Biorefinery Perspective Research Articles

Tomato Residue Management from a Biorefinery Perspective and towards a Circular Economy.

The tomato industry is a relevant socio-economic activity in the European Union, while it generates a large variety of residues. Tomatoes unfit for consumption, tomato peels, seeds, industrial pomace, and plants are examples of residues of this industry. Commonly, some of the residues can be left in the field, composted, used for animal feeding, or valorized through anaerobic digestion. However, more economic value can be attributed to these residues if a biorefinery approach is applied. Indeed, many value-added compounds can be obtained by the integration of different processes while closing the carbon and nutrient loops. The extraction of bioactive compounds followed by anaerobic digestion and composting seems to be a viable proposal for a biorefinery approach. Thus, this study aims to review the biorefinery strategies for valorizing tomato residues, highlighting the main processes proposed. The recovery of lycopene, β-carotene, and phenolic compounds has been widely studied at the lab scale, while energy recovery has already been applied at the industrial scale. Although techno-economic analysis is scarce for tomato residue valorization processes, positive net present values (NPV) and low payback times (PBT) have been reported in the literature. Thus, more work comparing multiple extraction technologies and biorefinery strategies coupled with economic and environmental assessment should be performed to select the most promising management route for tomato residues.

A Review on Biolubricants Based on Vegetable Oils through Transesterification and the Role of Catalysts: Current Status and Future Trends

The use of biolubricants as an alternative to petroleum-based products has played an important role in the last decade. Due to the encouragement of global policies, which mainly support green chemistry and circular economy, there has been an increasing interest in bio-based products, including biolubricants, from scientific and industrial points of view. Their raw materials, production, and characteristics might vary, as biolubricants present different applications for a wide range of practical uses, making this field a continuously changing subject of study by researchers. The aim of this work was to study biolubricant production from vegetable oil crops from a bio-refinery perspective, paying attention to the main raw materials used, the corresponding production methods (with a special focus on double transesterification), the role of catalysts and some techno-economic studies. Thus, the main factors affecting quality parameters such as viscosity or oxidative stability have been covered, including catalyst addition, reaction temperature, or the use of raw materials, reagents, or additives were also analyzed. In conclusion, the search for suitable raw materials, the use of heterogeneous catalysts to improve the effectiveness and efficiency of the process, and the optimization of chemical conditions seem to be the most interesting research lines according to the literature.

A biorefinery model for the production of oil and biomethane using castor plants

AbstractCastor (Ricinus communis L.) is an important oilseed crop worldwide whose inedible oil is widely used in the industrial, pharmaceutical, and agricultural sectors. Castor plants show high conversion potential for use as biorefining feedstocks. The present study was conducted to investigate the effects of two nitrogen fertilization levels (0 and 120 kg N ha−1) on seed and oil yield. From a biorefinery perspective, the residual biomass of seed processing was analyzed in terms of fiber composition and biomethane production carrying out a biological pretreatment using two white‐rot fungi (Pleurotus ostreatus and Irpex lacteus). Nitrogen fertilization resulted in an increase in seed and oil yields and a difference in capsule husk composition. Fungal pretreatment of capsule husks showed promising effects on anaerobic digestion, increasing the biomethane yield compared to untreated biomass. The highest lignin degradation and the lowest cellulose loss during pretreatment were obtained with I. lacteus, and this fungal pretreatment resulted in the highest biomethane yield (103.2 NmL g−1 volatile solids) for the fertilized biomass.

Semi-continuous production of polyhydroxybutyrate (PHB) in the Chlorophyta Desmodesmus communis

Polyhydroxyalkanoates (PHAs) are promising alternatives that accumulate as energy and carbon storage material in various microorganisms, including bacteria and microalgae, being biodegradable and suitable for a wide variety of applications. Among these compounds, the most prevalent and well-characterized biopolymer is polyhydroxybutyrate (PHB), which belongs to the short-chain PHAs.The present study was designed to evaluate algae-based PHB production in two Chlorophyta (Desmodesmus communis and Chlorella vulgaris) under a two-phase nutritional mode of cultivation, namely a phototrophic growth phase (PGP) and a mixotrophic stress phase (MSP) with N,P-depleted media and organic carbon supply (i.e., glucose or sodium acetate, NaOAc). The highest PHB productivity (0.11 g PHB/g biomass/d; 0.015 g PHB/L/d), corresponding to 32.1 % w/w of intracellular PHB, was observed for D. communis after 3 days of cultivation under mixotrophic conditions in batch cultures (e.g., low light, phosphorus-free medium, 1 g/L of NaOAc). A scaled-up cultivation (10 L) was set up to evaluate for the first time PHB yields and biomass composition in a semi-continuous system. A PHB content of 34 % w/w was achieved on day 8, corresponding to a maximum PHB productivity of 0.10 g PHB/g biomass/d (or 0.011 g PHB/L/d), which increased up to 54 % w/w on day 15. The biomass was composed of about 30 % w/w proteins, 6 % w/w polysaccharides, and 11 % w/w lipids, which can be valorised from a biorefinery perspective. The scaled-up D. communis cultivation in 10 L PBRs confirmed the potential utilization of this algal species for PHB production with productivity up to 2-times higher than those reported for several cyanobacterial species and similar to the maximum value obtained with batch cultures in previous works performed with Scenedesmaceae.

Bioplastics from orange processing byproducts by an ecoefficient hydrothermal approach

Valorization of orange processing byproducts into bioplastics represents a sustainable alternative to virgin plastics for some applications. In this study, we obtained three films based on such biomass, namely, orange peel (OPe), orange pomace (OPo), and a combination of peel, pomace, and finisher pulp (OPPP). The byproducts were submitted to a “clean” hydrothermal pretreatment at 121 °C for 30 min at 1.2 kgf.cm−2. They were then added with glycerol, homogenized, cast into films, and dried. The OPe film presented higher water vapor permeability and poorer overall tensile properties compared to the other films, possibly due to the lower polysaccharide contents in the peel compared to those in the pomace. The OPPP film was considered the most interesting from a biorefinery perspective since it is made from three orange processing byproducts instead of only one. Moreover, all films exhibited high antioxidant and UV-absorption capacities, indicating their potential applicability as active packaging materials for oxidizable products.

Bioconversion of Cheese Whey and Food By-Products by Phaeodactylum tricornutum into Fucoxanthin and n-3 Lc-PUFA through a Biorefinery Approach.

This study investigates the potential of utilizing three food wastes: cheese whey (CW), beet molasses (BM), and corn steep liquor (CSL) as alternative nutrient sources for the cultivation of the diatom Phaeodactylum tricornutum, a promising source of polyunsaturated eicosapentaenoic acid (EPA) and the carotenoid fucoxanthin. The CW media tested did not significantly impact the growth rate of P. tricornutum; however, CW hydrolysate significantly enhances cell growth. BM in cultivation medium enhances biomass production and fucoxanthin yield. The optimization of the new food waste medium was conducted through the application of a response surface methodology (RSM) using hydrolyzed CW, BM, and CSL as factors. The results showed a significant positive impact of these factors (p < 0.005), with an optimized biomass yield of 2.35 g L-1 and a fucoxanthin yield of 3.64 mg L-1 using a medium composed of 33 mL L-1 of CW, 2.3 g L-1 of BM, and 2.24 g L-1 of CSL. The experimental results reported in this study showed that some food by-products from a biorefinery perspective could be utilized for the efficient production of fucoxanthin and other high-added-value products such as eicosapentaenoic acid (EPA).

Extraction of phytostimulant molecules from Scenedesmus almeriensis using different extractor systems

There is an increasing demand for bio-based fertilizers and phytostimulants. Microalgae biomass contains a number of compounds that have positive effects on plant growth (for instance, phenolic compounds). Other valuable substances are simultaneously produced in the biomass, enabling a biorefinery approach to be applied. Downstream processing optimization for sustainable economic biostimulant production must involve the use of microalgal wet paste instead of dry biomass. The present study investigated the effect of different parameters, such as the solvent, temperature, and time, on the extraction of biostimulant molecules from Scenedesmus almeriensis microalgal biomass. The extraction process optimization was determined by calculating the germination index in the watercress seed bioassays. Since phenols and other bioactives are extracted together, and purification should be avoided, biological methods are preferred for assessing biostimulation. Water was compared to organic solvents of lower polarity such as acetone, ethanol (96%), and an ethanol:hexane:water (76:18:6 v/v/v) mixture. Different solvent extraction ratios (0.5–8 mL solvent g−1 of dry biomass), temperatures (25–50 ºC), and extraction times (0.5–6 h) were tested, after which the best combination was selected for each solvent. The optimal conditions were obtained with organic green solvents (acetone or ethanol), which resulted in a Germination Index above 120% (at least 20% above the distilled water control). Consequently, from a biorefinery perspective, this process was considered to be the most suitable for microalgal biomass exploitation.Graphical

Rhodotorula sp. as a cell factory for production of valuable biomolecules.

Rhodotorula sp. are well-known for their ability to biosynthesize a diverse range of valuable biomolecules, including carotenoids, lipids, enzymes, and polysaccharides. Despite the high number of studies conducted using Rhodotorula sp. at the laboratory scale, most of these do not address all processual aspects necessary for scaling up these processes for industrial applications. This chapter explores the potential of Rhodotorula sp. as a cell factory for the production of distinct biomolecules, with a particular emphasis on exploring their use from a biorefinery perspective. Through in-depth discussions of the latest research and insights into non-conventional applications, we aim to provide a comprehensive understanding of Rhodotorula sp.'s ability to produce biofuels, bioplastics, pharmaceuticals, and other valuable biochemicals. This book chapter also examines the fundamentals and challenges associated with the optimizing upstream and downstream processing of Rhodotorula sp-based processes. We believe that through this chapter, readers with different levels of expertise will gain insights into strategies for enhancing the sustainability, efficiency, and effectiveness of producing biomolecules using Rhodotorula sp.

Protease-Assisted Mild Extraction of Soluble Fibre and Protein from Fruit By-Products: A Biorefinery Perspective.

By-products from the fruit supply chain, especially seeds/kernels, have shown great potential to be valorised, due to their high content of macronutrients, such as lipids, protein, and fibre. A mild enzymatic assisted extraction (EAE) involving the use of a protease was tested to evaluate the feasibility of a cascade approach to fractionate the main fruit by-products components. Protease from Bacillus licheniformis (the enzyme used in the AOAC 991.43 official method for dietary fibre quantification) was used, and besides protein, the conditions of hydrolysis (60 °C, neutral pH, overnight) allowed us to dissolve a portion of soluble fibres, which was then separated from the solubilized peptide fraction through ethanol precipitation. Good protein extraction yields, in the range 35-93%, were obtained. The soluble fibre extraction yield ranged from 1.6% to 71% depending on the by-product, suggesting its applicability only for certain substrates, and it was found to be negatively correlated with the molecular weight of the fibre. The monosaccharide composition of the soluble fibres extracted was also diverse. Galacturonic acid was present in a low amount, indicating that pectin was not efficiently extracted. However, a predominance of arabinose and galactose monomers was detected in many fractions, indicating the isolation of a fruit soluble fibre portion with potential similarity with arabinogalactans and gum arabic, opening up perspectives for technological applications. The residual solid pellet obtained after protease assisted extraction was found to be an excellent fibre-rich substrate, suitable for being subjected to more "hard" processing (e.g., sequential pectin and hemicellulose extraction) with the objective to derive other fractions with potential great added economic value.

Chemical composition, morphology, antioxidant, and fuel properties of pine nut shells within a biorefinery perspective

Chemical composition, morphology, antioxidant, and fuel properties of pine nut shells within a biorefinery perspective

Biomethane and biodiesel production from sunflower crop: A biorefinery perspective

As an industrial energy plant, the whole parts of the sunflower crop were used for biofuel production through a biorefinery approach. Two scenarios were suggested for this biorefinery, i.e., using all parts of the crop separately and the whole residues as a mixture. The oil extracted from seeds was applied for biodiesel production through transesterification using a 6:1 methanol to oil molar ratio with 0.7% catalyst at 50 °C for 65 min. The process resulted in a 96.2% biodiesel yield with a heating value of 41.6 MJ/kg, corresponding to 84 kg biodiesel per ton of sunflower crop and 108.8 L gasoline-equivalent. Three physiochemical pretreatments were employed for structural modification of lignocellulosic residues, and the solid and liquid phases of the pretreatments were anaerobically digested for biomethane production. The effects of hot water (180 °C, 1 h), concentrated phosphoric acid (50 °C, 1 h, 85%), and sodium carbonate (142 °C, 18 min, 4%) pretreatments on composition, crystallinity, morphology, and biogas production of solid samples were evaluated. The highest methane yield of solid fractions was obtained from samples treated with phosphoric acid, and the seed cake showed the maximum yield of 342.7 N mL/g VS among all parts. Furthermore, the liquid phase of the hot water and alkaline pretreatments produced a high amount of biomethane, contrary to the acidic pretreatment. The overall mass balance showed that 11095.0 MJ/t energy (containing 346.7 L gasoline energy) was produced through the optimum biorefinery, where the untreated mixture and seed cake were used for biomethane production and the extracted oil for biodiesel production.

Lignin from Residual Sawdust of Eucalyptus spp.—Isolation, Characterization, and Evaluation of the Antioxidant Properties

Lignin is an abundant biopolymer, as well as cellulose and hemicellulose. Thus, this work aimed at isolating and characterizing the lignin from Eucalyptus spp. Sawdust—a lignocellulosic waste generated in large amounts in sawmills—to evaluate its antioxidant capacity. A biorefinery perspective was utilized: the biomass was fractionated using a sequential acid-alkaline treatment to recover the hemicellulosic carbohydrates, preserving the cellulose-rich solid fraction and isolating the lignin. The physicochemical characterization of isolated lignin was carried out using thermogravimetric (TGA), Fourier-transform infrared spectroscopy (FTIR), and nuclear magnetic resonance (NMR) analyses, while the antioxidant property was evaluated employing electron transfer and using DPPH and ABTS assays. After sequential acid-alkaline treatment, 68.15% of the hemicellulosic carbohydrates were recovered using mild acid treatment. The specific yield of lignin was 69.38%, and the remaining solid fraction contained 60.42% of cellulose. The antioxidant activity of lignin was evaluated using a DPPH radical test, and it showed an inhibition of 81.58% and IC50 of 60 μg/mL. For the ABTS test, the inhibition was 99.86%, and the IC50 was 7.39 µg/mL. Therefore, the lignin isolated from residual eucalyptus sawdust using sequential acid-alkaline treatment presented interesting antioxidant properties, which should be further investigated and evaluated for different applications.

Factorial Optimization of Ultrasound-Assisted Extraction of Phycocyanin from Synechocystis salina: Towards a Biorefinery Approach.

PC is a bioactive and colorant compound widely sought in the food, nutraceutical and cosmetic industries, and one of the most important pigments produced by Synechocystis salina. However, the general extraction process is usually time-consuming and expensive, with low extraction yields—thus compromising a feasible and sustainable bioprocess. Hence, new extraction technologies (e.g., ultrasound assisted-extraction or UAE) emerged in the latest years may serve as a key step to make the overall bioprocess more competitive. Therefore, this study aimed at optimizing the yields of phycocyanin (PC) rich-extracts of S. salina by resorting to UAE; in attempts to explore this process in a more economically feasible way; valorization of the remaining cyanobacterial biomass, via extraction of other bioactive pigments and antioxidants, was tackled within a biorefinery perspective. A two-stage extraction (using ethanol and water) was thus performed (because it favors PC extraction); other bioactive pigments, including chlorophyll a (chl a), carotenoids, and other phycobiliproteins (PBPs), but also antioxidant (AOX) capacity and extraction yields were also evaluated for their optimum UAE yields. A factorial design based on Box–Behnken model was developed; and the influence of such extraction parameters as biomass to solvent ratio (B/S ratio = 1.5–8.5 mg·mL−1), duty cycle (DT = 40–100%), and percentage of amplitude (A = 40–100%) were evaluated. The model predicted higher PC yields with high B/S ratio = 6 mg·mL−1, lower DT = 80% and an A = 100%. Classical extraction was compared with UAE under the optimum conditions found; the latter improved PC yields by 12.5% and 47.8%, when compared to freeze-thawing extraction, and bead beater homogenization-based extraction, respectively. UAE successive extractions allowed to valorize other important bioactive compounds than PC, by reusing biomass, supporting a favorable contribution to the economic feasibility of the S. salina-based process towards a biorefinery approach.

Increasing Value of Winery Residues through Integrated Biorefinery Processes: A Review

The wine industry is one of the most relevant socio-economic activities in Europe. However, this industry represents a growing problem with negative effects on the environment since it produces large quantities of residues that need appropriate valorization or management. From the perspective of biorefinery and circular economy, the winery residues show high potential to be used for the formulation of new products. Due to the substantial quantities of phenolic compounds, flavonoids, and anthocyanins with high antioxidant potential in their matrix, these residues can be exploited by extracting bioactive compounds before using the remaining biomass for energy purposes or for producing fertilizers. Currently, there is an emphasis on the use of new and greener technologies in order to recover bioactive molecules from solid and liquid winery residues. Once the bio compounds are recovered, the remaining residues can be used for the production of energy through bioprocesses (biogas, bioethanol, bio-oil), thermal processes (pyrolysis, gasification combustion), or biofertilizers (compost), according to the biorefinery concept. This review mainly focuses on the discussion of the feasibility of the application of the biorefinery concept for winery residues. The transition from the lab-scale to the industrial-scale of the different technologies is still lacking and urgent in this sector.

Advances in Catalytic Routes for the Homogeneous Green Conversion of the Bio-Based Platform 5-Hydroxymethylfurfural.

5‐Hydroxymethylfufural (HMF) is an intriguing platform molecule that can be obtained from biomasses and that can lead to the production of a wide range of products, intermediates, or monomers. The presence of different moieties in HMF (hydroxy, aldehyde, furan ring) allows to carry out different transformations such as selective oxidations and hydrogenations, reductive aminations, etherifications, decarbonylations, and acetalizations. This is a great chance in a biorefinery perspective but requires the development of active and highly selective catalysts. In this view, homogeneous catalysis can lead to efficient conversion of HMF at mild reaction conditions. This Review discussed the recent achievements in homogeneous catalysts development and application to HMF transformations. The effects of metal nature, ligands, solvents, and reaction conditions were reported and critically reviewed. Current issues and future chances have been presented to drive future studies toward more efficient and scalable processes.

Xylo-oligosaccharides, fermentable sugars, and bioenergy production from sugarcane straw using steam explosion pretreatment at pilot-scale

This study investigated the production of xylo-oligosaccharides (XOS) from sugarcane straw (SCS) using steam explosion (SE) pretreatment at pilot-scale, as well as co-production of fermentable sugars and lignin-rich residues for bioethanol and bioenergy, respectively. SE conditions 200 °C; 15 bar; 10 min led to 1) soluble XOS yields of up to 35 % (w/w) of initial xylan with ∼50 % of the recovered XOS corresponding to xylobiose and xylotriose, considered the most valuable sugars for prebiotic applications; 2) fermentable glucose yields from the enzymatic hydrolysis of SE-pretreated SCS of up to ∼78 %; 3) increase in the energy content of saccharified SCS residues (16 %) compared to the untreated material. From an integrated biorefinery perspective, it demonstrated the potential use of SCS for the production of value-added XOS ingredients as well as liquid and solid biofuel products.

Screening for suitable mixed microbial consortia from anaerobic sludge and animal dungs for biodegradation of brewery spent grain

Lignocellulosic wastes, such as brewery spent grain (BSG), represent valuable resources from a biorefinery perspective, being sources of both chemical and energy production. Improving degradation rates of these recalcitrant feedstocks is a necessity, and bioaugmentation with specialised microbial consortia can be a viable means of achieving this. Six sources of mixed microbial consortia were screened, using biodegradation activity tests, for their capacity to enhance production of both chemicals (volatile fatty acids or ethanol) and energy (biogas) from BSG. The inocula used were anaerobic granular sludge as i) intact granules and ii) crushed granules, iii) bovine rumen fluid, and a number of animal manures including iv) giraffe, v) rhinoceros, and vi) tiger. Amplicon sequencing was used to investigate prokaryotic communities within these inocula on day 0 and day 21. Despite herbivore dung harbouring the largest hydrolytic community, the best solids destruction was achieved using anaerobic granular sludge, either intact (64.8 ± 11.9%) or crushed (63.4 ± 3.7% VS destruction). Granular sludge also resulted in the highest gas production, followed by giraffe manure. Contrastingly, the highest volatile fatty acid accumulation was achieved using rhinoceros and tiger manure, at 3.86 (±0.55) and 3.20 (±0.74) gCOD L−1, respectively. Despite these two manure samples having the highest relative abundances of bacteria associated with cellulose and hemicellulose degradation, they supported the poorest solids destruction, perhaps due to the VFA accumulation therein. Thus, while some inocula aided BSG degradation, further research is required to determine the inhibitors of hydrolysis and therefore BSG degradation.

Valorization Potentials of Rapeseed Meal in a Biorefinery Perspective: Focus on Nutritional and Bioactive Components.

Rapeseed meal (RSM), a by-product of oilseed extraction connected to the agri-food and biofuel sectors, is currently used as animal feed and for other low-value purposes. With a biorefinery approach, RSM could be valorized as a source of bio-based molecules for high-value applications. This study provides a chemical characterization of RSM in the perspective of its valorization. A qualitative study of main functional groups by fourier transform infrared (FTIR) spectroscopy was integrated with a chemical characterization of macronutrients, minerals by inductively coupled plasma optical emission spectrometry (ICP-OES), phenolic acids and lipid components by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), HPLC-diode-array detector (HPLC-DAD) and gas chromatography-mass spectrometry/flame ionization detector (GC-MS/FID). The study, conducted on different lots of RSM collected over a one-year period from an oil pressing factory serving a biofuel biorefinery, highlighted a constant quality over time of RSM, characterized by high protein (31–34%), fiber (33–40%) and mineral (5.5–6.8%) contents. Polyphenol extracts showed a significant antioxidant activity and a prevalence of sinapic acid, accounting for more than 85% of total phenolic acids (395–437 mg kg−1 RSM). Results highlight the potentialities of RSM for further valorization strategies that may lead to the creation of new cross-sector interconnections and bio-based value chains with improvement of the economics and sustainability of the bioeconomy sectors involved.

Spent coffee grounds based circular bioeconomy: Technoeconomic and commercialization aspects

Coffee consumption produces enormous amount of spent coffee grounds (SCG), a material that contain plenty of lipids, polyphenols, carbohydrates, proteins, and various other components. Valorisation of SCG is a contour for sustainable value added product recovery with greater attention in determining economic and ecological tasks. The integrated biorefinery approach in valorisation brings more valuable products meanwhile reduces the residue waste formation which enhance the environment and economy. The primary techno-economic and life cycle assessment of SCG biorefinery were discussed as compared to the single phase biorefinery under its operating condition for small scale collection of SCG. This review explains the various SCG biorefinery routes and its effective bioconversion, different value added products recovery and profitable integration approaches. For instance, extraction of fatty acids and carbohydrates with subsequent conversion of by products into bioenergy, biofuel and biochemicals in circular economy loop has profitable potencies. Besides, the various biorefinery strategies to expose the possibilities of SCG for deriving multiple products and its impact on economics were highlighted. The sustainable biorefinery for SCG valorisation were developed by applying the principles of circular bioeconomy. The future SCG biorefinery perspective shows that the higher valued bioactive compounds production and bioenergy production to industrial scale to achieve higher economic viability. The outcome of this review reveals that SCG is an excellent raw material for a variety of industrial integrated biotechnological approaches, reduces the cost associated with of raw materials, saves the landfill and promotes the bioeconomy.

Characterization of the de-oiled yeast biomass for plausible value mapping in a biorefinery perspective

Oleaginous yeast fermentation process has gained attention for yeast single cell oil production. However, after lipid extraction, the leftover de-oiled yeast biomass has not been investigated in detail for its suitability for thermochemical conversion. To understand the structural and morphological changes, the comparative characterization of yeast and de-oiled yeast biomass before and post lipid extraction is necessary. The present study investigates the characteristics of an oleaginous yeast Rhodotorula mucilaginosa IIPL32′s de-oiled biomass for its potential utilization. FTIR, XRD, SEM, EDX, XRF, and TGA analysis were performed to understand the biomass properties. Increased surface area and structural changes were observed in de-oiled yeast biomass with an increase in crystallinity, indicating chitosan availability. Maximum thermal degradation temperature was reduced to 260 °C for de-oiled yeast biomass from 300 °C for dried yeast after lipid extraction. The findings favored de-oiled yeast biomass for multiple applications that merit further detailed investigation with different thermochemical interventions.