Large amounts of agricultural waste, especially marine product waste, are produced annually. These wastes can be used to produce compounds with high-added value. Chitosan is one such valuable product that can be obtained from crustacean wastes. Various biological activities of chitosan and its derivatives, especially antimicrobial, antioxidant, and anticancer properties, have been confirmed by many studies. The unique characteristics of chitosan, especially chitosan nanocarriers, have led to the expansion of using chitosan in various sectors, especially in biomedical sciences and food industries. On the other hand, essential oils, known as volatile and aromatic compounds of plants, have attracted the attention of researchers in recent years. Like chitosan, essential oils have various biological activities, including antimicrobial, antioxidant, and anticancer. In recent years, one of the ways to improve the biological properties of chitosan is to use essential oils encapsulated in chitosan nanocarriers. Among the various biological activities of chitosan nanocarriers containing essential oils, most studies conducted in recent years have been in the field of antimicrobial activity. It was documented that the antimicrobial activity was increased by reducing the size of chitosan particles in the nanoscale. In addition, the antimicrobial activity was intensified when essential oils were in the structure of chitosan nanoparticles. Essential oils can increase the antimicrobial activity of chitosan nanoparticles with synergistic effects. Using essential oils in the structure of chitosan nanocarriers can also improve the other biological properties (antioxidant and anticancer activities) of chitosan and increase the application fields of chitosan. Of course, using essential oils in chitosan nanocarriers for commercial use requires more studies, including stability during storage and effectiveness in real environments. This review aims to overview recent studies on the biological effects of essential oils encapsulated in chitosan nanocarriers, with notes on their biological mechanisms.

Potato peel waste (PPW) is a carbohydrate-rich waste from potato industries, which is an environmental threat worldwide. In this study, it was evaluated for biobutanol production via acetone-butanol-ethanol fermentation by Clostridium acetobutylicum. The results showed that PPW contained a considerable amount of glycoalkaloids, severe inhibitors for the bacterium. Thus, three processes, i.e., dilute acid pretreatment (Process I), the inhibitors extraction followed by dilute acid hydrolysis (Process II) and ethanol organosolv pretreatment (Process III), were employed before hydrolysis and fermentation to produce ABE. The extraction of glycoalkaloids with ethanol, dilute acid hydrolysis at 180 °C for 60 min, and enzymatic hydrolysis led to a hydrolysate with 36 g/L glucose, which was successfully fermented to 11.6 g/L ABE. In process II, the organosolv pretreatment led to the removal of the major fraction of inhibitors, in the range of 77–88% of glycoalkaloids. The enzymatic hydrolysis of PPW pretreated with 75% ethanol at 180 °C for 60 min resulted in a fermentable hydrolysate with 38 g/L glucose. The fermentation of overall hydrolysate resulted in a high ABE concentration of 24.8 g/L, indicating that PPW is an appropriate substrate for butanol production after the removal of its bacterial inhibitors.

Co-processing of lignocellulosic wastes, e.g., garden and paper wastes, and the organic matters fraction of municipal solid waste (OMSW) in an integrated bioprocess is a possible approach to realize the potential of wastes for biobutanol production. Dilute acid pretreatment is a multi-functional stage for breaking the recalcitrant lignocellulose’s structure, hydrolyzing hemicellulose, and hydrolyzing/solubilizing starch, leading to a pretreated solid and a rich hydrolysate. In this study, dilute-acid pretreatment of the combination of wastepaper and OMSW, composite I, as well as garden waste and OMSW, composite II, at severe conditions resulted in “pretreatment hydrolysates” containing 33.7 and 19.4 g/L sugar along with 18.9 and 33.2 g/L soluble starch, respectively. In addition, the hydrolysis of solid remained after the pretreatment of composite I and II resulted in “enzymatic hydrolysates” comprising 19.4 and 33 g/L sugar, respectively. The fermentation of the pretreatment hydrolysates and enzymatic hydrolysates resulted in 3.5 and 6.4 g/L ABE from composite I and 15 and 5.2 g/L ABE from composite II, respectively. In this process, 148 and 173 g ABE (60 and 100 g gasoline equivalent/kg) was obtained from each kg composite I and composite II, respectively, where co-processing of OMSW with lignocellulosic wastes resulted in 10 and 49% higher ABE than that produced from the individual substrates.

The microbial pathway of butanol biosynthesis is a unique route for the production of a biomass-derived advanced biofuel with high potential to be utilized in place of the fossil fuels. In the present study, Nesterenkonia sp. strain F was applied as a beneficial partner for Clostridium acetobutylicum in “starch-to-butanol process”. The capability of Nesterenkonia sp. strain F in secreting organic solvent-tolerant amylase was utilized for upgrading the yield of solvent, i.e., acetone, butanol, and ethanol (ABE), production under aerobic conditions. Monitoring the amylolytic activity and glucose concentration throughout the micro-aerobic co-culture revealed higher amylase activity and glucose concentration in comparison with the monoculture. The co-culture led to 63% higher amylase activity through the microaerobic cultivation on starch. After optimizing the conditions with response surface methodology (RSM), 10.6 g/L butanol was produced from untreated potato starch (UPS) with a high yield of 0.23 g ABE/g starch, leading to 30% improvement in ABE production. To assess its performance at larger scale, the fermentation was conducted in a 5 L fermenter continually aerated with a rate of 0.05 vvm and 150 rpm. This led to production of 9.7 g/L butanol, 5.0 g/L acetone, and 0.3 g/L ethanol with a yield and productivity of 0.20 g/g and 0.21 g/L.h, respectively. Furthermore, ABE production from tannin-containing sorghum grain was improved by about 3-fold.

Despite its advantages, lignocellulosic butanol cannot become a real alternative without processes for obtaining credits from non-cellulosic fraction of lignocellulose. In this study, the process of “cellulosic butanol” was integrated with “hemicellulosic methane” process, i.e., anaerobic digestion (AD), for higher energy return on investment (EROI). Aqueous pretreatment was evaluated as a connecting chain between the processes. The alkaline (1% NaOH), acidic (1% H₂SO₄), and neutral (autohydrolysis) pretreatments were utilized at 140, 160, and 180 °C for bioenergy recovery from triticale straw. Enzymatic hydrolysis of the straw pretreated by alkaline (180 °C), dilute acid (140 °C), and autohydrolysis (180 °C) and fermentation of the hydrolysates by Clostridium acetobutylicum led to 13.6, 8.5, and 10.2 g/L acetone-butanol-ethanol (ABE), respectively. AD of the liquors remained after pretreatment by alkaline, dilute acid, and autohydrolysis led to 83–121, 240–247, and 380–430 mL/g VSS methane leading to more than 60% increase in EROI.

Bioenergy systems are expected to expand over the coming decades due to their potential to address energy security and environmental pollution challenges. Nevertheless, any renewable energy project can only survive if approved environmentally superior to its conventional counterparts. Life cycle assessment (LCA) is an internationally standardized and validated methodology to evaluate and quantify the environmental impacts of bioenergy systems. However, due to its methodological scope, the LCA method measures only the environmental consequences of the target products of energy systems. The LCA approach can neither allocate the environmental impacts at the component level nor measure the environmental impacts of intermediate products. These challenges can be substantially resolved by systematically integrating the LCA approach with the thermodynamically-rooted exergy, offering a powerful environmental sustainability assessment tool known as “exergoenvironmental analysis“. Due to the unique methodological and conceptual characteristics of exergoenvironmental analysis in revealing the possibilities and trends for improvement, it has recently received increasing attention to mitigate the environmental impacts of bioenergy systems. Therefore, this review is aimed to thoroughly summarize and critically discuss the evaluation of sustainability aspects of bioenergy systems based on exergoenvironmental analysis. The pros and cons of using exergoenvironmental analysis in bioenergy research are also outlined to identify possible future directions for the field. Overall, exergoenvironmental analysis can offer more detailed information on the environmental consequences of each flow and component of bioenergy production plants, thereby diagnosing the breakthrough points for additional environmental improvements.

The growing volume of municipal solid waste (MSW) generated worldwide often undergoes open dumping, landfilling, or uncontrolled burning, releasing massive pollutants and pathogens into the soil, water, and air. On the other hand, MSW can be used as a valuable feedstock in biological and thermochemical conversion processes to produce bioenergy carriers, biofuels, and biochemicals in line with the United Nations’ Sustainable Development Goals (SDGs). Valorizing MSW using advanced technologies is highly energy-intensive and chemical-consuming. Therefore, robust and holistic sustainability assessment tools should be considered in the design, construction, and operation phases of MSW treatment technologies. Exergy-based methods are promising tools for achieving SDGs due to their capability to locate, quantify, and comprehend the thermodynamic inefficiencies, cost losses, and environmental impacts of waste treatment systems. Therefore, the present review paper aims to comprehensively summarize and critically discuss the use of exergetic indicators for the sustainability assessment of MSW treatment systems. Generally, consolidating thermochemical processes (mainly incineration and gasification) with material recycling methods (plastic waste recovery), heat and power plants (steam turbine cycle and organic Rankine cycle), modern power technologies (fuel cells), and carbon capture and sequestration processes could improve the exergetic performance of MSW treatment systems. Typically, the overall exergy efficiency values of integrated MSW treatment systems based on the incineration and gasification processes were found to be in the ranges of 17–40% and 22–56%, respectively. The syngas production through the plasma gasification process could be a highly favorable waste disposal technique due to its low residues and rapid conversion rate; however, it suffers from relatively low exergy efficiency resulting from its high torch power consumption. The overall exergy efficiency values of integrated anaerobic digestion-based MSW processing systems (34–73%) were generally higher than those based on the thermochemical processes. Exergy destruction and exergy efficiency were the most popular exergetic indicators used for decision-making in most published works. However, exergoeconomic and exergoenvironmental indices have rarely been used in the published literature to make decisions on the sustainability of waste treatment pathways. Future studies need to focus on developing and realizing integrated waste biorefinery systems using advanced exergy, exergoeconomic, and exergoenvironmental methods.

The recently developed technologies for immobilization of cellulase may address the challenges in costly hydrolysis of cellulose for cellulosic butanol production. In this study, a “hybrid” hydrolysis was developed based on chemical hydrolysis of cellulose to its oligomers followed by enzymatic post-hydrolysis of the resulting “soluble oligomers” by cellulase immobilized on chitosan-coated Fe₃O₄ nanoparticles. This hybrid hydrolysis stage was utilized in the process of biobutanol production from a waste textile, jeans waste, leading to selective formation of glucose and high yield of butanol production by Clostridium acetobutylicum. After validating the immobilization process, the optimum immobilization parameters including enzyme concentration and time were achieved on 8 h and 15.0 mg/mL, respectively. The reusability of immobilized enzyme showed that immobilized cellulase could retain 51.5% of its initial activity after three times reuses. Dilute acid hydrolysis of regenerated cellulose at 120–180 °C for 60 min 0.5–1.0% phosphoric acid led to less than 10 g/L glucose production, and enzymatic post-hydrolysis of the oligomers resulted in up to 51.5 g/L glucose. Fermentation of the hydrolysate was accompanied by 5.3 g/L acetone-butanol-ethanol (ABE) production. The simultaneous co-saccharification and fermentation (SCSF) of soluble and insoluble oligomers of cellulose led to 17.4 g/L ABE production.

Liquid transportation biofuel production is a promising strategy to reduce greenhouse gas emissions. Hydrothermal gasification (HTG) has shown great potential as an effective method for valorizing wet biomass. The high-quality syngas produced using the HTG process can be chemically/biochemically converted to liquid biofuels. Therefore, this paper aims to comprehensively review and critically discuss syngas production from biomass using the HTG process and its conversion into liquid biofuels. The basics and mechanisms of biomass HTG processing are first detailed to provide a comprehensive and deep understanding of the process. Second, the effects of the main operating parameters on the performance of the HTG process are numerically analyzed and mechanistically discussed. The syngas cleaning/conditioning and Fischer-Tropsch (FT) synthesis are then detailed, aiming to produce liquid biofuels. The economic performance and environmental impacts of liquid biofuels using the HTG-FT route are evaluated. Finally, the challenges and prospects for future development in this field are presented. Overall, the maximum total gas yield in the HTG process is obtained at temperature, pressure, and residence time in the range of 450–500 °C, 28–30 MPa, and 30–60 min, respectively. The highest C₅₊ liquid hydrocarbon selectivity in the FT process is achieved at temperatures between 200 and 240 °C. Generally, effective conversion of biomass to syngas using the HTG process and its successful upgrading using the FT process can offer a viable route for producing liquid biofuels. Future studies should use HTG technology in the biorefinery context to maximize biomass valorization and minimize waste generation.

Chitosan is one of the valuable products obtained from crustacean waste. The unique characteristics of chitosan (antimicrobial, antioxidant, anticancer, and anti-inflammatory) have increased its application in various sectors. Besides unique biological properties, chitosan or chitosan-based compounds can stabilize emulsions. Nevertheless, studies have shown that chitosan cannot be used as an efficient stabilizer because of its high hydrophilicity. Hence, this review aims to provide an overview of recent studies dealing with improving the emulsifying properties of chitosan. In general, two different approaches have been reported to improve the emulsifying properties of chitosan. The first approach tries to improve the stabilization property of chitosan by modifying its structure. The second one uses compounds such as polysaccharides, proteins, surfactants, essential oils, and polyphenols with more wettability and emulsifying properties than chitosan’s particles in combination with chitosan to create complex particles. The tendency to use chitosan-based particles to stabilize Pickering emulsions has recently increased. For this reason, more studies have been conducted in recent years to improve the stabilizing properties of chitosan-based particles, especially using the electrostatic interaction method. In the electrostatic interaction method, numerous research has been conducted on using proteins and polysaccharides to increase the stabilizing property of chitosan.

Chitin, as the main component of the exoskeleton of Arthropoda, is a highly available natural polymer that can be processed into various value-added products. Its most important derivative, i.e., chitosan, comprising β-1,4-linked 2-amino-2-deoxy-β-d-glucose (deacetylated d-glucosamine) and N-acetyl-d-glucosamine units, can be prepared via alkaline deacetylation process. Chitosan has been used as a biodegradable, biocompatible, non-antigenic, and nontoxic polymer in some in-vitro applications, but the recently found potentials of chitosan for in-vivo applications based on its biological activities, especially antimicrobial, antioxidant, and anticancer activities, have upgraded the chitosan roles in biomaterials. Chitosan approval, generally recognized as a safe compound by the United States Food and Drug Administration, has attracted much attention toward its possible applications in diverse fields, especially biomedicine and agriculture. Despite some favorable characteristics, the chitosan’s structure should be customized for advanced applications, especially due to its drawbacks, such as low drug-load capacity, low solubility, high viscosity, lack of elastic properties, and pH sensitivity. In this context, derivatization with relatively inexpensive and highly available mono- and di-saccharides to soluble branched chitosan has been considered a “game changer”. This review critically scrutinizes the emerging technologies based on the synthesis and application of lactose- and galactose-modified chitosan as two important chitosan derivatives. Some characteristics of chitosan derivatives and biological activities have been detailed first to understand the value of these natural polymers. Second, the saccharide modification of chitosan has been discussed briefly. Finally, the applications of lactose- and galactose-modified chitosan have been scrutinized and compared to native chitosan to provide an insight into the current state-of-the research for stimulating new ideas with the potential of filling research gaps.

Depending on its physicochemical properties and antibacterial activities, chitosan can have a wide range of applications in food, pharmaceutical, medicine, cosmetics, agriculture, and aquaculture. In this experimental study, chitosan was extracted from shrimp waste through conventional extraction, microwave-assisted extraction, and conventional extraction under microwave process conditions. The effects of the heating source on the physicochemical properties and antibacterial activity were investigated. The results showed that the heating process parameters affected the physicochemical properties considerably. The conventional procedure yielded high molecular weight chitosan with a 12.7 % yield, while the microwave extraction procedure yielded a porous medium molecular weight chitosan at 11.8 %. The conventional extraction under microwave process conditions led to medium molecular weight chitosan with the lowest yield (10.8 %) and crystallinity index (79 %). Antibacterial assessment findings revealed that the chitosan extracted using the conventional method had the best antibacterial activity in the agar disk diffusion assay against Listeria monocytogenes (9.48 mm), Escherichia coli. (8.79 mm), and Salmonella Typhimurium (8.57 mm). While the chitosan obtained by microwave-assisted extraction possessed the highest activity against E. coli. (8.37 mm), and Staphylococcus aureus (8.05 mm), with comparable antibacterial activity against S. Typhimurium (7.34 mm) and L. monocytogenes (6.52 mm). Moreover, the minimal inhibitory concentration and minimal bactericidal concentration assays demonstrated that among the chitosan samples investigated, the conventionally-extracted chitosan, followed by the chitosan extracted by microwave, had the best antibacterial activity against the target bacteria.

The utilization of renewable fuel alternatives holds promise for reducing the financial burden of regulatory compliance and the social responsibility associated with greenhouse gas emissions. Hydrothermal liquefaction (HTL) is one of the most versatile technologies for converting renewable biomass feedstocks (especially in the wet state) into biofuel (biocrude oil) in a compact plant. Therefore, this review is devoted to thoroughly reviewing and critically discussing biocrude oil production from biomass feedstocks through the HTL process. This review starts by discussing the principles of biomass HTL processing and product upgrading, aiming to provide a grounded and broad understanding of current developments in this domain. The data reported in the published literature are analyzed and visualized in order to scrutinize the effects of the main process parameters on the quantity, quality, cost, and environmental impacts of resultant biofuels. Higher biocrude oil yields are obtained at temperatures, pressures, and residual times between 300 and 350 °C, 24–27 MPa, and 15–25 min, respectively. Concerning yield and calorific value, biocrude oil derived from homogeneous catalysts demonstrates figures of 23.6 % and 32.1 MJ/kg, whereas that from heterogeneous catalysts exhibits percentages of 66.8 % and 40 MJ/kg, respectively. The challenges and prospects for the future development of biocrude oil are also discussed. HTL has a long way to go before being used for biofuel production on a large scale. Future studies appear to be directed towards the use of HTL technology under the biorefinery framework to maximize the exploitation of biomass into value-added products, while minimizing waste generation.

A multi-stage approach was evaluated for biohydrogen production from organic fraction of municipal solid waste and pruning, including pine, cypress, and mulberry wastes. The process consists of three stages: “starchy dark fermentation”, “intermediary autogenous acidic pretreatment”, and “lignocellulosic dark fermentation”. These stages synergistically contribute to the efficient conversion of organic waste into biohydrogen, offering an innovative solution for waste management while promoting sustainable energy production. In the first stage, easily degradable materials (starch) were utilized and converted into biohydrogen, underscoring the necessity of preventing their loss during the subsequent pretreatment stage. In the first stage, 72–78 % of starch was consumed, yielded 494–2,274 mL biohydrogen per 100 g waste. The second stage involved improving the structure of lignocellulose-rich solids through the application of volatile fatty acid-rich liquor generated in the first stage for pretreatment. In the second stage, the substrate was subjected to 120–180 °C for 60 min to pretreat the lignocelluloses catalyzed by the volatile fatty acids generated in the first stage. The third stage produced 119–3,154 mL biohydrogen from 100 g waste. At optimum conditions, the three-stage process yielded an overall of 5,228 mL hydrogen from 100 g of untreated substrate, 2.4-fold higher than one-stage dark fermentation.

Bio-hydrogen (bio-H₂) production from dark co-fermentation of pruning wastes, from pine, cypress, and berry trees, and food-rich municipal solid waste (FMSW) was evaluated as a promising way to combine waste management and renewable energy production. The inoculum was initially optimized by heat-shock pretreatment at 65, 75, 85, and 95 ℃ for 15, 30, and 45 min in order to maximize bio-H₂ yields. The optimum pretreatment conditions (75 °C for 45 min) were applied for dark co-fermentation analyses. The highest bio-H₂ production yield of 84 ± 6 mL/g VS was obtained by dark co-fermentation of 20 g/L pruning wastes and FMSW under initially neutral conditions. The fermentation of individual substrates led to 40.9, 0.2, 0.1, and 0.2 mL/g VS from FMSW, pine, berry, and cypress, respectively, 85% lower than obtained through dark co-fermentation. Therefore, co-processing of a “stiff substrate”, lignocellulose, with a “loose part”, starchy FMSW, leads to a higher bio-H₂ yield. Dark co-fermentation led to the bio-conversion of more than 76% of starch, 31% of glucan, and 41% of hemicellulose, besides 41% lignin removal. The modified Gompertz model (MGM) and Logistic model (MLM) were well-fitted on kinetic data (with R² values ≥0.98), and the kinetic parameters were calculated.

Food fraud is a pressing global challenge with far-reaching implications, necessitating robust preventive measures. The safeguarding of consumers from hazardous products, the preservation of supply chain integrity, and the assurance of fair competition all rely on effective anti-fraud strategies. Intelligent packaging technologies are pivotal in reducing food fraud through anti-tampering measures and traceability. However, standalone intelligent packaging technologies cannot alone establish comprehensive traceability within the food chain. This review asserts that integrating blockchain and artificial intelligence (AI) technologies can bolster traceability and combat food fraud. Blockchain enhances transparency, while AI enables precise analysis of extensive datasets. This comprehensive review critically examines the potential of combining blockchain and AI technologies with intelligent packaging to address food fraud. It thoroughly delineates the strengths and limitations of these technologies in detecting and mitigating fraud across the supply chain. The amalgamation of diverse technologies within intelligent packaging presents a holistic approach to mitigating significant fraud, contingent upon the effective resolution of technical, cost, and safety challenges. In conclusion, integrating sophisticated technologies into intelligent packaging offers a promising avenue to effectively combat food fraud, instill consumer trust, and maintain the integrity of the food supply chain.

Synergy in the co-processing of lignocellulosic wastes and municipal biowaste (MB) can unlock their potential for biobutanol production. This study assessed the potential for biobutanol production through the co-processing of lignocellulosic waste and MB. Specifically, it compared the co-processing of paper waste with MB to that of garden waste and MB. Ethanol organosolv pretreatment served as a dual-function process for both pretreatment and detoxification purposes. Initial fermentation of hydrolysates from untreated paper waste using Clostridium acetobutylicum produced 0.9 g/L of acetone and ethanol but no detectable butanol. Organosolv pretreatment led to a significant increase in acetone and ethanol production but did not yield butanol. Co-processing paper waste with MB using organosolv pretreatment resulted in the production of 2.8–3.2 g/L butanol, along with increased acetone and ethanol production. Furthermore, co-processing a 1:1 (w/w) mixture of paper waste and MB under mild and severe pretreatment conditions produced 45.5 g and 43.4 g butanol, respectively, compared to 34.8 g and 14.4 g butanol when processing these waste streams separately. The study also explored the positive impact of co-processing garden waste with MB, a distinct lignocellulosic source, enhancing acetone-butanol-ethanol (ABE) yield by 27–40%. These findings highlight the potential of synergistic waste co-processing for achieving a more suitable balance of nutrients to enhance biobutanol and ABE production from biowastes. Additionally, the simultaneous treatment of lignocellulosic waste and municipal biowaste offers a simplified approach to waste processing, contributing to advancements in sustainable biomass utilization and bioenergy production.

The utilization of biogas as a renewable energy source necessitates a reduction in its CO₂ content. “Ex-situ biomethanation” is employed to convert CO₂ in biogas to CH₄ through hydrogenotrophic methanogens. In this study, a biogas stream (32-36% CO₂) originating from cow manure digestion was subjected to treatment in a trickle bed bioreactor (4 liters). The presence of microorganisms on the packing material was confirmed by using a 16 S rRNA test and SEM images. This study stands out by considering all four combinations of thermophilic and mesophilic conditions, monitoring the transition and steady-state phases in a two-reactor series setup. The mesophilic-thermophilic mode yielded the highest purity (92%) with an 86% CO₂ conversion rate and an energy density of 13,870 kJ/m³. Additionally, the performance consistency was also assessed using a larger TBB (8 liters). Extending the residence time, the thermophilic-thermophilic mode yielded the highest CH₄ concentration at 98%. The 16 S rRNA results revealed that, influenced by the designated growth conditions encompassing culture media, pH, temperature, and reactor retention time, an enrichment of hydrogenotrophic methanogens occurred. Furthermore, promising results in terms of CH₄ concentration and process efficiency were demonstrated by the trickled bed bioreactor employing liquid-in-gas dispersion.

Abstract

Rice straw was hydrolyzed and fermented to acetone, butanol, and ethanol by Clostridium acetobutylicum bacterium. Concentrated phosphoric acid and alkaline treatment with NaOH were used for pretreatment of the straw prior to enzymatic hydrolysis using commercial cellulase and b-glucosidase. The enzymatic hydrolysates were then anaerobically fermented by C. acetobutylicum. Hydrolysis of the alkaline pretreated straw resulted in production of 163.5 g glucose from each kg of untreated rice straw which was then fermented to 45.2 g butanol, 17.7 g acetone, and 1.2 g ethanol. Additionally, concentrated phosphoric acid pretreatment and subsequent hydrolysis resulted in production of 192.3 g glucose from each kg straw from which 44.2 g butanol, 18.2 g acetone, and 0.6 g ethanol were produced after 72 h fermentation. Increasing the produced ABE from less than 10 g to higher than 62 g from each kg straw by the treatments suggested the alkaline and phosphoric acid pretreatments as promising processes for efficient production of ABE from rice straw.

Abstract

5-Hydroxymethylfurfural (HMF) and furfural, both of which can be derived from renewable sources, are key components for the production of different chemicals and fuels. In this study, rice straw, a cheap, abundant, and mainly unused agricultural waste, is converted to furans by a dilute acid hydrolysis process. The highest yield of HMF in a single-phase hydrolysis was 15.3 g/kg straw, attained at 180 °C during 3 h with 0.5% sulfuric acid, while the maximum yield of furfural, 59 g/kg straw, was obtained at 150 °C during 5 h. Different extracting solvents, including 2-PrOH, 1-BuOH, methyl isobutyl ketone (MIBK), and acetone at 180 °C for 3 h as well as tetrahydrofuran (THF) at 150 °C for 5 h were examined in biphasic systems. Use of the solvents generally improved the production of HMF compared to the single aqueous phase process. The best results of HMF production, more than 59 g/kg straw, were obtained in the systems containing either 2-PrOH or 1-BuOH. Using THF as an extracting solvent, a relatively high furfural yield, 118.2 g/kg straw, was obtained, and 96% of furfural produced in this system was extracted into THF during the process.

Abstract

Organosolv pretreatment was used to improve solid-state anaerobic digestion (SSAD) form ethane production from three different lignocellulosic substrates (hardwood elm, softwood pine, and agricultural waste rice straw). Pretreatments were conducted at 150 and 180∘C for 30 and 60 min using 75% ethanol solution as an organic solvent with addition of sulfuric acid as a catalyst. The statistical analyses showed that pretreatment temperature was the significant factor affecting methane production. Optimum temperature was 180∘C for elm wood while it was 150∘C for both pinewood and rice straw. Maximum methane production was 152.7, 93.7, and 71.4 liter per kg carbohydrates (CH), which showed up to 32, 73, and 84% enhancement for rice straw, elm wood, and pinewood, respectively, compared to those from the untreated substrates. An inverse relationship between the total methane yield and the lignin content of the substrates was observed. Kinetic analysis of the methane production showed that the process followed a first-order model for all untreated and pretreated lignocelluloses.

Abstract

Acetone–butanol–ethanol (ABE) was produced from rice straw using a process containing ethanol organosolv pretreatment, enzymatic hydrolysis, and fermentation by Clostridium acetobutylicum bacterium. Pretreatment of the straw with 75% (v/v) aqueous ethanol containing 1% w/w sulfuric acid at 150 °C for 60 min resulted in the highest total sugar concentration of 31 g/L in the enzymatic hydrolysis. However, the highest ABE concentration and productivity (10.5 g/L and 0.20 g/L h, respectively) were obtained from the straw pretreated at 180 °C for 30 min. Enzymatic hydrolysis of the straw pretreated at 180 °C for 30 min with 5% solid loading resulted in glucose yield of 46.2%, which was then fermented to 80.3 g butanol, 21.1 g acetone, and 22.5 g ethanol, the highest overall yield of ABE production. Thus, the organosolv pretreatment can be applied for efficient production of the solvents from rice straw.

Acetone–butanol–ethanol (ABE) production from grains, bagasse, and juice of sweet sorghum was conducted by Clostridium acetobutylicum. Delignification with acetone, one of the ABE fermentation products, was evaluated as a pretreatment for the improvement of ABE production from bagasse. Different modes of hydrolysis and fermentation of “separate hydrolysis and fermentation (SHF)” (process I), “simultaneous saccharification and fermentation (SSF)” (process II), and “simultaneous saccharification and co-fermentation (SSCF)” (process III) were compared for ABE production from delignified bagasse. Direct ABE fermentation of stalks without juice extraction was also evaluated (process IV). Along with the stalks, the starchy grains of the sorghum plant were directly utilized in the ABE fermentation. Total concentration of acetone, butanol, and ethanol (ABE) of 10.6 g/L, containing 3.17 g/L acetone, 6.34 g/L butanol, and 1.06 g/L ethanol, was obtained through SSF process at pH 5.8 and 37 °C from the bagasse pretreated at 180 °C for 60 min. Through the SSCF process, solvents production was increased by 27–36% as compared to the SSF. From each kg sweet sorghum plant, 156, 136, 101, and 110 g total acetone, butanol, and ethanol (g ABE) was produced through process I, II, III, and IV, respectively. It was concluded that utilizing all parts of sweet sorghum plant, as an energy crop, is a promising approach for ABE production.

Industrial scale production of biobutanol has been hampered by substrate cost and availability. Sweet sorghum grain is an inexpensive substrate for acetone-butanol-ethanol (ABE) production by Clostridium acetobutylicum. Amylolytic activity of C. acetobutylicum eliminates the need for the hydrolysis of starchy grain prior to fermentation. However, untreated grain contains phenolic compounds, i.e. tannins, which exhibit inhibitory effects against amylolytic activity and ABE fermentation. Less than 3 g/L ABE was obtained from untreated sweet sorghum grain at different substrate concentrations. Concentration of 0.2 mM gallic acid equivalent (GAE) of sorghum tannins was detected as the critical concentration which inhibits severely ABE fermentation. Applying a multi-stage hot water treatment resulted in tannins removal and significant enhancement in total ABE production up to 18 g/L. For efficient butanol production from 40, 60, and 80 g/L sorghum grain, hot water treatment with two, five, and six stages were found to be essential for efficient butanol production, respectively. Moreover, the amylolytic activity of C. acetobutylicum was inhibited by sorghum grain tannins, more than twice as high as the effects on the ABE fermentation pathway. Furthermore, unlike most substrates, sweet sorghum grain could provide all nutrients required for ABE fermentation, eliminating the need for supplementing expensive additional nutrients.

The biodegradable fraction of municipal solid waste (BMSW), dominantly composed of starchy and lignocellulosic materials, has high potential to be used for liquid biofuel production. Hot water or dilute acid treatment at high temperature was utilized for the solubilization or hydrolysis of the starch fraction and pretreatment of the lignocellulosic fraction. The treatment liquor, which was rich in sugars and starch, was evaluated for acetone, butanol, and ethanol (ABE) production by Clostridium acetobutylicum, and it was found that phenolic compounds, especially tannins, critically inhibited the butanol production. To improve ABE production, the extraction of phenolic compounds prior to hot water or dilute acid treatment was evaluated. Among the evaluated extractants, i.e., acetone, ethanol, butanol, and water, ethanol showed the highest amount of tannin extraction, resulting in an 87% reduction in tannin content. Dilute acid treatment of the ethanol extracted BMSW at 140 °C for 60 min resulted in a liquor containing 23 g/L glucose and 41 g/L soluble starch, which was fermented to the highest ABE concentration of 17 g/L with productivity of 0.24 g/L/h. The fermentation of liquor obtained by dilute acid treatment of butanol, acetone, and water-extracted BMSW was accompanied by 9, 6, and 4 g/L ABE production. Even by hot water treatment, the liquor obtained from ethanol extracted BMSW was fermented to the highest ABE concentration of 8 g/L. In addition to the liquor, the pretreated lignocellulosic material was subjected to enzymatic hydrolysis and ABE fermentation, leading to production of 5–6 g/L ABE. This process resulted in the production of 83.9 g butanol, 36.6 g acetone, and 20.8 g ethanol from each kg of BMSW. Moreover, the co-production of ethanol by ABE fermentation reduced concerns about organic extractor loss in the extraction process, which was inescapable in the tannin extraction process.

To move biobutanol toward a commercialized biofuel, its production process should be developed based on renewable and cost-effective carbon sources. In this study, it was shown that cotton, a commodity that typically ends in landfill sites or incinerators, can be utilized as a feasible source after the phosphoric acid-acetone process. The treatment with phosphoric acid (19 g/g) resulted in 94% cotton dissolution after 60 min, and the addition of acetone (41 g/g) was accompanied by 97% precipitation. Enzymatic hydrolysis of regenerated cellulose (15 filter paper unit per mL (FPU/mL)) followed by fermentation by Clostridium acetobutylicum resulted in 5.4 g/L acetone-butanol-ethanol (ABE). In this process, 208 g acid and 138 FPU cellulase were used for production of each g ABE. Increasing enzyme dosage to 25 FPU/g resulted in 79% higher butanol production (161 g ABE/kg). Through cyclic acid re-concentration, phosphoric acid consumption decreased to 82 g/g ABE. Furthermore, by applying an additional dilute phosphoric acid pretreatment, the enzyme consumption reduced to 113 FPU/g ABE.

Butanol is acknowledged as a drop-in biofuel that can be used in the existing transportation infrastructure, addressing the needs for sustainable liquid fuel. However, before becoming a thoughtful alternative for fossil fuel, butanol should be produced efficiently from a widely-available, renewable, and cost-effective source. In this regard, lignocellulosic materials, the main component of organic wastes from agriculture, forestry, municipalities, and even industries seems to be the most promising source. The butanol-producing bacteria, i.e., Clostridia sp., can uptake a wide range of hexoses, pentoses, and oligomers obtained from the hydrolysis of cellulose and hemicellulose content of lignocelluloses. The present work is dedicated to reviewing different processes containing pretreatment and hydrolysis of hemicellulose and cellulose developed for preparing fermentable hydrolysates for biobutanol production.

Municipal solid waste (MSW) was used as a source for biobutanol production via acetone, butanol, and ethanol (ABE) fermentation. Organosolv pretreatment was used for simultaneous extraction of inhibitors, particularly tannins, and pretreatment of lignocellulosic fraction prior to hydrolysis. The hydrolysates of the pretreated MSW contained appreciable amounts of sugars and soluble starch together with a tolerable amount of inhibitors for Clostridium acetobutylicum. The hydrolysate obtained from MSW pretreated with 85% ethanol at 120 °C for 30 min fermented to the highest ABE concentration of 13.06 g/L with the yield of 0.33 g/g carbon source. Through this process, 102.4 mg butanol, 40.16 mg acetone, and 13.14 mg ethanol were produced from each g of organic fraction of MSW (OFMSW). The pretreatment at mild conditions with higher ethanol concentration accompanied with the lowest glucose yield (0.145 g/g) and the highest starch recovery resulted in the uppermost ABE yield of 0.16 g/g OFMSW.

Sweet sorghum plant, a widely grown energy crop, was utilized through a biorefinery process, by which its grains were hydrolyzed by the crude amylases produced from its bagasse. The hemicellulosic part of the bagasse was hydrolyzed with 0.5–1.0% sulfuric acid at 140–180 °C for 30–60 min and applied for amylase production using halotolerant bacterium Nesterenkonia sp. strain F. In the hydrolysate obtained at 140 °C for 60 min using 1% acid, Nesterenkonia showed 73.3 U/mL amylase activity by the consumption of 16.2 g/L xylose and 8.3 g/L other sugars. Supplementation of the hydrolysates with sorghum grain resulted in 38–67% higher amylase production. Furthermore, addition of biocompatible surfactants of Tween 20 and Tween 80 (0.1 g/L) increased the activity to 93 and 97 U/mL, respectively. The resulting crude enzyme was used in the process of ethanol production from both tannin-containing and tannin-free sorghum grains (6%), leading to 17.7 and 17.0 g/L bioethanol production, respectively. Through the cultivation of Nesterenkonia on the hemicellulosic hydrolysates, 5–10 g/L volatile fatty acids (VFA), 0.36–0.69 g/L acetone-butanol-ethanol (ABE), and 468–721 mg/L single cell protein (SCP) were also produced. The obtained SCP contained most of the essential amino acids and relatively high amounts of phenylalanine (8%), threonine (7%), methionine (6%), and lysine (6%).

Different process alternatives were assessed for production of hemicellulosic and cellulosic butanol from sweet sorghum bagasse (SSB) based on integration of autohydrolysis, enzymatic hydrolysis, and ABE fermentation. The liquor obtained through single or two-stage autohydrolysis was subjected to post-hydrolysis using a commercial hemicellulases blend and fermentation by Clostridium acetobutylicum. The pretreated solids obtained at each stage of autohydrolysis were also used for ABE production through separated hydrolysis and fermentation (SHF) or simultaneous saccharification and fermentation (SSF) using a commercial cellulase blend. The two-stage autohydrolysis (at 150 °C for 30 min; 120 °C for 60 min) followed by enzymatic post-hydrolysis resulted in 6.6 g/L sugar and fermented to 4.6 g/L ABE. On the other hand, enzymatic hydrolysis and ABE fermentation of the pretreated SSB led to 4.7–5.4 g/L ABE. In this process, 32 g hemicellulosic and 85 g cellulosic ABE were produced from each kg SSB. Besides, other thirteen process alternatives were compared based on the overall yield of ABE production from SSB. In the most compact process, the four enzymatic hydrolysis and fermentation stages were combined into a single stage named “simultaneous co-saccharification and fermentation (SCSF)” leading to 21−22 g ABE/kg SSB.

Butanol attracted interests as a drop-in biofuel obtainable from cellulosic wastes. However, the process typically used for cellulose bioconversion, i.e., separate hydrolysis and fermentation (SHF) of pretreated cellulose (Process I), is insufficient for energy-efficient production of fuel grade butanol due to the limited obtainable butanol titer. Recently, post-hydrolysis of chemically formed water-soluble cellulose oligomers was suggested for acetone-butanol-ethanol (ABE) production in SHF mode of operation (Process II). In this study, it was found that simultaneous saccharification and fermentation of the soluble oligomers (oligomeric-SSF) (Process III) and simultaneous co-saccharification and fermentation (SCSF) of soluble oligomers along with regenerated cellulose (Process IV) are promising alternatives for upgrading the titer and yield of cellulosic butanol production by Clostridium acetobutylicum. In Process III, utilizing the oligomeric hydrolysate obtained through dilute acid hydrolysis at 120 °C for 60 min using 1% acid through oligomeric-SSF led to 14.2 g/L ABE production, i.e., 65% higher than Process I. In addition, using the oligomeric hydrolysate in SCSF resulted in 24 g/L ABE (16 g/L butanol) production with an overall yield of 182 g ABE/kg cellulose. Process IV showed 191% higher titer and 14% higher yield of ABE production, compared with Process I.