be separated and allows the use of different pressures and types of heating and cooling utilities. This paper is the first to present the process design and rigorous simulation (implemented in Aspen Plus) of a new pass-through distillation process for bioethanol (∼100 ktonne/y plant capacity), proving its effectiveness in concurrent alcohol recovery and fermentation (CARAF). Combining PTD with heat pumps leads to low recovery costs of 0.122 $/kgEtOH and energy requirements of only 1.723 kWthh/kgEtOH. Alternatively, combining PTD with multi-effect distillation resulted in 0.131 $/kgEtOH recovery costs and 1.834 kWthh/kgEtOH energy intensity.
Lignocellulosic biomass potentially represents a great feedstock for biofuel production, but its’ pretreatment needs to be enhanced in order to make biorefineries competitive with fossil fuel based alternatives. One way to make biorefineries more economically viable is to recover and valorize all generated by-products during the biomass pretreatment step. The main goal of this original research is to design an optimal process for recovering valuable by-products after hot-liquid water pretreatment of poplar biomass. Rigorous models for all operations included in the recovery process are developed using Aspen Plus as a CAPE tool. An optimal downstream processing sequence, consisting of multiple distillation steps, is designed to recover several valuable components, such as acetic acid, formic acid, furfural and 5-hydroxymethylfurfural (HMF).
Turning waste into value
Eco-efficient recovery of by-products from biomass pretreatment in lignocellulosic biorefineries
This original research contributes to enhancing the viability of biorefineries through recovering valuable by-products from the liquid remaining after the biomass pretreatment by hot liquid water. A novel downstream processing method is developed for the recovery of acetic acid, formic acid, furfural and 5-hydroxymethylfurfural (HMF) by enhanced distillation. The major challenge in this research is the processing of the highly diluted initial solution (>96 wt% water) and the thermodynamic limitations owing to possible formation of several azeotropes. This new process recovers 78.7% of the acetic acid (99.8 wt%), while the rest of it is recycled back to the biomass pretreatment step together with most of the separated water from the initial solution. Over 99.5% of formic acid, furfural and HMF is also recovered, at purities of 74.7, 98.0 and 100 wt%, respectively. Vapor recompression and heat integration are implemented to decrease the energy use. The results demonstrate a 77.4% decrease in total annual costs (from $3.44 to 0.78/kgproduct), a 75.0% reduction in minimum average selling price (from $3.50 to 0.87/kgproduct), an 81.1% reduction in energy requirements (from 77.41 to 14.66 kWthh/kgproduct) and an up to 99.7% decrease in CO2 emissions (from 11.17 to 0.03 kgCO2/kgproduct).