Biofuel from wastewater-grown microalgae: A biorefinery approach using hydrothermal liquefaction and catalyst upgrading.

Third-generation biofuels from microalgae are becoming necessary for sustainable energy. In this context, this study explores the hydrothermal liquefaction (HTL) of microalgae biomass grown in wastewater, consisting of 30% Chlorella vulgaris, 69% Tetradesmus obliquus, and 1% cyanobacteria Limnothrix planctonica, and the subsequent upgrading of the produced bio-oil. The novelty of the work lies in integrating microalgae cultivation in wastewater with HTL in a biorefinery approach, enhanced using a catalyst to upgrade the bio-oil. Different temperatures (300, 325, and 350 °C) and reaction times (15, 30, and 45 min) were tested. The bio-oil upgrading occurred with a Cobalt-Molybdenum (CoMo) catalyst for 1 h at 375 °C. Post-HTL, although the hydrogen-to-carbon (H/C) ratio decreased from 1.70 to 1.38-1.60, the oxygen-to-carbon (O/C) ratio also decreased from 0.39 to 0.079-0.104, and the higher heating value increased from 20.6 to 36.4-38.3 MJ kg-1. Palmitic acid was the main component in all bio-oil samples. The highest bio-oil yield was at 300 °C for 30 min (23.4%). Upgrading increased long-chain hydrocarbons like heptadecane (5%), indicating biofuel potential, though nitrogenous compounds such as hexadecanenitrile suggest a need for further hydrodenitrogenation. Aqueous phase, solid residues, and gas from HTL can be used for applications such as biomass cultivation, bio-hydrogen, valuable chemicals, and materials like carbon composites and cement additives, promoting a circular economy. The study underscores the potential of microalgae-derived bio-oil as sustainable biofuel, although further refinement is needed to meet current fuel standards.

Biohythane production via anaerobic digestion process: fundamentals, scale-up challenges, and techno-economic and environmental aspects.

Biohythane, a balanced mixture comprising bioH2 (biohydrogen) and bioCH4 (biomethane) produced through anaerobic digestion, is gaining recognition as a promising energy source for the future. This article provides a comprehensive overview of biohythane production, covering production mechanisms, microbial diversity, and process parameters. It also explores different feedstock options, bioreactor designs, and scalability challenges, along with techno-economic and environmental assessments. Additionally, the article discusses the integration of biohythane into waste management systems and examines future prospects for enhancing production efficiency and applicability. This review serves as a valuable resource for researchers, engineers, and policymakers interested in advancing biohythane production as a sustainable and renewable energy solution.

Ultra-Dilute SnCl4-Catalyzed Conversion of Concentrated Glucose to 5-Hydroxymethylfurfural in Aqueous Deep Eutectic Solvent.

5-Hydroxymethylfurfural(HMF) is a versatile chemical synthesized from glucose dehydration catalyzed by metal chloride (MClx) in deep eutectic solvents (DESs). However, the low glucose concentration and high catalyst dosage hinder large-scale HMF production. Herein, we report an aqueous DES of tetraethylammonium bromide(TEAB)-glucose for converting concentrated glucose (40 wt%, relative to TEAB) using ultra-dilute SnCl4 (0.25 mol%), achieving a 62% yield of HMF. Ultra-dilute MClx-catalyzed selective conversion of glucose is feasible only when combining SnCl4 with Br-based DES, which is elucidated by density functional theory and molecular dynamic calculations. Using SnCl4 is essential due to its higher glucose isomerization activity than AlCl3 and CrCl3, which can be attributed to its low-barrier coordination with glucose and its barrier-free separation from fructose. Halide anions in DESs strongly interact with glucose, hindering the MClx-glucose coordination and thereby reducing MClx's activity for glucose isomerization. Consequently, Br-based DESs facilitate higher activity of MClx than Cl-based DESs, due to the weaker interaction between halide anion and glucose. In addition, we elucidated the side reactions including condensation, polymerization, and isomerization, and proposed a reaction network. Our findings clarify the differential activity of MClx and the impact of halide anions in DESs on MClx's activity.

Escherichia coli-based biorefining process yields optically pure lactic acid from fermented second-generation feedstocks.

Within the circular bioeconomy the production of optically pure LA from 2nd generation feedstocks would be ideal but it is very challenging. In this paper genetically engineered Escherichia coli strains were created to resolve racemic LA solutions synthesised and produced from the fermentation of organic waste or ensiled grass. Refining LA racemic mixtures into either a D- or L-LA was achieved by cells being able to consume one LA isomer as a sole carbon and energy source while not being able to consume the other. A D-LA refining strain JSP0005 was grown on fermented source-sorted organic household waste and different grass silage leachates, which are 2nd generation feedstocks containing up to 33 g/L lactic acid racemate. In all growth experiments, L-LA was completely removed leaving D-LA as the only LA stereoisomer, i.e. resulting in optically pure D-LA, which also increased by as much as 248.6 % from its starting concentration, corresponding to 38 g/L. The strains resulting from this study are a promising first step towards a microbial based LA biorefining process.

Assessing the environmental footprint of alternative green biorefinery protein extraction techniques from grasses and legumes.

The significant grasslands of Europe and its member states represents a significant feedstock opportunity for circular bioeconomy development. The development of green biorefineries (GBR), to supply protein for the feed industry from grass, could help many European member states to address significant deficits in protein availability and reduce imports. The current study assesses the environmental footprint of alternative GBR protein extraction techniques from grasses and legumes using life cycle assessment. The focus is on comparing feedstock and technology pathways that could displace soya bean imports. The study finds that leaf protein concentrate (LPC) produced from grass had an improved environmental performance when compared to soya bean meal (SBM), across the assessed feedstock (perennial ryegrass or grass-clover mixtures) and technology pathways (one-stage maceration versus multi-stage maceration). For example, in the case of Climate Change the emission intensity for LPC was 57-85 % lower per tonne of crude protein (CP) compared with SBM. Acidification burdens were 54-88 % lower, and Eutrophication: Freshwater burdens were 74-89 % lower. Some scenarios of GBR produced LPC with a larger Energy Resources: Non-Renewable burden than SBM, though this could be mitigated with higher renewable energy (biogas and wind energy) integration within the scenario. Grass-clover scenarios generally achieved a lower intensity of emissions compared to ryegrass scenarios, particularly in the category of Climate Change, where feedstock cultivation represented a significant contributor to impacts. Overall, GBR can produce high quality protein with a lower environmental burden than SBM, but choice of feedstock and system design are critical factors for overall environmental performance.

Copper(II) and Zinc(II) Complexes with Bacterial Prodigiosin Are Targeting Site III of Bovine Serum Albumin and Acting as DNA Minor Groove Binders.

The negative environmental and social impacts of food waste accumulation can be mitigated by utilizing bio-refineries' approach where food waste is revalorized into high-value products, such as prodigiosin (PG), using microbial bioprocesses. The diverse biological activities of PG position it as a promising compound, but its high production cost and promiscuous bioactivity hinder its wide application. Metal ions can modulate the electronic properties of organic molecules, leading to novel mechanisms of action and increased target potency, while metal complex formation can improve the stability, solubility and bioavailability of the parent compound. The objectives of this study were optimizing PG production through bacterial fermentation using food waste, allowing good quantities of the pure natural product for further synthesizing and evaluating copper(II) and zinc(II) complexes with it. Their antimicrobial and anticancer activities were assessed, and their binding affinity toward biologically important molecules, bovine serum albumin (BSA) and DNA was investigated by fluorescence emission spectroscopy and molecular docking. The yield of 83.1 mg/L of pure PG was obtained when processed meat waste at 18 g/L was utilized as the sole fermentation substrate. The obtained complexes CuPG and ZnPG showed high binding affinity towards target site III of BSA, and molecular docking simulations highlighted the affinity of the compounds for DNA minor grooves.

Lignin self-assembly phenomena and valorization strategies for pulping, biorefining, and materials development: Part 1. The physical chemistry of lignin self-assembly.

Physical chemistry aspects are emphasized in this comprehensive review of self-assembly phenomena involving lignin in various forms. Attention to this topic is justified by the very high availability, low cost, and renewable nature of lignin, together with opportunities to manufacture diverse products, for instance, polymers/resins, bioplastics, carbon fibers, bio-asphalt, sunscreen components, hydrophobic layers, and microcapsules. The colloidal lignin material, nanoparticles, and microstructures that can be formed as a result of changes in solvent properties, pH, or other adjustments to a suspending medium have been shown to depend on many factors. Such factors are examined in this work based on the concepts of self-assembly, which can be defined as an organizing principle dependent on specific attributes of the starting entities themselves. As a means to promote such concepts and to facilitate further development of nano-scale lignin products, this article draws upon evidence from a wide range of studies. These include investigations of many different plant sources of lignin, processes of delignification, solvent systems, anti-solvent systems or other means of achieving phase separation, and diverse means of achieving colloidal stability (if desired) of resulting self-assembled lignin structures. Knowledge of the self-organization behavior of lignin can provide significant structural information to optimize the use of lignin in value-added applications. Examples include chemical conditions and preparation procedures in which lignin-related compounds of particles organize themselves as spheres, hollow spheres, surface-bound layers, and a variety of other structures. Published articles show that such processes can be influenced by the selection of lignin type, pulping or extraction processes, functional groups such as phenolic, carboxyl, and sulfonate, chemical derivatization reactions, solvent applications, aqueous conditions, and physical processes, such as agitation. Precipitation from non-aqueous solutions represents a key focus of lignin self-assembly research. The review also considers stabilization mechanisms of self-assembled lignin-related structures.

Enhanced astaxanthin production in Haematococcus lacustris by electrochemical stimulation of cyst germination.

This study investigated the technical feasibility of using electrogermination to activate dormant cysts as an inoculum for subsequent 14-d photosynthetic astaxanthin production in Haematococcus lacustris. Electrotreatment affected the cell viability, surface charge, and morphology of H. lacustris cysts. At an optimal voltage of 2 V for 60 min, the cyst germination rate peaked at 44.6 % after 1 d, representing a 2.2-fold increase compared with that of the untreated control. Notably, electrogermination significantly enhanced both the astaxanthin content (44.9 mg/g cell) and productivity (13.2 mg/L/d) after 14 d of photobioreactor cultivation, corresponding to 1.7- and 1.5-fold increases compared with those in control, respectively. However, excessive electrotreatment, particularly at voltages exceeding 2 V or for durations beyond 60 min, did not enhance the astaxanthin production capability of H. lacustris. Proper optimization of renewable electrogermination can enable sustainable algal biorefinery to produce multiple bioactive products without compromising cell viability and astaxanthin productivity.

Metal-organic framework-enabled biomass conversion technologies for microalgae bio-refinery in the food industry.

Biomass is a valuable renewable energy adapted as an alternative to traditional fossil fuels. Apart from fuels, biomass is synthesized into highly valuable products that are used in various forms including biofuels, biochemical, bioproducts, packing material, and find practice in pharmaceutical, cosmetics, and nutraceuticals industries. Particularly, microalgae a third-generation feedstock known for its rich carbon content possesses protein lipids and carbohydrates produces a variety of green products such as bioethanol, biohydrogen, biodiesel, and biomethane, and also fixes carbon emission to a certain amount in the atmosphere. However, microalgae conversion in the presence of a catalyst such as a metal-organic framework (MOF) yields high-quality valuable products. A MOF is a porous crystalline material where the structure and pore size can be controlled making it suitable for catalytic reactions and appropriate conversion paths. This review briefly explains the prevailing status of microalgae as a sustainable biomass and features its components for microalgae biorefinery into valuable products and its application in the food industry. MOF properties, characteristics and various MOF-based conversion technologies for biomass conversion with its application are elaborated. In addition, usage of value products produced from microalgae biorefinery in the food industry and its importance is elucidated. In addition, the challenges in integrating biorefinery processes with food industry operations and their solutions are also presented. © 2024 Society of Chemical Industry.

A high-performance anion-exchange chromatographic method for the fast analysis and precise determination of varied glucose-derived acids during biomass biorefinery.

Glucose-derived acids for the further production of value-added medicine, food additives, and polymers, will promote lignocellulosic biomass biorefinery industry. In response to the diversity and complexity, a new method was established by employing high performance anion exchange chromatography (HPAEC) coupled with a CarboPac™ PA200 column, for the precise and fast determination of glucose, gluconic acid, glucuronic acid, 2-ketogluconic acid, 5-ketogluconic acid and glucaric acid. Based on the analysis of tiny varieties in retention behavior, a gradient elution mode was designed and optimized for the quantitative and qualitative analysis. The protocol displayed acceptable linearity (R2 ≥ 0.995), commendable average recovery rate (95.28% âˆ¼ 99.89%), satisfactory precision (RSD% ≤ 1.5%), and sufficient resolution (R > 6). Additionally, this method was successfully applied to the high-value biorefining process, which confirmed the practicability and accuracy. The results demonstrated that HPAEC has good detection performance for glucose and its derivative acids, and provide key identification technical support for the high-value utilization of lignocellulose.

Direct Itaconate Production from Brown Macroalgae Using Engineered Vibrio sp. dhg.

Itaconate is a promising platform chemical with broad applicability, including the synthesis of poly(methyl methacrylate). Most studies on microbial itaconate production entail the use of crop-based feedstock, which imposes constraints due to its limited supply. Brown macroalgae have recently gained attention as next-generation biomass owing to their high biomass productivity and carbohydrate content and amenability to mass production. Therefore, the use of macroalgae for itaconate production warrants exploration. In this study, the direct production of itaconate from brown macroalgae was demonstrated using engineered Vibrio sp. dhg, which has emerged as an efficient platform host for brown macroalgal biorefineries. Specifically, to enhance production, cis-aconitate decarboxylase (Cad) from Aspergillus terreus was heterologously expressed and isocitrate dehydrogenase (icd) was deleted. Notably, the resulting strain, VIC, achieved itaconate titers of 2.5 and 1.5 g/L from a mixture of alginate and mannitol (10 g/L of each) and 40 g/L of raw Saccharina japonica (S. japonica), respectively. Overall, this study highlights the utility of brown macroalgae as feedstock, as well as that of Vibrio sp. dhg as a platform strain for improving itaconate bioproduction.

Obtention and Characterization of Microcrystalline Cellulose from Industrial Melon Residues Following a Biorefinery Approach.

Residual melon by-products were explored for the first time as a bioresource of microcrystalline cellulose (MCC) obtention. Two alkaline extraction methods were employed, the traditional (4.5% NaOH, 2 h, 80 °C) and a thermo-alkaline in the autoclave (2% NaOH, 1 h, 100 °C), obtaining a yield of MCC ranging from 4.76 to 9.15% and 2.32 to 3.29%, respectively. The final MCCs were characterized for their chemical groups by Fourier-transform infrared spectroscopy (FTIR), crystallinity with X-ray diffraction, and morphology analyzed by scanning electron microscope (SEM). FTIR spectra showed that the traditional protocol allows for a more effective hemicellulose and lignin removal from the melon residues than the thermo-alkaline process. The degree of crystallinity of MCC ranged from 51.51 to 61.94% and 54.80 to 55.07% for the thermo-alkaline and traditional processes, respectively. The peaks detected in X-ray diffraction patterns indicated the presence of Type I cellulose. SEM analysis revealed microcrystals with rough surfaces and great porosity, which could remark their high-water absorption capacity and drug-carrier capacities. Thus, these findings could respond to the need to valorize industrial melon by-products as raw materials for MCC obtention with potential applications as biodegradable materials.

Advancements in medium chain fatty acids production through chain elongation: Key mechanisms and innovative solutions for overcoming rate-limiting steps.

The depletion of fossil fuels has prompted an urgent search for alternative chemicals from renewable sources. Current technology in medium chain fatty acids (MCFAs) production though chain elongation (CE) is becoming increasingly sustainable, hence the motivation for this review, which provides the detailed description, insights and analysis of the metabolic pathways, substrates type, inoculum and fermentation process. The main rate-limiting steps of microbial MCFAs production were comprehensively revealed and the corresponding innovative solutions were also critically evaluated. Innovative strategies such as substrate pretreatment, electrochemical regulation, product separation, fermentation parameter optimization, and electroactive additives have shown significant advantages in overcoming the rate-limiting steps. Furthermore, novel regulatory strategies such as quorum sensing and electronic bifurcation are expected to further increase the MCFAs yield. Finally, the techno-economic analysis was carried out, and the future research focuses were also put forward.

Chemicals and fuels from lipid-containing biomass: A comprehensive exploration.

In response to address the climate crisis, there has been a growing focus on substituting conventional refinery-derived products with those derived from biorefineries. The utilization of lipids as primary materials or intermediates for the synthesis of chemicals and fuels, which are integral to the existing chemical and petrochemical industries, is a key step in this transition. This review provides a comprehensive overview of the production of sustainable chemicals (acids and alcohols), biopolymers, and fuels (including gasoline, kerosene, biodiesel, and heavy fuel oil) from lipids derived from terrestrial and algal biomass. The production of chemicals from lipids involves diverse methods, including polymerization, epoxidation, and separation/purification. Additionally, the transformation of lipids into biofuels can be achieved through processes such as catalytic cracking, hydroprocessing, and transesterification. This review also suggests future research directions that further advance the lipid valorization processes, including enhancement of catalyst durability at harsh conditions, development of deoxygenation process with low H2 consumption, investigation of precise separation of target compounds, increase in lipid accumulation in algal biomass, and development of methods that utilize residues and byproducts generated during lipid extraction and conversion.

Chemical approaches for the biomass valorisation: a comprehensive review of pretreatment strategies.

The most abundant natural renewable resource in the world, lignocellulosic biomass (LCB), has the potential to be exploited as a substitute green feedstock for the synthesis of various chemicals, materials, and biofuels. The annual global production of 13 billion tonnes of LCB offers an opportunity to cater to the increasing energy and materials requirement of process industries and also restricts the discharge of greenhouse gases. Although LCB is enriched with valuable ingredients such as cellulose, lignin, and hemicellulose, its recalcitrant nature limits its efficient utilisation. These components of LCB are strongly interlinked with each other, which resists their isolation and conversion valorisation into useful products. To disrupt the complicated structure of LCB and to isolate the lignocellulosic components in pure form, pretreatment is a crucial process in the bio-refinery, ensuring the economic feasibility of downstream processes. This review provides an outline of the structure, composition, and various sources of LCB; and the necessity of the pretreatment. Moreover, this article provides an in-depth analysis of the underlying mechanisms, advantages, and limitations of various pretreatment methods, such as physical, chemical, biological, and physicochemical. Further, the impact of chemical pretreatment techniques on the physicochemical characteristics of the material that is extracted from the biomass is also covered in detail through the rigorous evaluation of performance metrics, including substrate digestibility, sugar yield, inhibitor production, and energy requirements. This review provides a balanced and comprehensive overview of the state-of-the-art pretreatment strategies and their impact on biomass valorisation that will be useful to the scientists, engineers, and policy makers interested in biomass conversion technologies.

Resource recovery and contaminants of emerging concern mitigation by microalgae treating wastewater.

This study aimed to investigate the recovery of agricultural biostimulants and biogas from microalgae treating wastewater, in the framework of a circular bioeconomy. To this end, municipal wastewater was treated in demonstrative raceway ponds, and microalgal biomass (Scenedesmus sp.) was then harvested and downstream processed to recover biostimulants and biogas in a biorefinery approach. The effect of microalgal biostimulants on plants was evaluated by means of bioassays, while the biogas produced was quantified in biochemical methane potential (BMP) tests. Furthermore, the fate of contaminants of emerging concern (CECs) over the process was also assessed. Bioassays confirmed the biostimulant effect of microalgae, which showed gibberellin-, auxin- and cytokinin-like activity in watercress seed germination, mung bean rooting, and wheat leaf chlorophyll retention. In addition, the downstream process applied to raw biomass acted as a pre-treatment to enhance anaerobic digestion performance. After biostimulant extraction, the residual biomass represented 91% of the methane yield from the raw biomass (276 mLCH4·g-1VS). The kinetic profile of the residual biomass was 43% higher than that of the unprocessed biomass. Co-digestion with primary sludge further increased biogas production by 24%. Finally, the concentration of CECs in wastewater was reduced by more than 80%, and only 6 out of 22 CECs analyzed were present in the biostimulant obtained. Most importantly, the concentration of those contaminants was lower than in biosolids that are commonly used in agriculture, ensuring environmental safety.

Tailoring Cu-SiO2 Interaction through Nanocatalyst Architecture to Assemble Surface Sites for Furfural Aqueous-Phase Hydrogenation to Cycloketones.

In this contribution, nanocatalysts with rather diverse architectures were designed to promote different intimacy degrees between Cu and SiO2 and consequently tune distinct Cu-SiO2 interactions. Previously synthesized copper nanoparticles were deposited onto SiO2 (NPCu/SiO2) in contrast to ordinarily prepared supported Cu/SiO2. NPCu@SiO2 and SiO2@Cu core-shell nanocatalysts were also synthesized, and they were all bulk and surface characterized by XRD, TGA, TEM/HRTEM, H2-TPR, XANES, and XPS. It was found that Cu0 is the main copper phase in NPCu/SiO2 while Cu2+ rules the ordinary Cu/SiO2 catalyst, and Cu0 and electron-deficient Cuδ+ species coexist in the core-shell nanocatalysts as a consequence of a deeper metal-support interaction. Catalytic performance could not be associated with the physical properties of the nanocatalysts derived from their architectures but was associated with the more refined chemical characteristics tuned by their design. Cu/SiO2 and NPCu/SiO2 catalysts led to the formation of furfuryl alcohol, evidencing that catalysts holding weak or no metal-support interaction have no significant impact on product distribution even in the aqueous phase. The establishment of such interactions through advanced catalyst architecture, allowing the formation of electron-deficient Cuδ+ moieties, particularly Cu2+ and Cu+ as unveiled by spectroscopic investigations, is critical to promoting the hydrogenation-ring rearrangement cascade mechanism leading to cycloketones.

Pressure-driven membrane processes for the recovery and recycling of deep eutectic solvents: A seaweed biorefinery case study.

Deep eutectic solvents (DES) are green alternatives for conventional solvents. They have gained attention for their potential to extract valuable compounds from biomass, such as seaweed. In this framework, a case study was developed to assess the feasibility of pressure-driven membrane processes as an efficient tool for the recovery of deep eutectic solvents and targeted biomolecules. For this purpose, a mixture composed of the DES choline chloride - ethylene glycol (ChCl-EG) 1:2, water and alginate was made to mimic a DES extraction from seaweed. An integrated separation process design was proposed where ultrafiltration-diafiltration-nanofiltration (UF-DF-NF) was coupled. UF and DF were found to be effective for the separation of alginate with an 85 % yield. DES was likewise recovered by 93 %, proving the membrane filtrations' technical feasibility. The NF performance to separate the DES from the water, for its recycling, laid by a 45 %-50 % retention and a final concentrated DES solution of 18 %(v/v).

Towards Sustainable Production of Polybutylene Adipate Terephthalate: Non-biological Catalytic Syntheses of Biomass-derived Constituents.

Renewable chemicals, which are made from renewable resources such as biomass, have attracted significant interest as substitutes for natural gas- or petroleum-derived chemicals to enhance the sustainability of the chemical and petrochemical industries. Polybutylene adipate terephthalate (PBAT), which is a copolyester of 1,4-butanediol (1,4-BDO), adipic acid (AA), and dimethyl terephthalate (DMT) or terephthalic acid (TPA), has garnered significant interest as a biodegradable polymer. This study assesses the non-biological production of PBAT monomers from biomass feedstocks via heterogeneous catalytic reactions. The biomass-based catalytic routes to each monomer are analyzed and compared to conventional routes. Although no fully commercialized catalytic processes for direct conversion of biomass into 1,4-BDO, AA, DMT, and TPA are available, emerging and promising catalytic routes have been proposed. The proposed biomass-based catalytic pathways toward 1,4-BDO, AA, DMT, and TPA are not yet fully competitive with conventional fossil fuel-based pathways mainly due to high feedstock prices and the existence of other alternatives. However, given continuous technological advances in the renewable production of PBAT monomers, bio-based PBAT should be economically viable in the near future.