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Sustainable Development and Application of Renewable Chemicals from Biomass and Waste II

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Applied Chemistry".

Deadline for manuscript submissions: 30 June 2024 | Viewed by 14458

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Guest Editor
School of Chemical Sciences, Universiti Sains Malaysia, Penang, Malaysia
Interests: nanomaterials; biomass reutilization; material chemistry; nanocomposite; microbial fuel cells; wastewater treatment
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Advancements in efficient energy sources have played a pivotal role in determining the present world energy structure. Renewable biomass energy has been incorporated in industrial regulations and policies in many European countries. Based on the statistics, more than one-seventh of the total world energy consumption is generated from biomass.

The renewable energies movement was prompted by two important factors: (a) growing world energy consumption and (b) the abundance of generated biomass residues, especially in agriculture. In the case of the first, batteries containing different metals are considered, as is the production of items for human consumption (food, clothing, home comfort, etc.). In the second case, the biomass waste from plants and animals, as byproducts of cultivating and production process, is the main source of generated waste.

In agriculture, for example, rice paddies generate rice husks, wheat generates wheat straws, oil palm generates empty fruit bunches, and there are many more relevant examples. In animal breeding, manure and crustacean shells are some of the byproducts. Consequently, the annual global production of waste, through its considerable increase, has caused serious problems in the soils in which it is present, and its possible conversion and reuse is being explored. Biomass can be used as an alternative material for certain applications due to its carbon-rich structure. In such applications, biomass typically starts by concentrating the carbon in the structure by removing other elements, known as carbonization. Researchers are mainly focused on biomass as activated carbon, due to its cost-effectiveness. Biomass, when converted into a material similar to graphene or graphite, can be used as clean energy in products with added value, such as an electrode in batteries, solar cells, fuel cells, etc.

The waste that is produced by human activities can be used in different technological activities with a sustainable basis. Among them, hygienic paints and fabrics for antimicrobial use have been the object of study for different research groups in recent years.

This Special Issue welcomes full papers, short communications, and review articles highlighting aspects of the current trends in the area of development and application of renewable chemicals from biomass and waste.

Dr. Mohamad Nasir Mohamad Ibrahim
Guest Editor

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Keywords

  • biomass waste reutilization
  • applications of lignin
  • applications of cellulose and hemicellulose
  • energy generation from biomass/waste
  • biochemistry of biomass/waste
  • hygienic paints
  • antimicrobial fabrics

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Published Papers (11 papers)

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Research

Jump to: Review

27 pages, 5789 KiB  
Article
Prediction of Individual Gas Yields of Supercritical Water Gasification of Lignocellulosic Biomass by Machine Learning Models
by Kapil Khandelwal and Ajay K. Dalai
Molecules 2024, 29(10), 2337; https://doi.org/10.3390/molecules29102337 - 16 May 2024
Viewed by 250
Abstract
Supercritical water gasification (SCWG) of lignocellulosic biomass is a promising pathway for the production of hydrogen. However, SCWG is a complex thermochemical process, the modeling of which is challenging via conventional methodologies. Therefore, eight machine learning models (linear regression (LR), Gaussian process regression [...] Read more.
Supercritical water gasification (SCWG) of lignocellulosic biomass is a promising pathway for the production of hydrogen. However, SCWG is a complex thermochemical process, the modeling of which is challenging via conventional methodologies. Therefore, eight machine learning models (linear regression (LR), Gaussian process regression (GPR), artificial neural network (ANN), support vector machine (SVM), decision tree (DT), random forest (RF), extreme gradient boosting (XGB), and categorical boosting regressor (CatBoost)) with particle swarm optimization (PSO) and a genetic algorithm (GA) optimizer were developed and evaluated for prediction of H2, CO, CO2, and CH4 gas yields from SCWG of lignocellulosic biomass. A total of 12 input features of SCWG process conditions (temperature, time, concentration, pressure) and biomass properties (C, H, N, S, VM, moisture, ash, real feed) were utilized for the prediction of gas yields using 166 data points. Among machine learning models, boosting ensemble tree models such as XGB and CatBoost demonstrated the highest power for the prediction of gas yields. PSO-optimized XGB was the best performing model for H2 yield with a test R2 of 0.84 and PSO-optimized CatBoost was best for prediction of yields of CH4, CO, and CO2, with test R2 values of 0.83, 0.94, and 0.92, respectively. The effectiveness of the PSO optimizer in improving the prediction ability of the unoptimized machine learning model was higher compared to the GA optimizer for all gas yields. Feature analysis using Shapley additive explanation (SHAP) based on best performing models showed that (21.93%) temperature, (24.85%) C, (16.93%) ash, and (29.73%) C were the most dominant features for the prediction of H2, CH4, CO, and CO2 gas yields, respectively. Even though temperature was the most dominant feature, the cumulative feature importance of biomass characteristics variables (C, H, N, S, VM, moisture, ash, real feed) as a group was higher than that of the SCWG process condition variables (temperature, time, concentration, pressure) for the prediction of all gas yields. SHAP two-way analysis confirmed the strong interactive behavior of input features on the prediction of gas yields. Full article
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17 pages, 1380 KiB  
Article
Sustainable Recovery of Platinum Group Metals from Spent Automotive Three-Way Catalysts through a Biogenic Thiosulfate-Copper-Ammonia System
by Mariacristina Compagnone, José Joaquín González-Cortés, María Pilar Yeste, Domingo Cantero and Martín Ramírez
Molecules 2023, 28(24), 8078; https://doi.org/10.3390/molecules28248078 - 14 Dec 2023
Viewed by 977
Abstract
This study explores an eco-friendly method for recovering platinum group metals from a synthetic automotive three-way catalyst (TWC). Bioleaching of palladium (Pd) using the thiosulfate-copper-ammonia leaching processes, with biogenic thiosulfate sourced from a bioreactor used for biogas biodesulfurization, is proposed as a sustainable [...] Read more.
This study explores an eco-friendly method for recovering platinum group metals from a synthetic automotive three-way catalyst (TWC). Bioleaching of palladium (Pd) using the thiosulfate-copper-ammonia leaching processes, with biogenic thiosulfate sourced from a bioreactor used for biogas biodesulfurization, is proposed as a sustainable alternative to conventional methods. Biogenic thiosulfate production was optimized in a gas-lift bioreactor by studying the pH (8–10) and operation modes (batch and continuous) under anoxic and microaerobic conditions for 35 d. The maximum concentration of 4.9 g S2O32− L−1 of biogenic thiosulfate was reached under optimal conditions (batch mode, pH = 10, and airflow rate 0.033 vvm). To optimize Pd bioleaching from a ground TWC, screening through a Plackett–Burman design determined that oxygen and temperature significantly affected the leaching yield negatively and positively, respectively. Based on these results, an optimization through an experimental design was performed, indicating the optimal conditions to be Na2S2O3 1.2 M, CuSO4 0.03 M, (NH4)2SO4 1.5 M, Na2SO3 0.2 M, pH 8, and 60 °C. A remarkable 96.2 and 93.2% of the total Pd was successfully extracted from the solid at 5% pulp density using both commercially available and biogenic thiosulfate, highlighting the method’s versatility for Pd bioleaching from both thiosulfate sources. Full article
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15 pages, 2604 KiB  
Article
Pyrolysis of Solid Recovered Fuel Using Fixed and Fluidized Bed Reactors
by Myeongjong Lee, Hyeongtak Ko and Seacheon Oh
Molecules 2023, 28(23), 7815; https://doi.org/10.3390/molecules28237815 - 28 Nov 2023
Viewed by 1129
Abstract
Currently, most plastic waste stems from packaging materials, with a large proportion of this waste either discarded by incineration or used to derive fuel. Accordingly, there is growing interest in the use of pyrolysis to chemically recycle non-recyclable (i.e., via mechanical means) plastic [...] Read more.
Currently, most plastic waste stems from packaging materials, with a large proportion of this waste either discarded by incineration or used to derive fuel. Accordingly, there is growing interest in the use of pyrolysis to chemically recycle non-recyclable (i.e., via mechanical means) plastic waste into petrochemical feedstock. This comparative study compared pyrolysis characteristics of two types of reactors, namely fixed and fluidized bed reactors. Kinetic analysis for pyrolysis of SRF was also performed. Based on the kinetic analysis of the pyrolytic reactions using differential and integral methods applied to the TGA results, it was seen that the activation energy was lower in the initial stage of pyrolysis. This trend can be mainly attributed to the initial decomposition of PP components, which was subsequently followed by the decomposition of PE. From the kinetic analysis, the activation energy corresponding to the rate of pyrolysis reaction conversion was obtained. In conclusion, pyrolysis carried out using the fluidized bed reactor resulted in a more active decomposition of SRF. The relatively superior performance of this reactor can be attributed to the increased mass and heat transfer effects caused by fluidizing gases, which result in greater gas yields. Regarding the characteristics of liquid products generated during pyrolysis, it was seen that the hydrogen content in the liquid products obtained from the fluidized bed reactor decreased, leading to the formation of oils with higher molecular weights and higher C/H ratios, because the pyrolysis of SRF in the fluidized bed reactor progressed more rapidly than that in the fixed bed reactor. Full article
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15 pages, 1623 KiB  
Article
Primary Products from Fast Co-Pyrolysis of Palm Kernel Shell and Sawdust
by David O. Usino, Päivi Ylitervo and Tobias Richards
Molecules 2023, 28(19), 6809; https://doi.org/10.3390/molecules28196809 - 26 Sep 2023
Viewed by 883
Abstract
Co-pyrolysis is one possible method to handle different biomass leftovers. The success of the implementation depends on several factors, of which the quality of the produced bio-oil is of the highest importance, together with the throughput and constraints of the feedstock. In this [...] Read more.
Co-pyrolysis is one possible method to handle different biomass leftovers. The success of the implementation depends on several factors, of which the quality of the produced bio-oil is of the highest importance, together with the throughput and constraints of the feedstock. In this study, the fast co-pyrolysis of palm kernel shell (PKS) and woody biomass was conducted in a micro-pyrolyser connected to a Gas Chromatograph–Mass Spectrometer/Flame Ionisation Detector (GC–MS/FID) at 600 °C and 5 s. Different blend ratios were studied to reveal interactions on the primary products formed from the co-pyrolysis, specifically PKS and two woody biomasses. A comparison of the experimental and predicted yields showed that the co-pyrolysis of the binary blends in equal proportions, PKS with mahogany (MAH) or iroko (IRO) sawdust, resulted in a decrease in the relative yield of the phenols by 19%, while HAA was promoted by 43% for the PKS:IRO-1:1 pyrolysis blend, and the saccharides were strongly inhibited for the PKS:MAH-1:1 pyrolysis blend. However, no difference was observed in the yields for the different groups of compounds when the two woody biomasses (MAH:IRO-1:1) were co-pyrolysed. In contrast to the binary blend, the pyrolysis of the ternary blends showed that the yield of the saccharides was promoted to a large extent, while the acids were inhibited for the PKS:MAH:IRO-1:1:1 pyrolysis blend. However, the relative yield of the saccharides was inhibited to a large extent for the PKS:MAH:IRO-1:2:2 pyrolysis blend, while no major difference was observed in the yields across the different groups of compounds when PKS and the woody biomass were blended in equal amounts and pyrolysed (PKS:MAH:IRO-2:1:1). This study showed evidence of a synergistic interaction when co-pyrolysing different biomasses. It also shows that it is possible to enhance the production of a valuable group of compounds with the right biomass composition and blend ratio. Full article
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15 pages, 1346 KiB  
Article
A Novel Kinetic Modeling of Enzymatic Hydrolysis of Sugarcane Bagasse Pretreated by Hydrothermal and Organosolv Processes
by João Moreira Neto, Josiel Martins Costa, Antonio Bonomi and Aline Carvalho Costa
Molecules 2023, 28(14), 5617; https://doi.org/10.3390/molecules28145617 - 24 Jul 2023
Cited by 2 | Viewed by 1277
Abstract
Lignocellulosic biomasses have a complex and compact structure, requiring physical and/or chemical pretreatments to produce glucose before hydrolysis. Mathematical modeling of enzymatic hydrolysis highlights the interactions between cellulases and cellulose, evaluating the factors contributing to reactor scale-up and conversion rates. Furthermore, this study [...] Read more.
Lignocellulosic biomasses have a complex and compact structure, requiring physical and/or chemical pretreatments to produce glucose before hydrolysis. Mathematical modeling of enzymatic hydrolysis highlights the interactions between cellulases and cellulose, evaluating the factors contributing to reactor scale-up and conversion rates. Furthermore, this study evaluated the influence of two pretreatments (hydrothermal and organosolv) on the kinetics of enzymatic hydrolysis of sugarcane bagasse. The kinetic parameters of the model were estimated using the Pikaia genetic algorithm with data from the experimental profiles of cellulose, cellobiose, glucose, and xylose. The model considered the phenomenon of non-productive adsorption of cellulase on lignin and inhibition of cellulase by xylose. Moreover, it included the behavior of cellulase adsorption on the substrate throughout hydrolysis and kinetic equations for obtaining xylose from xylanase-catalyzed hydrolysis of xylan. The model for both pretreatments was experimentally validated with bagasse concentration at 10% w/v. The Plackett–Burman design identified 17 kinetic parameters as significant in the behavior of process variables. In this way, the modeling and parameter estimation methodology obtained a good fit from the experimental data and a more comprehensive model. Full article
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17 pages, 2499 KiB  
Article
Improving the Cellulose Enzymatic Digestibility of Sugarcane Bagasse by Atmospheric Acetic Acid Pretreatment and Peracetic Acid Post-Treatment
by Yuchen Bai, Mingke Tian, Zhiwei Dai and Xuebing Zhao
Molecules 2023, 28(12), 4689; https://doi.org/10.3390/molecules28124689 - 10 Jun 2023
Viewed by 1046
Abstract
Pretreatment of sugarcane bagasse (SCB) by aqueous acetic acid (AA), with the addition of sulfuric acid (SA) as a catalyst under mild condition (<110 °C), was investigated. A response surface methodology (central composite design) was employed to study the effects of temperature, AA [...] Read more.
Pretreatment of sugarcane bagasse (SCB) by aqueous acetic acid (AA), with the addition of sulfuric acid (SA) as a catalyst under mild condition (<110 °C), was investigated. A response surface methodology (central composite design) was employed to study the effects of temperature, AA concentration, time, and SA concentration, as well as their interactive effects, on several response variables. Kinetic modeling was further investigated for AA pretreatment using both Saeman’s model and the Potential Degree of Reaction (PDR) model. It was found that Saeman’s model showed a great deviation from the experimental results, while the PDR model fitted the experimental data very well, with determination coefficients of 0.95–0.99. However, poor enzymatic digestibility of the AA-pretreated substrates was observed, mainly due to the relatively low degree of delignification and acetylation of cellulose. Post-treatment of the pretreated cellulosic solid well improved the cellulose digestibly by further selectively removing 50–60% of the residual linin and acetyl group. The enzymatic polysaccharide conversion increased from <30% for AA-pretreatment to about 70% for PAA post-treatment. Full article
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10 pages, 5008 KiB  
Article
Development of Photothermal Catalyst from Biomass Ash (Bagasse) for Hydrogen Production via Dry Reforming of Methane (DRM): An Experimental Study
by Ittichai Kanchanakul, Thongchai Rohitatisha Srinophakun, Sanchai Kuboon, Hiroaki Kaneko, Wasawat Kraithong, Masahiro Miyauchi and Akira Yamaguchi
Molecules 2023, 28(12), 4578; https://doi.org/10.3390/molecules28124578 - 6 Jun 2023
Cited by 2 | Viewed by 1482
Abstract
Conventional hydrogen production, as an alternative energy resource, has relied on fossil fuels to produce hydrogen, releasing CO2 into the atmosphere. Hydrogen production via the dry forming of methane (DRM) process is a lucrative solution to utilize greenhouse gases, such as carbon [...] Read more.
Conventional hydrogen production, as an alternative energy resource, has relied on fossil fuels to produce hydrogen, releasing CO2 into the atmosphere. Hydrogen production via the dry forming of methane (DRM) process is a lucrative solution to utilize greenhouse gases, such as carbon dioxide and methane, by using them as raw materials in the DRM process. However, there are a few DRM processing issues, with one being the need to operate at a high temperature to gain high conversion of hydrogen, which is energy intensive. In this study, bagasse ash, which contains a high percentage of silicon dioxide, was designed and modified for catalytic support. Modification of silicon dioxide from bagasse ash was utilized as a waste material, and the performance of bagasse ash-derived catalysts interacting with light irradiation and reducing the amount of energy used in the DRM process was explored. The results showed that the performance of 3%Ni/SiO2 bagasse ash WI was higher than that of 3%Ni/SiO2 commercial SiO2 in terms of the hydrogen product yield, with hydrogen generation initiated in the reaction at 300 °C. Using the same synthesis method, the current results suggested that bagasse ash-derived catalysts had better performance than commercial SiO2-derived catalysts when exposed to an Hg-Xe lamp. This indicated that silicon dioxide from bagasse ash as a catalyst support could help improve the hydrogen yield while lowering the temperature in the DRM reaction, resulting in less energy consumption in hydrogen production. Full article
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17 pages, 4572 KiB  
Article
Bioenergy Generation and Phenol Degradation through Microbial Fuel Cells Energized by Domestic Organic Waste
by Asim Ali Yaqoob, Nabil Al-Zaqri, Muhammad Alamzeb, Fida Hussain, Sang-Eun Oh and Khalid Umar
Molecules 2023, 28(11), 4349; https://doi.org/10.3390/molecules28114349 - 25 May 2023
Cited by 13 | Viewed by 1658
Abstract
Microbial fuel cells (MFCs) seem to have emerged in recent years to degrade the organic pollutants from wastewater. The current research also focused on phenol biodegradation using MFCs. According to the US Environmental Protection Agency (EPA), phenol is a priority pollutant to remediate [...] Read more.
Microbial fuel cells (MFCs) seem to have emerged in recent years to degrade the organic pollutants from wastewater. The current research also focused on phenol biodegradation using MFCs. According to the US Environmental Protection Agency (EPA), phenol is a priority pollutant to remediate due to its potential adverse effects on human health. At the same time, the present study focused on the weakness of MFCs, which is the low generation of electrons due to the organic substrate. The present study used rotten rice as an organic substrate to empower the MFC’s functional capacity to degrade the phenol while simultaneously generating bioenergy. In 19 days of operation, the phenol degradation efficiency was 70% at a current density of 17.10 mA/m2 and a voltage of 199 mV. The electrochemical analysis showed that the internal resistance was 312.58 Ω and the maximum specific capacitance value was 0.00020 F/g on day 30, which demonstrated mature biofilm production and its stability throughout the operation. The biofilm study and bacterial identification process revealed that the presence of conductive pili species (Bacillus genus) are the most dominant on the anode electrode. However, the present study also explained well the oxidation mechanism of rotten rice with phenol degradation. The most critical challenges for future recommendations are also enclosed in a separate section for the research community with concluding remarks. Full article
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11 pages, 4644 KiB  
Article
Application of Alkali Lignin and Spruce Sawdust for the Effective Removal of Reactive Dyes from Model Wastewater
by Kateřina Hájková, Michaela Filipi, Roman Fojtík and Ali Dorieh
Molecules 2023, 28(10), 4114; https://doi.org/10.3390/molecules28104114 - 16 May 2023
Viewed by 1296
Abstract
Today, the emphasis is on environmentally friendly materials. Alkali lignin and spruce sawdust are suitable natural alternatives for removing dyes from wastewater. The main reason for using alkaline lignin as a sorbent is the recovery of waste black liquor from the paper industry. [...] Read more.
Today, the emphasis is on environmentally friendly materials. Alkali lignin and spruce sawdust are suitable natural alternatives for removing dyes from wastewater. The main reason for using alkaline lignin as a sorbent is the recovery of waste black liquor from the paper industry. This work deals with removing dyes from wastewater using spruce sawdust and lignin at two different temperatures. The decolorization yields were calculated as the final values. Increasing the temperature during adsorption leads to higher decolorization yields, which may be due to the fact that some substances react only at elevated temperatures. The results of this research are useful for the treatment of industrial wastewater in paper mills, and the waste black liquor (alkaline lignin) can be used as a biosorbent. Full article
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21 pages, 6228 KiB  
Article
Valoration of the Synthetic Antioxidant Tris-(Diterbutyl-Phenol)-Phosphite (Irgafos P-168) from Industrial Wastewater and Application in Polypropylene Matrices to Minimize Its Thermal Degradation
by Joaquín Hernández-Fernández, Heidis Cano and Ana Fonseca Reyes
Molecules 2023, 28(7), 3163; https://doi.org/10.3390/molecules28073163 - 2 Apr 2023
Cited by 2 | Viewed by 2544
Abstract
Industrial wastewater from petrochemical processes is an essential source of the synthetic phenolic phosphite antioxidant (Irgafos P-168), which negatively affects the environment. For the determination and analysis of Irgafos P-168, DSC, HPLC-MS, and FTIR methodologies were used. Solid phase extraction (SPE) proved to [...] Read more.
Industrial wastewater from petrochemical processes is an essential source of the synthetic phenolic phosphite antioxidant (Irgafos P-168), which negatively affects the environment. For the determination and analysis of Irgafos P-168, DSC, HPLC-MS, and FTIR methodologies were used. Solid phase extraction (SPE) proved to be the best technique for extracting Irgafos from wastewater. HPLC-MS and SPE determined the repeatability, reproducibility, and linearity of the method and the SPE of the standards and samples. The relative standard deviations, errors, and correlation coefficients for the repeatability and reproducibility of the calibration curves were less than 4.4% and 4.2% and greater than 0.99955, respectively. The analysis of variance (ANOVA), using the Fisher method with confidence in 95% of the data, did not reveal significant differences between the mentioned parameters. The removal of the antioxidant from the wastewater by SPE showed recovery percentages higher than 91.03%, and the chemical characterization of this antioxidant by FTIR spectroscopy, DSC, TGA, and MS showed it to be structurally the same as the Irgafos P-168 molecule. The recovered Irgafos was added to the polypropylene matrix, significantly improving its oxidation times. An OIT analysis, performed using DSC, showed that the recovered Irgafos-blended polypropylene (PP) demonstrated oxidative degradation at 8 min. With the addition of the Irgafos, the oxidation time was 13 min. This increases the polypropylene’s useful life and minimizes the environmental impact of the wastewater. Full article
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Review

Jump to: Research

27 pages, 1354 KiB  
Review
Renewable Energy Potential: Second-Generation Biomass as Feedstock for Bioethanol Production
by Chidiebere Millicent Igwebuike, Sary Awad and Yves Andrès
Molecules 2024, 29(7), 1619; https://doi.org/10.3390/molecules29071619 - 4 Apr 2024
Viewed by 940
Abstract
Biofuels are clean and renewable energy resources gaining increased attention as a potential replacement for non-renewable petroleum-based fuels. They are derived from biomass that could either be animal-based or belong to any of the three generations of plant biomass (agricultural crops, lignocellulosic materials, [...] Read more.
Biofuels are clean and renewable energy resources gaining increased attention as a potential replacement for non-renewable petroleum-based fuels. They are derived from biomass that could either be animal-based or belong to any of the three generations of plant biomass (agricultural crops, lignocellulosic materials, or algae). Over 130 studies including experimental research, case studies, literature reviews, and website publications related to bioethanol production were evaluated; different methods and techniques have been tested by scientists and researchers in this field, and the most optimal conditions have been adopted for the generation of biofuels from biomass. This has ultimately led to a subsequent scale-up of procedures and the establishment of pilot, demo, and large-scale plants/biorefineries in some regions of the world. Nevertheless, there are still challenges associated with the production of bioethanol from lignocellulosic biomass, such as recalcitrance of the cell wall, multiple pretreatment steps, prolonged hydrolysis time, degradation product formation, cost, etc., which have impeded the implementation of its large-scale production, which needs to be addressed. This review gives an overview of biomass and bioenergy, the structure and composition of lignocellulosic biomass, biofuel classification, bioethanol as an energy source, bioethanol production processes, different pretreatment and hydrolysis techniques, inhibitory product formation, fermentation strategies/process, the microorganisms used for fermentation, distillation, legislation in support of advanced biofuel, and industrial projects on advanced bioethanol. The ultimate objective is still to find the best conditions and technology possible to sustainably and inexpensively produce a high bioethanol yield. Full article
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