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This study evaluated the use of a renewable organic acid (citric acid) as homogeneous catalyst for the pretreatment of raw sugarcane bagasse (SB). A 22 central composite design with two factors (reaction time and citric acid concentration) was used to evaluate the effect of the factors on the chemical composition of the pretreated SB samples and enzymatic hydrolysis efficiency. The enzymatic hydrolysis experiments of the pretreated SB samples were performed using the enzymatic cocktail Cellic® CTec 3 and the total reducing sugars (TRS) released after enzymatic hydrolysis was determined. In addition, scanning electron microscopy and X-ray diffraction were used to examine the changes in the morphology and structure of the pretreated SB samples. The changes in the structure and chemical composition of the pretreated SB resulted in a high TRS concentration (28.2 g L−1) after enzymatic hydrolysis, for the pretreatment condition employing 6 wt% citric acid and 102.4 min, compared to the raw SB (3.06 g L−1). The pretreatment showed potential for application since a moderate conversion of polysaccharides in TRS was obtained, even though it was a pretreatment carried out under milder conditions. The pretreatment studied has the advantage of using weak and environmentally friendly acid catalyst, atmospheric pressure, and low temperature. • Pretreatment of sugarcane bagasse (SB) with citric acid was studied. • Chemical, structural and morphological changes of SB was investigated. • Changes in the SB was effective in improve sugar conversion by enzymatic hydrolysis. • High concentrations of total reducing sugars (28.2 g L−1) in comparison to the raw SB (3.06 g L−1) was obtained. [ABSTRACT FROM AUTHOR]

In this study, five fungal strains (Aspergillus niger SCBM1 – Ni, Aspergillus fumigatus SCBM6 – Fu, Trametes versicolor 561 – Tr, Ganoderma lucidum 601 – Ga and Pleurotus ostreatus PL06 – Pl) were cultivated individually and in consortium for biosynthesis of lignocellulose-degrading enzymes by solid-state fermentation (SSF). The enzyme production was investigated using a 25−1 fractional factorial design, with a total of 16 experiments (F1–F16) using raw sugarcane bagasse and raw wheat bran as substrates. Among the enzymatic extracts produced, Ni (F1) exhibited the highest production of endoglucanase (82.70 U/gds) (units per gram of dry substrate), exoglucanase (80.48 U/gds), β-xylosidase (145.01 U/gds) and manganese peroxidase (3.38 U/gds). For filter paper cellulase, Tr cocktail (F5) was the one that stood out (9.45 U/gds). Among the extracts produced in consortium, Ni + Tr + Pl (F6) presented the highest production of β-glucosidase (171.09 U/gds), β-xylosidase (139.99 U/gds) and manganese peroxidase (3.29 U/gds). For FPase, Ni + Fu + Ga (F12) exhibited the best production (10.46 U/gds). The highest xylanase biosynthesis (2582.38 U/gds) was obtained in Ni + Fu + Pl extract (F4). For laccase, the maximum biosynthesis (25.27 U/gds) was obtained in Tr + Ga + Pl (F13). The cocktails that presented the best enzyme production were: Ni (F1), Ni + Fu + Pl (F9), Ni + Tr + Pl (F6) and Ni + Ga + Pl (F10), demonstrating that the use of microbial consortium can be a promising alternative to obtain enzymatic cocktails with high synergism. • Fungal species were cultivated for biosynthesis of lignocellulose-degrading enzymes. • A total of 16 solid-state fermentations (SSF) were carried out. • Highest productions were obtained in Ni, Ni + Fu + Pl, Ni + Tr + Pl and Ni + Ga + Pl enzymatic cocktails. • The fungal consortia can be a promising alternative to obtain cocktails with high synergism. [ABSTRACT FROM AUTHOR]

One of the bottlenecks related to the extraction of protein from lignocellulosic biomass is the development of an efficient, selective, economical, and environmentally friendly process. This study investigated the reduced-pressure alkaline pretreatment (RPAP) as an innovative approach for protein extraction from brewer's spent grain (BSG). Experiments were carried out at different temperatures (30–70 °C), pressures (150–1025 mBar), times (1–7 h), and NaOH concentrations (20–180 mM) to obtain a high-yield and selective protein extraction associated with low CO 2 emissions and high processing capacity per batch. Protein concentration, total CO 2 emissions per protein extracted, selectivity (related to sugars), and processing capacity were the responses considered for optimization. The optimum condition (T = 70 °C; P = 455 mBar, t = 1 h, and [NaOH] = 180.00 mM) was able to extract 80% of the total protein present in BSG composition. This condition was also selective (76.8%) and had a low carbon footprint (0.43 g CO 2 g protein extracted −1). Glutamic acid was the most abundant amino acid in both raw BSG (23.4%) and protein hydrolysate (24.7%), followed by leucine (9.5% and 8.4%, respectively), proline (8.4% and 11.8%, respectively), and aspartic acid (9.0% and 8.1%, respectively). RPAP was demonstrated to be an efficient and sustainable technology for protein extraction from BSG. This opens up new opportunities for BSG and other protein-rich lignocellulosic materials valorization in a biorefinery. [Display omitted] • Brewer's spent grain (BSG) is an important source of protein for food fortification. • Reduced-pressure alkaline pretreatment (RPAP) was efficient to extract protein from BSG. • Optimum RPAP condition extracted protein with high selectivity and low carbon footprint. • Glutamic acid was the most abundant amino acid in BSG and in the protein hydrolysate. [ABSTRACT FROM AUTHOR]

Organosolv delignification assisted by high–pressure carbon dioxide (HP–CO 2 ), a low cost, non–corrosive and recoverable compound was evaluated as a potential green pretreatment technology for lignin extraction from liquid hot water (LHW) pretreated sugarcane bagasse to produce fermentable sugars in a lignocellulosic biorefinery concept. In this study, LHW pretreated bagasse (180 °C for 20 min with a liquid–to–solid ratio ( LSR ) of 9 (v/w)) was delignified with an ethanol–water mixture (1:1, v/v) and HP–CO 2 as a co–solvent at milder temperatures (111.7–168.3 °C) and times (23.8–66.2 min) at a LSR of 5 (v/w). To evaluate the effects of varying operational conditions on the lignin content and delignification extent, while preserving the glucan fraction, a 2 2 central composite design was used as a factorial planning. Solid fractions with low lignin contents (7.35% and 10.78%) and high delignification extents (82.5% and 72.2%) with good glucan preservations (84.6% and 85.3%) were obtained at 140 °C for 45 min and 111.7 °C for 45 min, respectively. These solid fractions were subjected to enzymatic hydrolysis, yielding enzymatic conversions of 60.8% and 63.7%, respectively. [ABSTRACT FROM AUTHOR]

In this study, four different adsorbent materials: commercial powdered activated carbon (PAC) from pine tree (PAC-I) and coconut shell (PAC-III) agricultural crop wastes, coal (PAC-II), and carbon nanotubes (CNT) were tested and compared for the removal of sulfamethoxazole (SMX) from spiked aqueous solutions. The kinetic, extrathermodynamic, and thermodynamic parameters for the adsorption of SMX on PACs and CNT were also determined. The results indicate that PAC-I was the best adsorbent for SMX adsorption. SMX adsorption was only favorable with PAC-I and CNT, leading to Gibbs free energies in the range of −39 to −44 kJ mol −1 and showing that the adsorption process was spontaneous in all temperature ranges (15–45 °C) tested. Langmuir model best described SMX adsorption on PAC-I and led to maximum adsorption capacity of ∼131 mg g −1 (at 25 °C), which was ∼4.6 times higher than that observed for CNT. The mechanism of SMX adsorption on PAC-I and CNT was suggested with basis on thermodynamic and extrathermodynamic parameters. The kinetic studies showed the pseudo-second-order model best described SMX adsorption, yielding k 2 values of 0.0035 and 0.0016 g mg −1 min −1 for PAC-I and CNT, respectively. [ABSTRACT FROM AUTHOR]

Highlights: [•] LHW-HP-CO2 evaluated as a potential green technology for hemicelluloses extraction. [•] At 100°C for 30min and 115°C for 60min xylan equivalent ranged 10–12g/L. [•] At 115°C for 60min, the cellulose preservation achieved 97.2%. [•] Enzymatic hydrolysis yielded 30.43g/L glucose and 41.17% cellulose conversion. [ABSTRACT FROM AUTHOR]

In this study sugarcane bagasse was modified with succinic anhydride and EDTA dianhydride to obtain SCB 2 and EB adsorbents, respectively. These adsorbents were used to remove etherdiamine, which is used for iron ore flotation from single aqueous solutions. The removal and recovery of etherdiamine is important for environmental and economic reasons due to its toxicity and high cost. The results demonstrated that adsorption of etherdiamine by SCB 2 and EB was better fitted by a pseudo-second-order kinetic model than pseudo-first-order and Elovich models. Adsorption isotherms were better fitted by the Langmuir model rather than the Freundlich, Sips, and Temkin models. The maximum adsorption capacities (Q max) of SCB 2 and EB for etherdiamine adsorption were found to be 869.6 and 1203.5 mg/g, respectively. The calculated ΔG° values for adsorption of etherdiamine on SCB 2 (−22.70 kJ/mol) and EB (−19.10 kJ/mol) suggested that chemisorption is the main mechanism by which etherdiamine is removed from the aqueous solution for both adsorbents. The high Q max values showed that SCB 2 and EB are potential adsorbents for recovering the etherdiamine and treating effluents produced from iron ore flotation. [Copyright &y& Elsevier]

Abstract: In this study the adsorption of cationic dyes by modified sugarcane bagasse with EDTA dianhydride (EB) was examined using methylene blue (MB) and gentian violet (GV) as model compounds in aqueous single solutions. The synthesized adsorbent (EB) was characterized by FTIR, elemental analysis, and BET. The capacity of EB to adsorb dyes was evaluated at different contact times, pH values, and initial dye concentrations. According to the obtained results, the adsorption processes could be described by a pseudo-second-order kinetic model. The adsorption isotherms were well fitted by the Langmuir model. Maximum adsorption capacities for MB and GV on EB were found to be 202.43 and 327.83 mg/g, respectively. The free energy change during adsorption of MB and GV was found to be −22.50 and −24.21 kJ/mol, respectively, suggesting that chemisorption is the main mechanism controlling the adsorption process. [Copyright &y& Elsevier]

Abstract: Sugarcane bagasse cellulose was subjected to the extremely low acid (ELA) hydrolysis in 0.07% H2SO4 at 190, 210 and 225°C for various times. The cellulose residues from this process were characterized by TGA, XRD, GPC, FTIR and SEM. A kinetic study of thermal decomposition of the residues was also carried out, using the ASTM and Kissinger methods. The thermal studies revealed that residues of cellulose hydrolyzed at 190, 210 and 225°C for 80, 40 and 8min have initial decomposition temperature and activation energy for the main decomposition step similar to those of Avicel PH-101. XRD studies confirmed this finding by showing that these cellulose residues are similar to Avicel in crystallinity index and crystallite size in relation to the 110 and 200 planes. FTIR spectra revealed no significant changes in the cellulose chemical structure and analysis of SEM micrographs demonstrated that the particle size of the cellulose residues hydrolyzed at 190 and 210°C were similar to that of Avicel. [Copyright &y& Elsevier]

Abstract: This paper describes the organosolv delignification of depithed bagasse using glycerol–water mixtures without a catalyst. The experiments were performed using two separate experimental designs. In the first experiment, two temperatures (150 and 190°C), two time periods (60 and 240min) and two glycerol contents (20% and 80%, v/v) were used. In the second experiment, which was a central composite design, the glycerol content was maintained at 80%, and a range of temperatures (141.7–198.3°C) and time (23–277min) was used. The best result, obtained with a glycerol content of 80%, a reaction time of 150min and a temperature of 198.3°C, produced pulps with 54.4% pulp yield, 7.75% residual lignin, 81.4% delignification and 13.7% polyose content. The results showed that high contents of glycerol tend to produce pulps with higher delignification and higher polyoses content in relation to the pulps obtained from low glycerol content reactions. In addition, the proposed method shows potential as a pretreatment for cellulose saccharification. [Copyright &y& Elsevier]

Abstract: This work describes the preparation of a new chelating material derived from wood sawdust, Manilkara sp., and not only the use of a new support, but also a chemically modified sugarcane bagasse synthesized in our previous work to remove Zn2+ from aqueous solutions and electroplating wastewater. The first part describes the chemical modification of wood sawdust and sugarcane bagasse using ethylenediaminetetraacetic dianhydride (EDTAD) as modifying agent in order to introduce carboxylic acid and amine functional groups into these materials. The obtained materials such as the modified sugarcane bagasse, EB, and modified wood sawdust, ES were then characterized by infrared spectroscopy (IR) and CHN. The second part evaluates the adsorption capacity of Zn2+ by EB and ES from aqueous single metal solutions and real electroplating wastewater, which concentration was determined through direct titration with EDTA and inductively coupled plasma (ICP-OES). Adsorption isotherms were developed using Langmuir model. Zn2+ adsorption capacities were found to be 80mg/g for ES and 105mg/g for EB whereas for the industrial wastewater these values were found to be 47mg/g for ES and 45mg/g for EB. Zn2+ adsorption in the wastewater was found to be lower than in Zn2+ spiked solution due to the competition between other cations and/or interference of other ions, mainly Ca2+ and Cl− that were present in the wastewater. [Copyright &y& Elsevier]

Abstract: In a previous work, chemically modified cellulose (EMC) and sugarcane bagasse (EMMB) were prepared from mercerized cellulose (MC) and twice-mercerized sugarcane bagasse (MMB) using ethylenediaminetetraacetic dianhydride (EDTAD) as modifying agent. In this work we described in detail the modification of these materials in function of reaction time and EDTAD amount in the reaction media. The resistance of ester bond at pH 1, 2, 11, and 12 was also evaluated by FTIR. The results were used to model the hydrolysis process and a kinetic model was proposed. The modified materials (EMMB and EMC) were used to adsorb Ca2+ and Mg2+ ions from aqueous single solutions. The adsorption isotherms were developed at two pH values. These materials showed maximum adsorption capacities for Ca2+ and Mg2+ ions ranging from 15.6 to 54.1mg/g and 13.5 to 42.6mg/g, respectively. The modified material from sugarcane bagasse (EMMB) showed larger maximum adsorption capacities than modified material from cellulose (EMC) for both metals. [Copyright &y& Elsevier]

Abstract: This study describes the preparation of two new chelating materials, MMSCB 3 and 5, derived from succinylated twice-mercerized sugarcane bagasse (MMSCB 1). MMSCB 3 and 5 were synthesized from MMSCB 1 using two different methods as described by . In the first method MMSCB 1 was activated with 1,3-diisopropylcarbodiimide and in the second with acetic anhydride (to form an internal anhydride) and later both were reacted with triethylenetetramine in order to obtain MMSCB 3 and 5. New obtained materials were characterized by mass percent gain, concentration of amine groups, FTIR, and elemental analysis. MMSCB 3 and 5 showed mass percent gain of 19.9 and 57.1%, concentration of amine groups of 2.0 and 2.1mmol/g, and nitrogen content of 5.8 and 4.4%. The capacity of MMSCB 3 and 5 to adsorb Cu2+, Cd2+, and Pb2+ from aqueous single metal ion solutions was evaluated at different contact times, pHs, and initial metal ion concentrations. Adsorption isotherms were well fitted by Langmuir model. Maximum adsorption capacities of MMSCB 3 and 5 for Cu2+, Cd2+, and Pb2+ were found to be 59.5 and 69.4, 86.2 and 106.4, 158.7 and 222.2mg/g, respectively. [Copyright &y& Elsevier]

Abstract: This work describes the preparation of new chelating materials derived from cellulose and sugarcane bagasse for adsorption of Cu2+, Cd2+, and Pb2+ ions from aqueous solutions. The first part involved the mercerization treatment of cellulose and sugarcane bagasse with NaOH 5mol/L. Non- and mercerized cellulose and sugarcane bagasse were then reacted with ethylenediaminetetraacetic dianhydride (EDTAD) in order to prepare different chelating materials. These materials were characterized by mass percent gain, X-ray diffraction, FTIR, and elemental analysis. The second part consisted of evaluating the adsorption capacity of these modified materials for Cu2+, Cd2+, and Pb2+ ions from aqueous single metal solutions, whose concentration was determined by atomic absorption spectroscopy. These materials showed maximum adsorption capacities for Cu2+, Cd2+, and Pb2+ ions ranging from 38.8 to 92.6mg/g, 87.7 to 149.0mg/g, and 192.0 to 333.0mg/g, respectively. The modified mercerized materials showed larger maximum adsorption capacities than modified non-mercerized materials. [Copyright &y& Elsevier]

Succinylated mercerized cellulose (cell 1) was used to synthesize an anion exchange resin. Cell 1, containing carboxylic acid groups was reacted with triethylenetetramine to introduce amine functionality to this material to obtain cell 2. Cell 2 was reacted with methyl-iodide to quaternize the amine groups from this material to obtain cell 3. Cells 2 and 3 were characterized by mass percent gain, degree of amination and quaternization, FTIR and CHN. Cells 2 and 3 showed degrees of amination and quaternization of 2.8 and 0.9mmol/g and nitrogen content of 6.07% and 2.13%, respectively. Cell 3 was used for Cr (VI) adsorption studies. Adsorption equilibrium time and optimum pH for Cr (VI) adsorption were found to be 300min and 3.1, respectively. The Langmuir isotherm was used to model adsorption equilibrium data. The adsorption capacity of cell 3 was found to be 0.829mmol/g. Kinetic studies showed that the rate of adsorption of Cr (VI) on cell 3 obeyed a pseudo-second-order kinetic model. [Copyright &y& Elsevier]

Abstract: This study describes the preparation of two new chelating materials derived from succinylated mercerized cellulose (cell 1). Cell 1 was activated through two different methods by using diisopropylcarbodiimide and acetic anhydride (to form an internal anhydride) and reacted with triethylenetetramine in order to obtain cell 2 and 4. New modified celluloses were characterized by mass percent gain, concentration of amine functions, elemental analysis, and infrared spectroscopy. Cell 2 and 4 showed degrees of amination of 2.8 and 2.3mmol/g and nitrogen content of 6.07% and 4.61%, respectively. The capacity of cell 2 and 4 to adsorb Cu2+, Cd2+, and Pb2+ ions from single aqueous solutions were examined. The effect of contact time, pH, and initial concentration of metal ions on the metal ions uptake was also investigated. Adsorption isotherms were well fitted by the Langmuir model. The maximum adsorption capacity of cell 2 and 4 were found to be 56.8 and 69.4mg/g for Cu2+; 68.0 and 87.0mg/g for Cd2+; and 147.1 and 192.3mg/g for Pb2+, respectively. [Copyright &y& Elsevier]

Abstract: This work describes the preparation of new chelating material from mercerized sugarcane bagasse. The first part treats the chemical modification of non-mercerized sugarcane bagasse (SCB) and twice-mercerized sugarcane bagasse (MMSCB) with succinic anhydride. Mass percent gains (mpg) and degrees of succinylation (DS) of succinylated non- and twice-mercerized sugarcane bagasse 1 (SCB 1 and MMSCB 1) were calculated. MMSCB 1 exhibited an increase in mpg and DS of 49.2% and 0.9mmol/g in relation to SCB 1. SCB 2 and MMSCB 2 were obtained by treatment of MMSCB 1 and SCB 1 with bicarbonate solution to release the carboxylate functions and characterized by FTIR. The second part evaluates and compares the adsorption capacity of SCB 2 and MMSCB 2 for Cu2+, Cd2+ and Pb2+ ions in an aqueous single metal solution. Adsorption isotherms were developed using Langmuir model. MMSCB 2 exhibited an increase in Q max for Cd2+ (43.6mg/g) and Pb2+ (83.3mg/g) in relation to SCB 2. [Copyright &y& Elsevier]

Abstract: This work describes the preparation of new chelating material from mercerized cellulose. The first part treats the chemical modification of non-mercerized cellulose (cell 1) and mercerized cellulose (cell 2) with succinic anhydride. Mass percent gains (mpg) and degree of succinylation (DS) of cell 3 (from cell 1) and cell 4 (from cell 2) were calculated. Cell 4 in relation to cell 3 exhibited an increase in mpg and in the concentration of carboxylic functions of 68.9% and 2.8mmol/g, respectively. Cells 5 and 6 were obtained by treatment of cells 3 and 4 with bicarbonate solution to release the carboxylate functions and characterized by FTIR. The second part compares the adsorption capacity of cells 5 and 6 for Cu2+, Cd2+, and Pb2+ ions in an aqueous single metal solution. Adsorption isotherms were developed using Langmuir model. Cell 6 in relation to cell 5 exhibited an increase in Q max for Cu2+ (30.4mg/g), Cd2+ (86.0mg/g) and Pb2+ (205.9mg/g). [Copyright &y& Elsevier]

Technical lignin (TL) is a solid waste generated in industrial activities including pulp and paper mills and second-generation (2G) biorefineries. After isolation processes, TL is available in large quantities and has favorable compositional characteristics to produce high-performance activated carbons (ACs), such as low amount of residual carbohydrates, high reactivity due to the presence of different functional groups, and high aromatic carbon content. The value of the AC market is projected to reach US$ 7 billion by 2028, led by the water treatment sector. This work provides a brief overview of the status quo in the production of new adsorbents from TL, focusing on biorefineries, together with a bibliometric and patentometric survey. This evidenced a scarcity of publications on this topic, with the primary focus being on chemical modification of TL. A notable increase was observed in the production of ACs for electrochemical applications. Only a few patents were found on the subject, with China predominating technological development in this area. The findings revealed a technical-scientific-economic potential that has been largely unexplored, as no TL-derived AC from 2G biorefineries has yet been produced and applied in water treatment. Hence, there is excellent potential for the wider commercialization of AC produced from TL, representing an excellent opportunity to recycle TL and support the bio-based circular carbon economy, while also contributing to carbon emission neutrality. The marketing of high-performance ACs produced from TL could make biorefineries more profitable and less sensitive to market price fluctuations, while becoming carbon-neutral multiproduct platforms. [Display omitted] • Technical lignin (TL) has untapped technical-scientific-economic potential. • Production of activated carbon is a technological way to add value to TL. • Bibliometrics and patentometrics indicate a scarcity of value-added TL products. • Biorefineries as key contributors to carbon neutral emissions in the energy sector. • New opportunities and challenges identified for excess TL in 2G ethanol plant. [ABSTRACT FROM AUTHOR]

This study evaluated the potential of energy generation using a combined heat and power co-generation system (CHP) from biogas produced during the anaerobic digestion of coffee husks (CH) pretreated with steam explosion. Pretreatment conditions assessed were time (1, 5, 15 and 60 min) and temperature (120, 180 and 210 °C). Polysaccharides solubilisation and biogas production were not correlated. While pretreatment with severities higher than 4 resulted in a highest solubilisation of cellulose, hemicelluloses and lignin; however, furans concentration in those cases hindered biomass biodegradation. Considering a CHP, all pretreatment conditions were worthwhile when compared to non-pretreated CH. The best condition was 120 °C for 60 min, in which a 2.37 severity showed the highest methane yield (144.96 NmL CH 4 g COD −1 ) and electricity production (0.59 kWh kg CH −1 ). However, even better results could be achieved using 120 °C for only 5 min, which would lead to a larger amount of CH daily processed. [ABSTRACT FROM AUTHOR]

In the context of a sugarcane biorefinery, sugarcane bagasse produced may be pretreated generating a solid and liquid fraction. The solid fraction may be used for 2G bioethanol production, while the liquid fraction may be used to produce biogas through anaerobic digestion. The aim of this study consisted in evaluating the anaerobic digestion performance of hemicellulose hydrolysate produced after hydrothermal pretreatment of sugarcane bagasse. For this, hydrothermal pretreatment was assessed in a continuous upflow anaerobic sludge blanket (UASB) reactor operated at a hydraulic retention time (HRT) of 18.4 h. Process performance was investigated by varying the dilution of sugarcane bagasse hydrolysate with a solution containing xylose and the inlet organic loading rate (OLR). Experimental data showed that an increase in the proportion of hydrolysate in the feed resulted in better process performance for steps using 50% and 100% of real substrate. The best performance condition was achieved when increasing the organic loading rate (OLR) from 1.2 to 2.4 g COD/L·d, with an organic matter removal of 85.7%. During this period, the methane yield estimated by the COD removal would be 270 L CH 4 /kg COD. Nonetheless, when further increasing the OLR to 4.8 g COD/L·d, the COD removal decreased to 74%, together with an increase in effluent concentrations of VFA (0.80 g COD/L) and furans (115.3 mg/L), which might have inhibited the process performance. On the whole, the results showed that anaerobic digestion of sugarcane bagasse hydrolysate was feasible and may improve the net energy generation in a bioethanol plant, while enabling utilization of the surplus sugarcane bagasse in a sustainable manner. [ABSTRACT FROM AUTHOR]

This study evaluated the pretreatment of sugarcane bagasse (SCB) with dilute citric acid solution for biogas production. The black liquor (BL) from pretreatment and residual solid fraction (RSF) obtained after enzymatic hydrolysis were used as substrates for the biogas production. After saccharifications of the pretreated solid fractions performed with Cellic® CTec 3 cocktail, the highest concentration of total reducing sugars (TRS) was in the range of 10.7–184.8 g L−1 and the sugar yields were in the range of 3.5–88.8%. For BL, the contents of glucose, xylose, and arabinose were in the range of 1.9–8.9 g L−1, 4.0–24.7 g L−1, and 0.2–5.4 g L−1, respectively. Biogas production from BL and RSF resulted, respectively, in maximum values of 563.6 and 57.8 NmL g COD −1, indicating the feasibility of using dilute citric acid pretreatment coupled to biogas production in biorefineries. Brief energy and economic assessment were carried out considering the energy balance (thermal energy generated by burning biogas - thermal energy spent in the pretreatment), as well as revenue from a possible sale of electricity generated in a combined heat and power system. [Display omitted] [ABSTRACT FROM AUTHOR]

This study described the anaerobic degradation of the azo dye Remazol Golden Yellow RNL (RGY-RNL) using cellulose-immobilized riboflavin (MC 3) as the redox mediator. This new solid support containing immobilized riboflavin was synthesized from succinylated mercerized cellulose, and was characterized by elemental analysis, FTIR, and solid-state 13 C NMR. MC 3 was resistant to pH 2–9, and anaerobic degradation of RGY-RNL using MC 3 in the presence of anaerobic sludge yielded a zero order degradation rate constant ( k 0,obs ) equal to 0.189 mg/L h, which was 56% better than experiments carried out without a redox mediator. Color removal efficiency after 48 h of degradation averaged 89.4% in experiments with MC 3 and 72% without the addition of a redox mediator. These results showed that MC 3 can be used to immobilize redox mediators, allowing reduction of wastewater treatment costs. [ABSTRACT FROM AUTHOR]

Highlights: [•] Novel application for adsorbents after treating solutions containing metal ions. [•] New biobased heterogeneous catalysts were prepared for monoterpenes oxidation. [•] Production of high economic value oxygenated derivatives from monoterpenes. [•] Conversions among 49 and 78% and combined selectivity up to 59% were obtained. [Copyright &y& Elsevier]

This work describes the application of raw and chemically modified cellulose and sugarcane bagasse for ipso-hydroxylation of aryl boronic acids in environmentally friendly reaction conditions. The catalytic efficiency of five support-[Cu] materials was compared in forming phenols from aryl boronic acids. Our investigation highlights that the CEDA-[Cu] material (6-deoxy-6-aminoethyleneamino cellulose loaded with Cu) leads to the best results under very mild reaction conditions. The optimized catalytic sequence, allowing a facile transformation of boronic acids to phenols, required the mandatory and joint presence of the support, Cu2O, and KOH at room temperature. CEDA-[Cu] was characterized using 13C solid-state NMR, ICP, and FTIR. The use of CEDA-[Cu] accounts for the efficacious synthesis of variously substituted phenol derivatives and presents very good recyclability after five catalytic cycles. [ABSTRACT FROM AUTHOR]

This study investigates the production of volatile fatty acids (VFAs) from anaerobic digestion of raw brewer's spent grains (RBSG) and the solid fraction of brewer's spent grains pretreated by alkaline extraction (PBSG). The variables pH (5−9) and temperature (20–50 ºC) were optimized using Doehlert experimental design. The maximum concentrations of VFAs obtained were 8126.6 ± 108.8 mg L−1 for RBSG and 8005.3 ± 267.9 mg L−1 for PBSG. Protein removal did not affect the fermentative production of VFAs from BSG. However, the type of substrate influenced the VFAs profile and the microbial community. Clostridiaceae and Peptostreptococcaceae were the most abundant members in the reactors fed with raw BSG. On the other hand, Bacteroidaceae and Oscillospiraceae played important roles in the anaerobic digestion of pretreated BSG, accounting for more than 52% of the identified microorganisms. A multiproduct biorefinery with protein removal and subsequent VFAs production had a higher potential revenue (US$ 37,909.00 per ton of RBSG), compared to VFAs production according to a single product model (US$ 258.80 per ton of RBSG) (pH 8 and temperature of 20 ºC). This study provides insights from physicochemical, biological, and engineering perspectives, paving the way for future research focused on utilizing RBSG and PBSG for VFAs production. [Display omitted] • Volatile fatty acids (VFAs) produced by fermentation of raw and pretreated BSG. • The operating parameters pH and temperature were optimized using a Doehlert design. • Carbon-to-nitrogen ratio affected VFAs profile and bacterial composition. • The production of valeric acid is correlated with the presence of protein. • Multiproduct biorefinery was more profitable than the single product layout. [ABSTRACT FROM AUTHOR]

[Display omitted] • The SBTEA synthesis used renewable chemicals on a bio-based circular economy concept. • SBTEA efficiently removed As(V) from contaminated groundwater samples by ion-exchange. • SBTEA can be regenerated and reused with desorption efficiency higher than 90%. • SBTEA could be used to provide As(V) free drinking water in developing countries. • The estimated cost of production for SBTEA was USD 1.37 per gram of biosorbent. A quaternary ammonium anion exchanger (SBTEA) was prepared from sugarcane bagasse (SB) employing an improved two-step synthesis method by chemical modification with epichlorohydrin (EPI) and triethylamine (TEA) using N , N -dimethylformamide as a solvent without catalyst. Two multivariate optimizations were utilized to determine optimum conditions for SBTEA synthesis using Doehlert experimental designs. The optimum synthesis conditions were: V EPI = 12.8 mL g SB −1; V TEA = 22.0 mL g SB −1; and T 1 (etherification step) = T 2 (amination step) = 100 °C. The chlorine and nitrogen contents of the SBTEA produced under these conditions with a 21-fold increase in the synthesis scale (SBTEA -LS) were 4.2 ± 0.1% and 1.485 ± 0.007%, respectively. The 13C Multi-CP SS NMR revealed that 1.7 quaternary ammonium groups were introduced for 10 cellobiose units. SBTEA- LS was used to remove As(V) from contaminated groundwater samples with high removal efficiency (95 ± 4%), even with strong competitors such as SO 4 2−. The interactions involved in the adsorption were investigated through macroscopic and microscopic measurements, which suggested that the adsorption of As(V) on SBTEA -LS occurred mainly by ion exchange. Desorption experiments proved that SBTEA -LS could be efficiently regenerated (E des > 90%) using an HNO 3 solution, reducing operating costs and favoring technology upscaling. [ABSTRACT FROM AUTHOR]

A bioadsorbent (CEDA) capable of adsorbing As(V) and Cu(II) simultaneously was prepared by tosylation of microcrystalline cellulose (MC) and nucleophilic substitution of the tosyl group by ethylenediamine. MC, tosyl cellulose, and CEDA were characterized by elemental C, H, N, and S analysis, infrared spectroscopy, and 13C solid-state nuclear magnetic resonance spectroscopy. The adsorption of As(V) and Cu(II) on CEDA was evaluated as a function of solution pH, contact time, and initial solute concentration. The maximum adsorption capacities of CEDA for As(V) and Cu(II) were 1.62 and 1.09 mmol g−1, respectively. The interactions of As(V) and Cu(II) with CEDA were elucidated using thermodynamic parameters, molecular quantum mechanics calculations, and experiments with ion exchange of Cd(II) by Cu(II), and As(V) by SO 4 2−. Adsorption enthalpies were determined as a function of surface coverage of the CEDA, using isothermal titration calorimetry, with Δ ads H ° values of −32.24 ± 0.07 and −93 ± 2 kJ mol−1 obtained for As(V) and Cu(II), respectively. The potential to reuse CEDA was evaluated and the interference of other ions in the adsorption of As(V) and Cu(II) was investigated. Multi-component experiments showed that Cd(II), Co(II), Ni(II), and Pb(II) did not interfere in the adsorption of Cu(II), while SO 4 2− inhibited As(V) adsorption. [ABSTRACT FROM AUTHOR]

Batch and continuous adsorption of Co2+ and Cu2+ from aqueous solutions by oxidized sugarcane bagasse (SBox) and oxidized cellulose (Cox) were investigated. The oxidation reaction of sugarcane bagasse and cellulose was made with a mixture of H3PO4‒NaNO2 to obtain SBox and Cox, with the introduction of high number of carboxylic acid functions, 4.5 and 4.8 mmol/g, respectively. The adsorption kinetics of Co2+ and Cu2+ on SBox and Cox were modeled using two models (pseudo-first-order and pseudo-second-order) and the rate-limiting step controlling the adsorption was evaluated by Boyd and intraparticle diffusion models. The Sips and Langmuir models better fitted the isotherms with values of maximum adsorption capacity Q max of 0.68 and 0.37 mmol/g for Co2+ and 1.20 and 0.57 mmol/g for Cu2+ adsorption on Cox and SBox, respectively. The reuse of both spent adsorbents was evaluated. Adsorption of Cu2+ and Co2+ on SBox in continuous was evaluated using a 22 factorial design with spatial time and initial metal concentration as independent variables and Q max and effective use of the bed as responses. The breakthrough curves were very well described by the Bohart–Adams original model and the Q max values for Co2+ and Cu2+ were 0.22 and 0.55 mmol/g. SBox confirmed to be a promising biomaterial for application on a large scale. [ABSTRACT FROM AUTHOR]

In the second part of this series of studies, the bicomponent adsorption of safranin-T (ST) and auramine-O (AO) on trimellitated sugarcane bagasse (STA) was evaluated using equimolar dye aqueous solutions at two pH values. Bicomponent batch adsorption was investigated as a function of contact time, solution pH and initial concentration of dyes. Bicomponent kinetic data were fitted by the pseudo-first-order and pseudo-second-order models and the competitive model of Corsel. Bicomponent equilibrium data were fitted by the real adsorbed solution theory model. The antagonistic interactions between ST and AO in the adsorption systems studied contributed to obtain values of maximum adsorption capacity in mono- (Q max,mono) and bicomponent (Q max,multi) lower than unity (Q max,multi / Q max,mono at pH 4.5 for ST of 0.75 and AO of 0.37 and at pH 7 for ST of 0.94 and AO of 0.43). Mono- and bicomponent adsorption of dyes in a fixed-bed column was evaluated at pH 4.5. The breakthrough curves were fitted by the Thomas and Bohart-Adams original models. Desorption of ST in a fixed-bed column was studied. The results obtained from the bicomponent batch and continuous adsorption showed that the presence of ST most affected the AO adsorption than the presence of AO affected the ST adsorption. [ABSTRACT FROM AUTHOR]

Sugarcane bagasse cellulose succinate trimellitate (SBST) was prepared by a one-pot synthesis method. The synthesis of this novel mixed ester was investigated by a 23-factorial design. The parameters investigated were time, temperature, and succinic anhydride mole fraction (χ SA). The responses evaluated were the adsorption capacity (q Co2+ and q Ni2+), weight gain (wg), and number of carboxylic acid groups (n T,COOH). 13C Multiple Cross-Polarization solid-state NMR spectroscopy, 1H NMR relaxometry, and Fourier-transform infrared spectroscopy were used to elucidate the SBST structure. The best SBST reaction conditions were 100 °C, 660 min, and χ SA of 0.2, which yielded SBST with a wg of 57.1%, n T,COOH of 4.48 mmol g−1, and q Co2+ and q Ni2+ of 0.900 and 0.963 mmol g−1, respectively. The maximum adsorption capacities (Q max) (pH 5.75, 25 °C) estimated by the Redlich-Peterson model for Co2+ and Ni2+ were 1.16 and 1.29 mmol g−1. The Δ ads H ° values for Co2+ and Ni2+ adsorption obtained by isothermal titration calorimetry were 8.03 and 6.94 kJ mol−1. Regeneration and reuse of SBST were investigated and the best conditions applied for fixed-bed column adsorption in five consecutive cycles. SBST was fully desorbed and Q max values for Co2+ (0.95 mmol g−1) and Ni2+ (1.02 mmol g−1) were estimated using the Bohart-Adams model. [ABSTRACT FROM AUTHOR]

Graphical abstract Abstract Sugarcane bagasse cellulose mixed ester succinate phthalate (SBSPh) was synthesized by a novel one-pot reaction method. The effects of temperature, time and mole fraction of succinic anhydride (χ SA) on the responses weight gain (wg), number of carboxylic acid groups (n T,COOH), and adsorption capacity (q) of Co2+ and Ni2+ were evaluated by a 23 experimental design. The chemical structure of the material was elucidated by Fourier transform infrared, 13C Multiple Cross-Polarization solid-state NMR spectroscopy and 1H NMR relaxometry. The best SBSPh synthesis condition (100 °C, 11 h, χ SA of 0.2) yielded a wg of 59.1%, n T,COOH of 3.41 mmol g−1, and values of q Co 2+ and q Ni 2+ of 0.348 and 0.346 mmol g−1, respectively. The Sips model fitted better the equilibrium data, and the maximum adsorption capacities (pH 5.75 and 25 °C) estimated by this model were 0.62 and 0.53 mmol g−1 for Co2+ and Ni2+, respectively. The Δ ads H ° values estimated by isothermal titration calorimetry were 8.43 and 7.79 kJ mol−1 for Co2+ and Ni2+, respectively. Desorption and re-adsorption efficiencies were evaluated by a 22 experimental design, which showed that SBSPh adsorbent can be recovered and reused without significant loss of adsorption capacity. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Bifunctionalized chitosan(C4) was synthesized for removal of both Cu2+ and Cr6+. • C4 was insoluble in water in a pH range of 1–10. • The maximum adsorption capacity of C4 for Cu2+ adsorption at pH 5.5 was 2.60 mmol/g. • The maximum adsorption capacity of C4 for Cr6+ adsorption at pH 2.0 was 3.50 mmol/g. • The re-adsorption efficiency of C4 was 106% for Cu2+ and 44% for oxyanions of Cr6+. Abstract This study describes the chemical modification of chitosan to produce a novel bifunctionalized adsorbent material (C4) for the removal of Cu2+ and oxyanions of Cr6+ from a single aqueous solution. The chemical modifications allowed C4 to be insoluble under acidic conditions, improving the chemical properties of the modified chitosan in aqueous solution. C4 adsorbent was synthesized by reaction of the amino group of chitosan with 2-pyridinecarboxaldehyde, a reduction of imine group, followed by esterification with EDTA dianhydride (EDTAD). C4 was characterized by solid-state 13C nuclear magnetic resonance, infrared spectroscopy, and elemental analysis. The adsorption studies of Cu2+ and oxyanions of Cr6+ in a batch mode were evaluated as a function of the contact time (kinetics), solution pH, and initial metal ion concentration. The maximum adsorption capacities (Q max) of C4 for the adsorption of Cu2+ (pH 5.5) and Cr6+ (pH 2.0) were 2.60 and 3.50 mmol/g, respectively. The reusability of the recovered C4 adsorbent was also evaluated. [ABSTRACT FROM AUTHOR]

Ozone pretreatment of coffee husks (CH) was evaluated to generate hydrolysates for biogas production and to preserve cellulose of the solid phase for 2G ethanol production. Pretreatment variables included liquid-to-solid ratio ( LSR ), pH and specific applied ozone load ( SAOL ). Considering single-stage anaerobic digestion (AD), the highest methane production (36 NmL CH 4 /g CH) was achieved with the hydrolysate generated in the experiment using LSR 10 mL/g, pH 11 and SAOL 18.5 mg O 3 /g CH, leading to 0.064 kJ/g CH energy recovery. Due to the presence of toxic compounds in the hydrolysate, the addition of powdered activated carbon (4 g/L) to the reactor enhanced biogas production, leading to 86 NmL CH 4 /g CH yield and 0.58 kJ/g CH energy recovery. When two-stage AD was applied, methane production resulted in 49 NmL CH 4 /g CH, with additional 19 NmL H 2 /g CH production, resulting in a net 0.26 kJ/g CH energy recovery. [ABSTRACT FROM AUTHOR]

In the second part of this series of studies, the monocomponent adsorption of Cu 2+ , Co 2+ and Ni 2+ onto STA adsorbent in a fixed-bed column was investigated and optimized using a 2 2 central composite design. The process variables studied were: initial metal ion concentration and spatial time, and the optimized responses were: adsorption capacity of the bed ( Q max ), efficiency of the adsorption process ( EAP ), and effective use of the bed ( H ). The higher Q max for Cu 2+ , Co 2+ and Ni 2+ were 1.060, 0.800 and 1.029 mmol/g, respectively. The breakthrough curves were modeled by the original Thomas and Bohart-Adams models. The changes in enthalpy (Δ ads H °) of adsorption of the metal ions onto STA were determined by isothermal titration calorimetry (ITC). The values of Δ ads H ° were in the range of 3.0–6.8 kJ/mol, suggesting that the adsorption process involved physisorption. Desorption ( E des ) and re-adsorption ( E re-ads ) of metal ions from the STA adsorbent were also investigated in batch mode, and the optimum conditions were applied for three cycles of adsorption/desorption in a fixed bed column. For these cycles, the lowest values of E des and E re-ads were 95 and 92.3%, respectively, showing that STA is a promising candidate for real applications on a large scale. [ABSTRACT FROM AUTHOR]

Trimellitated-sugarcane bagasse (STA) was used as an environmentally friendly adsorbent for removal of the basic dyes auramine-O (AO) and safranin-T (ST) from aqueous solutions at pH 4.5 and 7.0. Dye adsorption was evaluated as a function of STA dosage, agitation speed, solution pH, contact time, and initial dye concentration. Pseudo-first- and pseudo-second-order, Elovich, intraparticle diffusion, and Boyd models were used to model adsorption kinetics. Langmuir, Dubinin-Radushkevich, Redlich-Peterson, Sips, Hill-de Boer, and Fowler-Guggenheim models were used to model adsorption isotherms, while a Scatchard plot was used to evaluate the existence of different adsorption sites. Maximum adsorption capacities for removal of AO and ST were 1.005 and 0.638 mmol g −1 at pH 4.5, and 1.734 and 1.230 mmol g −1 at pH 7.0, respectively. Adsorption enthalpy changes obtained by isothermal titration calorimetry (ITC) ranged from −21.07 ± 0.25 to −7.19 ± 0.05 kJ mol −1 , indicating that both dyes interacted with STA by physisorption. Dye desorption efficiencies ranged from 41 to 51%, and re-adsorption efficiencies ranged from 66 to 87%, showing that STA can be reused in new adsorption cycles. ITC data combined with isotherm studies allowed clarification of adsorption interactions. [ABSTRACT FROM AUTHOR]

This study was designed to obtain simultaneous sulfate (SO 4 2− ) and As(III) ions removal by non-traditional sulfate-reducing bacteria (SRB) growing in the presence of a protein biomass (PCF), a solid residual material produced by the poultry industry. Microbial cells and PCF were immobilized into calcium alginate beads to reduce mass losses. Microbial consortium efficiency was tested under different operational conditions: sodium lactate, glycerol and PCF as carbon sources; increasing As(III) content; acidic pH (5.0). Microbial diversity was evaluated by PCR-DGGE. Pantoea agglomerans , Enterobacter sp., Citrobacter sp., Cupriavidus metallidurans , Ralstonia sp. and Burkholderia cepacia were found. With the aim to obtain SO 4 2− and As(III) simultaneous removal, three semi-continuous up-flow reactors were constructed and operated for more than 100 days to prove their feasibility and reliability. Both SO 4 2− and As(III) ions were removed with 74.8% and 80% efficiency, respectively. Solid products were characterized by SEM-EDX, confirming PCF and non-traditional SRB roles during arsenic immobilization. Arsenic/sulfur compounds (possibly As/sulfides) were produced by reaction between As(III) and biogenic sulfide. Microbial consortium proved its ability of growing in an acidic environment without losing its sulfate reductive capacity by using glycerol and PCF as alternative carbon sources and tap water as micronutrients source. The non-traditional SRB culture removed both SO 4 2− and As(III) ions simultaneously, with no prior step needed to guarantee As(III) oxidation to As(V). Two different mechanisms could be involved: (i) precipitation as arsenic sulfide or, (ii) adsorption onto PCF/cells calcium alginate beads. [ABSTRACT FROM AUTHOR]

In the third part of this series of studies, the adsorption of the basic textile dyes auramine-O (AO) and safranin-T (ST) on a carboxylated cellulose derivative (CTA) were evaluated in mono- and bi-component spiked aqueous solutions. Adsorption studies were developed as a function of solution pH, contact time, and initial dye concentration. Adsorption kinetic data were modeled by monocomponent kinetic models of pseudo-first- (PFO), pseudo-second-order (PSO), intraparticle diffusion, and Boyd, while the competitive kinetic model of Corsel was used to model bicomponent kinetic data. Monocomponent adsorption equilibrium data were modeled by the Langmuir, Sips, Fowler-Guggenhein, Hill de-Boer, and Konda models, while the IAST and RAST models were used to model bicomponent equilibrium data. Monocomponent maximum adsorption capacities for AO and ST at pH 4.5 were 2.841 and 3.691 mmol g −1 , and at pH 7.0 were 5.443 and 4.074 mmol g −1 , respectively. Bicomponent maximum adsorption capacities for AO and ST at pH 7.0 were 1.230 and 3.728 mmol g −1 . Adsorption enthalpy changes (Δ ads H ) were obtained using isothermal titration calorimetry. The values of Δ ads H ranged from −18.83 to −5.60 kJ mol −1 , suggesting that physisorption controlled the adsorption process. Desorption and re-adsorption of CTA was also evaluated. [ABSTRACT FROM AUTHOR]

The preparation, characterisation and application of two pyridine-modified chitosan derivatives ( C1 and C2 ) containing Cu(OAc) 2 adsorbed as catalysts for the conversion of benzaldehyde into 2-nitro-1-phenylethanol are described. Quantitative solid-state 13 C multiple-contact cross-polarization, magic-angle-spinning, nuclear magnetic resonance (MC-CP MAS NMR) measurements confirmed the successful grafting of 2-pyridinecarboxaldehyde and 6-methylpyridine-2-carboxaldehyde to the chitosan backbone and indicated that 47(±2)% of the NH 2 groups were grafted for both C1 and C2 . The use of C1 -Cu(OAc) 2 as a catalyst in the nitroaldol reaction led to 96(±1)% conversion and 19(±4)% enantiomeric excess (ee), while the use of C2 -Cu(OAc) 2 as a catalyst also promoted the nitroaldol reaction, affording almost quantitatively the expected 2-nitro-1-phenylethanol (98(±1)%) with 14.5(±1.5)% ee. [ABSTRACT FROM AUTHOR]

The present study investigated the potential of UASB inoculum, by itself or mixed to nitrogenous residue (fresh bovine manure – FBM) or to adapted microorganisms (bovine rumen – BR), for biomethanation of raw and pretreated sugarcane bagasse (SB) by solid-state anaerobic digestion. The influence of autohydrolysis and organosolv pretreatment conditions on the efficiency of biomethanation process was also evaluated by means of kinetic parameters. Akaike Information Criterion was used to statistically evaluate methane production, and the multi-stage model exhibited the highest fit among the models tested. FBM addition resulted in improvements in the C/N ratio, higher yield (143.3NL CH4 kg VS −1 ) and higher rate constant (3.05NL CH4 kg VS −1 day −1 ) for CH 4 production from raw SB without any lag phase when compared to UASB inoculum itself which exhibited 5.6 days of lag phase. The FBM also led to a better inoculum adaptation to substrates which contained inhibitors such as xylooligomers and lignin fragments, and had lower C5 sugar content. [ABSTRACT FROM AUTHOR]

In the present study, the ozonation of sugarcane bagasse (SB) at different operational conditions (pH, time, liquid-to-solid ratio ( LSR )) was evaluated with the aim of generating a soluble liquid fraction (SLF) suitable for biogas production (CH 4 and H 2 ) via anaerobic digestion and a solid fraction prone to enzymatic hydrolysis and 2G ethanol production. The SLFs obtained were characterized for sugars, total organic carbon (TOC), soluble lignin, furans and other components identified by GC/MS. The results showed that it was possible to solubilize 45.2% of lignin, 48.3% of hemicelluloses and 40.7% of cellulose with the use of ozone (8 mg min −1 ) at pH 11 for 15 min, employing a LSR of 13.3 mL g −1 . The best results of biochemical methane potential (BMP) and biochemical hydrogen potential (BHP) were 2.6 Nm 3 of CH 4 and 0.18 Nm 3 of H 2 per kg of TOC, respectively. An energy balance for the best pretreatment conditions indicates that the combustion of such biogas led to an energy surplus of 0.1 MJ kg −1 SB for methane and to an energy deficit of 0.191 MJ kg −1 SB for hydrogen. Potentially inhibitory compounds for anaerobic digestion such as oxalic acid, butanal, xylitol, furanone, benzaldehyde, d -erythrotetrofuranose, d -erythro-pentofuranose and 2,5-furandione were identified in the hydrolysates, which negatively affected the anaerobic digestion and the energy balance. Nevertheless, the energy generated from the hydrolysates (as biogas) and from the ozonized solid fraction (as 2G ethanol) offsets the ozonation energy input and led to positive energy balance. [ABSTRACT FROM AUTHOR]

This study evaluated the synergistic efficiency of crude enzymatic extracts (CEE) produced by fungal strains Aspergillus fumigatus SCBM6 (AFE) and Aspergillus niger SCBM1 (ANE) in the hydrolysis of alkali pretreated sugarcane bagasse (2% NaOH (w v −1 ), ∼100 °C, 4 h and liquid-to-solid ratio of 25 (v w −1 )). CEEs were produced by solid-state fermentation (SSF) and presented high concentration of β-glucosidase (AFE = 78.4 U g −1 and ANE = 43.02 U g −1 ), β-xylosidase (ANE = 78.0 U g −1 ) and xylanase (AFE = 1774.5 U g −1 and ANE = 3289.6 U g −1 ). A 2 4 full design of experiments was used to optimize the hydrolysis of pretreated bagasse as a function of time, temperature, amount of pretreated bagasse and AFE-to-ANE ratio. After hydrolysis optimization, the maximum concentration of total reducing sugars (TRS) was 21.68 g L −1 . It was also noticed a significant production of xylose (135.59 mg) and arabinose (58.10 mg) per gram of hemicelluloses and a slight production of glucose (20.18 mg) per gram of cellulose. As fungi consortium were excellent producers of hemicellulases, it is suggested that they could be used for pentoses saccharification and production of ethanol via C-5 fermentation, xylitol, biopolymers, among other bioproducts. [ABSTRACT FROM AUTHOR]

Bioethanol production from lignocellulose biomass offers a solution to current environmental challenges caused by fossil fuel energy resources, while satisfying the biorefinery concept. In this study, two-stage fractionation (autohydrolysis (AH) followed by glycerol organosolv delignification (GOD)) of sugarcane bagasse (SCB) was studied as a function of temperature, time, glycerol content and liquid-to-solid ( LSR ) ratio using experimental designs. The effect of three different AH pretreatment severities on delignification extents ( DE ) of the solid fractions were also evaluated. Scanning electron microscopy was used to examine the changes in the surface of SCB pretreated by AH. Energy balances of four fractionation conditions were estimated, and the use of pure and crude glycerol in GOD was evaluated based on DE and lignin contents. A DE of ∼64% was obtained at 210.3 °C, 40 min, LSR of 6.5 (v/w) and 80% (v/v) pure glycerol for GOD of SCB pretreated by AH at 175.8 °C, 49 min and LSR of 5.3 (v/w), which resulted in an energetic profitability ( EP ) of 141.48 MJ/kg SCB . The use of crude glycerol at 80% (v/v) under the same process conditions optimized for pure glycerol also proved to be feasible ( DE of ∼64% and EP of 142.67 MJ/kg SCB ), widening the possibilities for its direct use in GOD of SCB pretreated by AH in a 2G bioethanol integrated plant. [ABSTRACT FROM AUTHOR]

Carbonaceous materials have been extensively studied as highly efficient adsorbents for the removal of dyes from wastewater. However, investigations of thermodynamic aspects of the interactions between these materials and dyes remain scarce. This paper describes the thermodynamics of the interactions between the Ponceau 4R (PR), Congo Red (CR), and Allura Red (AR) dyes and multi-walled carbon nanotubes (MWCNTs). The interactions between the dyes and activated carbon (AC) were also evaluated for comparison. The investigation used a combination of adsorption isotherms and isothermal titration nanocalorimetry (ITC) measurements, and a thermodynamic approach provided full characterization of the adsorption process. For both MWCNT and AC, the amount of adsorbed dye ( Γ D ) increased in the order Γ D (PR) < Γ D (AR) < Γ D (CR), and the adsorption capacity normalized by the adsorbent specific area was up to 5.6 times higher for MWCNT. The maximum amount adsorbed ( Γ D,max ) reached values of up to 2.00 μmol m −2 for CR adsorption on MWCNT. For both adsorbents, the process of dye adsorption was enthalpically driven and entropically unfavorable. All the thermodynamic parameters depended on the surface coverage and the structures of both dye and adsorbent. The adsorption enthalpy change (Δ ads H ) and entropy change (TΔ ads S ref ) values were higher than −137.0 kJ mol −1 and −114.2 kJ mol −1 , respectively. In addition to the structural differences between MWCNT and AC, the ITC data suggested that the adsorption sites are heterogeneous and that the dyes preferentially adsorb on the more hydrophilic sites on the adsorbent surfaces. [ABSTRACT FROM AUTHOR]

Cellulose (Cel) and sugarcane bagasse (SB) were oxidized with an H 3 PO 4 -NaNO 2 mixture to obtain adsorbent materials with high contents of carboxylic groups. The oxidation reactions of Cel and SB were optimized using design of experiments (DOE) and response surface methodology (RSM). The optimized synthesis conditions yielded Cox and SBox with 4.8 mmol/g and 4.5 mmol/g of carboxylic acid groups, respectively. Cox and SBox were characterized by FTIR, TGA, PZC and solid-state 13 C NMR. The adsorption of the model cationic dyes crystal violet (CV) and auramine-O (AO) on Cox and SBox in aqueous solution was investigated as a function of the solution pH, the contact time and the initial dye concentration. The adsorption of CV and AO on Cox was described by the Elovich equation and the pseudo-first-order kinetic model respectively, while the adsorption of CV and AO on SBox was described by the pseudo-second-order kinetic model. Adsorption isotherms were well fitted by the Langmuir and Konda models, with maximum adsorption capacities ( Q max ) of 1117.8 mg/g of CV and 1223.3 mg/g of AO on Cox and 1018.2 mg/g of CV and 682.8 mg/g of AO on SBox. Desorption efficiencies were in the range of 50–52% and re-adsorption capacities varied from 65 to 81%, showing the possibility of reuse of both adsorbent materials. [ABSTRACT FROM AUTHOR]

This study describes the use of succinylated twice-mercerized sugarcane bagasse containing adsorbed Cu 2+ or Ni 2+ ions from spiked aqueous solutions (2MSBA-Cu and 2MSBA-Ni) as heterogeneous catalysts for the catalytic oxidation of n -hexane and n -heptane in gas phase. To the best of our knowledge, this is the first study in which a spent adsorbent material based on lignocellulose biomass is used in the catalytic oxidation of volatile organic compounds. The adsorbent and spent adsorbent materials were characterized by FTIR, TGA and XRD. The amount of Cu 2+ and Ni 2+ adsorbed on 2MSBA was 0.49 and 2.49 mmol g −1 , respectively. The catalysts were active for total oxidation of n -hexane and n -heptane, even at low temperatures. 2MSBA-Cu exhibited higher catalytic activity than 2MSBA-Ni and surprisingly their performances were comparable or superior to those of some catalysts reported in the literature, including noble metal-based catalysts. [ABSTRACT FROM AUTHOR]

In the second part of this series of studies, the competitive adsorption of three binary systems Cu 2+ –Co 2+ , Cu 2+ –Ni 2+ and Co 2+ –Ni 2+ on a carboxylated cellulose derivative (CTA) was evaluated in binary equimolar (1:1) metal–ion aqueous solutions. Bicomponent adsorption studies were developed as a function of contact time and initial metal ion concentration. Bicomponent adsorption kinetic data was modeled by monocomponent kinetic models of pseudo-first- (PFO) and pseudo-second-order (PSO) and a competitive kinetic model of Corsel. Bicomponent adsorption isotherm data was modeled by the ideal adsorbed solution theory (IAST) and real adsorbed solution theory (RAST) models. The monocomponent isotherm models implemented into the IAST were the Langmuir and Sips models, whereas for the RAST model only the Langmuir model was implemented because this model provided the best prediction of the bicomponent isotherm data. The surface of the CTA adsorbent after bicomponent adsorption of metal ions was also examined by SEM-EDX. The effect of one metal ion on the adsorption capacity of another metal ion was discussed in detail with basis on the kinetic and thermodynamics parameters. The selectivity and performance of the CTA adsorbent for the removal of Cu 2+ , Co 2+ and Ni 2+ was also evaluated and discussed. [ABSTRACT FROM AUTHOR]

A new carboxylated cellulose derivative (CTA) was prepared from the esterification of cellulose with 1,2,4-Benzenetricarboxylic anhydride. CTA was characterized by percent weight gain ( pwg ), amount of carboxylic acid groups ( n COOH ), elemental analysis, FTIR, TGA, solid-state 13 C NMR, X-ray diffraction (DRX), specific surface area, pore size distribution, SEM and EDX. The best CTA synthesis condition yielded a pwg and n COOH of 94.5% and 6.81 mmol g −1 , respectively. CTA was used as an adsorbent material to remove Co 2+ , Cu 2+ and Ni 2+ from monocomponent spiked aqueous solution. Adsorption studies were developed as a function of the solution pH, contact time and initial adsorbate concentration. Langmuir model better fitted the experimental adsorption data and the maximum adsorption capacities estimated by this model were 0.749, 1.487 and 1.001 mmol g −1 for Co 2+ , Cu 2+ and Ni 2+ , respectively. The adsorption mechanism was investigated by using isothermal titration calorimetry. The values of Δ ads H ° were in the range from 5.36 to 8.09 kJ mol −1 , suggesting that the mechanism controlling the phenomenon is physisorption. Desorption and re-adsorption studies were also performed. Desorption and re-adsorption efficiencies were closer to 100%, allowing the recovery of both metal ions and CTA adsorbent. [ABSTRACT FROM AUTHOR]

This study aimed at optimizing the net energy recovery from hydrogen and methane production through anaerobic digestion of the hemicellulose hydrolysate (HH) obtained by desirable conditions (DC) of autohydrolysis pretreatment (AH) of sugarcane bagasse (SB). Anaerobic digestion was carried out in a two-stage (acidogenic-methanogenic) batch system where the acidogenic phase worked as a hydrolysis and biodetoxification step. This allowed the utilization of more severe AH pretreatment conditions, i.e. T = 178.6 °C and t = 55 min (DC3) and T = 182.9 °C and t = 40.71 min (DC4). Such severe conditions resulted in higher extraction of hemicelluloses from SB (DC1 = 68.07%, DC2 = 48.99%, DC3 = 77.40% and DC4 = 73.90%), which consequently improved the net energy balance of the proposed process. The estimated energy from the combustion of both biogases (H 2 and CH 4 ) accumulated during the two-stage anaerobic digestion of HH generated by DC4 condition was capable of producing a net energy of 3.15 MJ·kg SB −1 dry weight . [ABSTRACT FROM AUTHOR]

This study describes the synthesis of a new chitosan derivative (C2) with zwitterionic characteristics and its use for the removal of cationic species Cu 2+ , Co 2+ , and Ni 2+ and anionic species of Cr 6+ in a single aqueous solution. The new adsorbent was synthesized by quaternization of the amine group of chitosan and esterification of hydroxyl groups with EDTA dianhydride. These combined reactions gave both cationic and anionic characteristics to C2 with the release of quaternary ammonium groups and carboxylic groups. The capacity of C2 to adsorb Cu 2+ , Co 2+ , Ni 2+ , and oxyanions of Cr 6+ was evaluated in a batch process with different contact times, pH values, and initial concentrations. Adsorption isotherms were best fitted to the Langmuir and Sips models. The maximum adsorption capacities ( Q max ) of C2 for adsorption of Cu 2+ , Co 2+ , Ni 2+ , and Cr 6+ were 0.698, 1.125, 0.725, and 1.910 mmol/g, respectively. The Δ ads G ° values were in the range from −20 to −28 kJ/mol. These values suggest a mixed mechanism controlling adsorption. Desorption studies using an aqueous solution consisting of 0.1 mol/L HNO 3 were carried out. The reusability of the recovered C2 adsorbent after desorption was also evaluated. [ABSTRACT FROM AUTHOR]