Syngas fermentation is a biochemical pathway to produce ethanol and has been commercialized successfully. The economic viability of this process could be further improved to become more competitive in the existing ethanol market. Improving gas utilization is the key, and can be done by recycling the unreacted syngas. This work is an early-stage techno-economic assessment of recycling in producing ethanol from Basic Oxygen Furnace (BOF) gas. Economic viability is measured in terms of Relative Competitive Percentage (RCP) and is a measure of closeness to the current market. Two scenarios, firstly a once-through process, and secondly a process with recycling (0.9 split ratio: recycle/purge) of gas is considered. None of them showed a positive RCP as compared to the current ethanol market. Comparing these scenarios, beyond the single pass conversion of 60%, the additional production costs due to recycling become dominating and lead to a lower RCP compared to once-through systems.@en

Microbial electrochemical technologies (METs) employ microorganisms utilizing solid-state electrodes as either electron sink or electron source, such as in microbial electrosynthesis (MES). METs reaction rate is traditionally normalized to the electrode dimensions or to the electrolyte volume, but should also be normalized to biomass amount present in the system at any given time. In biofilm-based systems, a major challenge is to determine the biomass amount in a non-destructive manner, especially in systems operated in continuous mode and using 3D electrodes. We developed a simple method using a nitrogen balance and optical density to determine the amount of microorganisms in biofilm and in suspension at any given time. For four MES reactors converting CO2 to carboxylates, >99% of the biomass was present as biofilm after 69 days of reactor operation. After a lag phase, the biomass-specific growth rate had increased to 0.12–0.16 days−1. After 100 days of operation, growth became insignificant. Biomass-specific production rates of carboxylates varied between 0.08–0.37 molC molX−1d−1. Using biomass-specific rates, one can more effectively assess the performance of MES, identify its limitations, and compare it to other fermentation technologies.@en

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).@en

Production of bio-based acetate is commonly hindered by the high costs of the downstream processing. In this paper, a model is developed to describe a new method that recovers acetate salts using anion exchange resins, and subsequently desorbs and upgrades them using CO2-expanded alcohol. The model consists of equilibrium parameters for both the adsorption and desorption step. The calculated parameters are: for the adsorption KCl- Ac- =0.125, KCl- HCO3 - =0.206 and KOV,HAc=0.674[Formula presented], and for the desorption pKMeCO3 - Ac- =3.71. The maximum experimental concentration of acetic acid obtained in CO2-expanded methanol is 0.427 mol/kg (20 g/LMeOH) at an operating pressure of 31 bar. The model represents the expected trends for all species, and can be used to design a multicolumn system for the recovery and upgrading of carboxylates.@en

Syngas fermentation is an up-and-coming technology that uses acetogenic microorganisms to produce ethanol at the commercial scale. Acetogens can produce many different types of products via their metabolic pathway called the Wood Ljugdahl Pathway (WLP). The WLP can natively produce many different fatty acids and alcohols, and with metabolic engineering, other molecules could be produced through syngas fermentation that are not native to the WLP. In this work isopropanol, 3-hydroxybutyric acid, hexanol, octanol, hexanoic acid, butyric acid and lactic acid were assessed for their feasibility to be produced through syngas fermentation. Two syngas cases were analysed; bio-syngas (H2:CO of 1:1.907) and basic oxygen furnace gas (H2:CO of 1:21.667). The feedstock capacity was fixed at 350 ktons/yr based on its availability. Using thermodynamic values, process reactions from the substrate to the product were found. To verify the metabolic feasibility, ATP yields were calculated based on the respective WLPs from the literature. Sensitivity studies of H2:CO ratios on the carbon yield are carried out to check its effect on the production yields of the product, biomass, and CO2. Sensitivity analysis showed that a higher H2:CO ratio in the feedstock will lead to higher production.@en

Syngas fermentation is an up-and-coming technology that uses acetogenic microorganisms to produce ethanol at the commercial scale. Acetogens can produce many different types of products via their metabolic pathway called the Wood Ljugdahl Pathway (WLP). The WLP can natively produce many different fatty acids and alcohols, and with metabolic engineering, other molecules could be produced through syngas fermentation that are not native to the WLP. In this work isopropanol, 3-hydroxybutyric acid, hexanol, octanol, hexanoic acid, butyric acid and lactic acid were assessed for their feasibility to be produced through syngas fermentation. Two syngas cases were analysed; bio-syngas (H2:CO of 1:1.907) and basic oxygen furnace gas (H2:CO of 1:21.667). The feedstock capacity was fixed at 350 ktons/yr based on its availability. Using thermodynamic values, process reactions from the substrate to the product were found. To verify the metabolic feasibility, ATP yields were calculated based on the respective WLPs from the literature. Sensitivity studies of H2:CO ratios on the carbon yield are carried out to check its effect on the production yields of the product, biomass, and CO2. Sensitivity analysis showed that a higher H2:CO ratio in the feedstock will lead to higher production.@en

Ion-exchange can be used for primary recovery of aqueous dicarboxylic acids at neutral pH, where there is almost complete acid dissociation. The equilibria of anion exchange of aqueous dicarboxylate anions (fumarate, itaconate, malate and succinate) with anions (Cl− and OH−) bound to quaternary ammonium compounds (Aliquat extractant and Dowex sorbent) were quantified. All equilibria could be described by the same model. The four dicarboxylates behaved similarly, and were exchanged by two Cl− or OH− anions. Sorption gave a much better exchange than extraction and OH− gave a much better exchange than Cl−. In batch equilibrium experiments most Cl− is not exchanged by dicarboxylate, pointing at the importance of column operation.@en

Downstream processing aims at recovering the target product at the required specifications from the bioreactor effluent. Research and development in this field relies on experimental and mathematical tools at the levels of chemical components, unit operations and processes. Recently, advances have been made in addressing the broth mixture complexity early on, in incorporating high-throughput experimentation for data generation and mechanistic understanding of the separation processes, in improving the materials and scalability of specific unit operations, as well as establishing the potential of process integration concepts. Further developments are expected considering the variety of (non-sugar) feedstocks currently under research, the need to transition to renewable energy sources, and the opportunities for improved scale-up through initiatives as Big Data and digital manufacturing.@en

In biochemical industry, downstream processing is often the cost-limiting factor during the production of pharmaceutical and fine-chemical products because low product concentrations are usually obtained from the reactor, requiring a large train of separation and purification steps. On the other hand, when fermentation or biotransformation is run to reach high product concentrations, volumetric productivity is often limited by either product inhibition or degradation, such that in situ product removal (ISPR) is useful in these cases. In this work, the synthesis of 6R-dihydro-oxoisophorone (DOIP), also known as levodione, is considered. Levodione is a white crystalline product, with a solubility of about 10 g.L-1 in water, and is an important intermediate in the production of some carotenoids and saffron flavors. The synthesis reaction (Figure 1) involves the asymmetric reduction of 4-oxoisophorone (OIP) using yeast such as Saccharomyces cerevisiae or Saccharomyces rouxii as biocatalyst [1-3]. An enantiomeric excess (e.e.) □ 98% for levodione is obtained in this process. The main product (levodione) is further degraded by the yeast mainly to (4S,6R)-actinol, an unwanted by-product in the process, such that in situ product removal by crystallization is employed to minimize degradation. ISPR by crystallization with external configuration has been successfully implemented using resting cells [1] and growing cells [2] of S. cerevisiae resulting in an efficient integrated fermentation- crystallization process. Relative to the conventional batch and fed-batch processes, the integrated fermentation-crystallization process configuration has a better performance in terms of final yield (85%), final selectivity (96-98.7%), and volumetric productivity (0.30-0.92 g.L-1.h-1) [1-2]. In order to further evaluate the process, a conceptual process design is done for the production of levodione implementing ISPR by crystallization, and is compared with the base case, which is a known conventional process equivalent [3]. On the same basis, the comparison indicates that employing ISPR by crystallization has potential advantages over the conventional process (base case) in terms of increased productivity and yield with corresponding decrease in the number of downstream processing steps as well as the quantity of waste streams. This leads to an economically more interesting process alternative.@en

BACKGROUND: Isopropanol and acetone production by syngas fermentation is a promising alternative to conventional fossil carbon-dependent production. However, this alternative technology has not yet been scaled up to an industrial level owing to the relatively low product concentrations (about 5 wt% in total). This original research aims to develop cost-effective and energy-efficient processes for the recovery of isopropanol and acetone from highly dilute fermentation broth (>94 wt% water) for large-scale production (about 100 ktIPA+AC y−1). RESULTS: Vacuum distillation and pass-through distillation enhanced with heat pumps or multi-effect distillation were efficiently coupled with regular atmospheric distillation and extractive distillation in several innovative intensified downstream processes. Over 99.2% of isopropanol and 100% of acetone were recovered as high-purity end-products (>99.8 wt%). Advanced heat pumping (mechanical vapor recompression) and heat integration techniques were implemented to decrease total annual costs (0.109–0.137 USD kgIPA+AC−1), reduce energy requirements (1.348–2.043 kWth h kgIPA+AC−1) and lower CO2 emissions (0.067–0.191 kgCO2 kgIPA+AC−1), resulting in highly competitive recovery processes. CONCLUSION: The proposed three novel isopropanol and acetone recovery processes from dilute broth significantly contribute to the expansion of sustainable industrial fermentation. Furthermore, this original research is the first one to develop novel pass-through distillation technology for the complex isopropanol–acetone–water system. All the designed processes are highly economically competitive and environmentally viable. In addition to recovering efficiently both isopropanol and acetone, the designed downstream processes offer the possibility to enhance the fermentation process by recycling all the present microorganisms and reducing fresh-water requirements.@en

The aim of this work was to recover a mixture of carboxylates ranging from 2 to 7 carbon atoms using a strong anion exchange resin, followed by desorption with CO2-expanded methanol. Medium chain carboxylates hexanoate and heptanoate adsorbed better than acetate, and the corresponding medium chain carboxylic acids desorbed easier than acetic acid. Consequently, hexanoate and heptanoate were concentrated up to 14.6 and 20.7 times, respectively. These findings will enable effective separation and purification of the produced carboxylic acids. Notably, the presence of inorganic ions in the sample, such as chloride, decreased the adsorption affinity compared to a synthetic mixture only of carboxylates.@en

Syngas fermentation to biofuels and chemicals is an emerging technology in the biobased economy. Mass transfer is usually limiting the syngas fermentation rate, due to the low aqueous solubilities of the gaseous substrates. Membrane bioreactors, as efficient gas–liquid contactors, are a promising configuration for overcoming this gas-to-liquid mass transfer limitation, so that sufficient productivity can be achieved. We summarize the published performances of these reactors. Moreover, we highlight numerous parameters settings that need to be used for the enhancement of membrane bioreactor performance. To facilitate this enhancement, we relate mass transfer and other performance indicators to the type of membrane material, module, and flow configuration. Hollow fiber modules with dense or asymmetric membranes on which biofilm might form seem suitable. A model-based approach is advocated to optimize their performance.@en

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.@en

In gas fermentations (using O2, CO, H2, CH4 or CO2), gas-to-liquid mass transfer is often regarded as one of the limiting processes. However, it is widely known that components in fermentation broths (e.g., salts, biomass, proteins, antifoam, and organic products such as alcohols and acids) have tremendous impact on the volumetric mass transfer coefficient kLa. We studied the influence of ethanol on mass transfer in three fermentation broths derived from syngas fermentation. In demineralized water, we observed that the addition of ethanol, the expected product, increased kLa two-fold in the 0–5 g L−1 range, after which near-constant kLa values were obtained. In the fermentation broths, kLa was increased significantly (2–4 fold compared to water) by ethanol supplementation, and to be highly influenced by broth salinity. Our results indicate that kLa is a dynamic parameter in gas fermentation experiments and can be significantly increased due to broth components.@en

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.@en