Aerobic post-treatment of effluent from anaerobic reactors fed with residues from 1G and 2G sugarcane biorefineries.

This study aimed to evaluate an activated sludge system as a post-treatment step of anaerobic effluents from the co-digestion of sugarcane vinasse and hemicelluloses hydrolysate. The system consisted, initially, of a two-stage anaerobic system followed by a continuously fed activated sludge, all in bench scale. After adaptation of aerobic microorganisms to effluent conditions, the anaerobic digestion was conducted in a single-stage anaerobic reactor, increasing the influent organic loading rate (OLR) of activated sludge from 0.73 to an average of 2.36 gCOD/L·day. Under optimal conditions (12-h hydraulic retention time [HRT]), a 62 ± 9% efficiency was observed on the aerobic post-treatment, resulting in effluent chemical oxygen demand (COD) of 414.3 ± 95 mg/L. Overall efficiency of the combined system (anaerobic + aerobic) averaged 88 ± 3%. Influent and effluent characteristics were then analyzed by Folin-Ciocalteau method, UV-Vis spectrophotometry, and gas chromatography-mass spectrometry (GC-MS) for identification of potentially toxic and recalcitrant compounds. Compounds that absorb light within the visible spectra were well removed by the combined treatment system. Most compounds identified by GC-MS in the influent were completely removed by aerobic microorganisms. Saturated fatty acids such as adipic acid, hexadecanoic acid, and octadecanoic acid were observed in the final effluent, as well as other potentially toxic compounds such as stigmasterol, di-isobutyl phthalate, and benzene. Activated sludge proved to be an efficient post-treatment for anaerobic co-digestion, able to cope with changes of anaerobic effluent quality and providing a final effluent of stable organic load. However, phenol removal was not efficient and further studies could be performed to optimize its degradation. PRACTITIONER POINTS: Conventional activated sludge with a 12-h HRT was capable of handling significant OLR variation, providing a final effluent with lower and stable COD concentration. Glucose addition for carbon supplementation was necessary during the start-up of activated sludge. Compounds that absorb light within the visible spectra were mostly removed by the combined (anaerobic-aerobic) treatment system. Most potentially toxic compounds were well removed in the post-treatment system. Saturated fatty acids, VFA, phenols, and low molecular weight aromatic compounds remained in the final effluent.

Batch and continuous adsorption of Cu(II) and Zn(II) ions from aqueous solution on bi-functionalized sugarcane-based biosorbent.

A new one-pot synthesis method optimized by a 23 experimental design was developed to prepare a biosorbent, sugarcane bagasse cellulose succinate pyromellitate (SBSPy), for the removal of Cu(II) and Zn(II) from single-component aqueous solutions, in batch and continuous modes. The bi-functionalization of the biosorbent with ligands of different chemical structures increased its selectivity, improving its performance for removing pollutants from contaminated water. The succinate moiety favored Cu(II) adsorption, while the pyromellitate moiety favored Zn(II) adsorption. Sugarcane bagasse (SB) and SBSPy were characterized using several techniques. Analysis by 13C Multi-CP SS NMR and FTIR revealed the best order of addition of each anhydride that maximized the chemical modification of SB. The maximum adsorption capacities of SBSPy for Cu(II) and Zn(II), in batch mode, were 1.19 and 0.95 mmol g-1, respectively. Homogeneous surface diffusion, intraparticle diffusion, and Boyd models were used to determine the steps involved in the adsorption process. Isothermal titration calorimetry was used to assess changes in enthalpy of adsorption as a function of SBSPy surface coverage. Fixed-bed column adsorption of Cu(II) and Zn(II) was performed in three cycles, showing that SBSPy has potential to be used in water treatment. Breakthrough curves were well fitted by the Thomas and Bohart-Adams models.

Methane production by co-digestion of poultry manure and lignocellulosic biomass: Kinetic and energy assessment.

Six typical Brazilian lignocellulosic biomasses (rice straw, corn cob, peanut shell, sawdust, coffee husk and sugarcane bagasse) were evaluated for methane production by solid-state anaerobic co-digestion with poultry manure. The results showed the highest methane production was obtained with corn cob and poultry manure (126.02 Nm3 CH4. ton residue-1) using a food to inoculum ratio of 0.5, which lowered volatile fatty acids accumulation. In this condition, the thermal energy production (1.73 MJ.kg live chicken-1) would be able to replace 53.2% of the energy with firewood in poultry farming. The high hemicellulose and low lignin content in corn cob seem to explain the biomethanation of such biomass, and this agrees with the microbial analysis which revealed the predominance of bacteria related to plant polysaccharides hydrolysis and carbohydrate conversion in the inoculum. The methane production was best modelled by Groot's multi-stage model, and the microbial adaptation to lignin might explain this.

Use of anaerobic co-digestion as an alternative to add value to sugarcane biorefinery wastes.

In this study the anaerobic co-digestion (AcD) of sugarcane biorefinery by-products, i.e. hemicelluloses hydrolysate (HH) (obtained by hydrothermal pretreatment of sugarcane bagasse), vinasse, yeast extract (YE) and sugarcane bagasse fly ashes (SBFA), was optimized by means of biochemical methane potential experiments. The best experimental conditions of AcD (25-75% HH-to-vinasse mixture ratio; 1.0 g L-1 YE; 15 g L-1 SBFA and 100-0% HH-to-Vinasse; 1.5 g L-1 YE; 45 g L-1 SBFA) led to the production of 0.279 and 0.267 Nm3 of CH4 per kg of chemical oxygen demand (COD) with an energy surplus of 0.43 and 0.34 MJ kg SB-1, respectively. Adsorption experiments using SBFA were carried out and showed this residue could adsorb up to 61.71 and 17.32 mg g-1 of 5-hydroxymethyl-2-furfuraldehyde and 2-furfuraldehyde, thereby reducing toxicity and improving biogas production.

Trimellitated sugarcane bagasse: A versatile adsorbent for removal of cationic dyes from aqueous solution. Part II: Batch and continuous adsorption in a bicomponent system.

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- (Qmax,mono) and bicomponent (Qmax,multi) lower than unity (Qmax,multi/Qmax,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.

Trimellitated sugarcane bagasse: A versatile adsorbent for removal of cationic dyes from aqueous solution. Part I: Batch adsorption in a monocomponent system.

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 ±â€¯0.25 to -7.19 ±â€¯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.

Production of biogas (methane and hydrogen) from anaerobic digestion of hemicellulosic hydrolysate generated in the oxidative pretreatment of coffee husks.

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 CH4/g CH) was achieved with the hydrolysate generated in the experiment using LSR 10 mL/g, pH 11 and SAOL 18.5 mg O3/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 CH4/g CH yield and 0.58 kJ/g CH energy recovery. When two-stage AD was applied, methane production resulted in 49 NmL CH4/g CH, with additional 19 NmL H2/g CH production, resulting in a net 0.26 kJ/g CH energy recovery.

Modeling adsorption of copper(II), cobalt(II) and nickel(II) metal ions from aqueous solution onto a new carboxylated sugarcane bagasse. Part II: Optimization of monocomponent fixed-bed column adsorption.

In the second part of this series of studies, the monocomponent adsorption of Cu2+, Co2+ and Ni2+ onto STA adsorbent in a fixed-bed column was investigated and optimized using a 22 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 (Qmax), efficiency of the adsorption process (EAP), and effective use of the bed (H). The higher Qmax for Cu2+, Co2+ and Ni2+ 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 (ΔadsH°) of adsorption of the metal ions onto STA were determined by isothermal titration calorimetry (ITC). The values of ΔadsH° were in the range of 3.0-6.8 kJ/mol, suggesting that the adsorption process involved physisorption. Desorption (Edes) and re-adsorption (Ere-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 Edes and Ere-ads were 95 and 92.3%, respectively, showing that STA is a promising candidate for real applications on a large scale.

Synthesis and application of a new carboxylated cellulose derivative. Part III: Removal of auramine-O and safranin-T from mono- and bi-component spiked aqueous solutions.

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 (ΔadsH) were obtained using isothermal titration calorimetry. The values of ΔadsH 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.

Synthesis and application of a new carboxylated cellulose derivative. Part II: Removal of Co2+, Cu2+ and Ni2+ from bicomponent spiked aqueous solution.

In the second part of this series of studies, the competitive adsorption of three binary systems Cu2+-Co2+, Cu2+-Ni2+ and Co2+-Ni2+ 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 Cu2+, Co2+ and Ni2+ was also evaluated and discussed.

Optimization of cellulose and sugarcane bagasse oxidation: Application for adsorptive removal of crystal violet and auramine-O from aqueous solution.

Cellulose (Cel) and sugarcane bagasse (SB) were oxidized with an H3PO4-NaNO2 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 4.8mmol/g and 4.5mmol/g of carboxylic acid groups, respectively. Cox and SBox were characterized by FTIR, TGA, PZC and solid-state 13C 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 (Qmax) of 1117.8mg/g of CV and 1223.3mg/g of AO on Cox and 1018.2mg/g of CV and 682.8mg/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.

Optimization of sugarcane bagasse autohydrolysis for methane production from hemicellulose hydrolyzates in a biorefinery concept.

This study aimed to optimize through design of experiments, the process variables (temperature - T, time - t and solid-to-liquid ratio - SLR) for sugarcane bagasse (SB) autohydrolysis (AH) to obtain hemicellulose hydrolyzates (HH) prone to anaerobic digestion (AD) and biochemical methane production (BMP). The results indicated that severe AH conditions, which lead to maximum hemicelluloses dissolution and sugar content in the HH, were not the best for BMP, probably due to the accumulation of toxic/recalcitrant compounds (furans and lignin). Mild AH conditions (170°C, 35min and SLR=0.33) led to the highest BMP (0.79Nm(3)kg TOC(-1)), which was confirmed by the desirability tool. HH produced by AH carried out at the desired condition DC2 (178.6°C, 43.6min and SLR=0.24) showed the lowest accumulation of inhibitory compounds and volatile fatty acids (VFA) and highest BMP (1.56Nm(3)kg TOC(-1)). The modified Gompertz model best fit the experimental data and led to a maximum methane production rate (R) of 2.6mmol CH4d(-1) in the best condition.

Evaluation of hydrogen and methane production from sugarcane bagasse hemicellulose hydrolysates by two-stage anaerobic digestion process.

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=55min (DC3) and T=182.9°C and t=40.71min (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 (H2 and CH4) accumulated during the two-stage anaerobic digestion of HH generated by DC4 condition was capable of producing a net energy of 3.15MJ·kgSB(-1)dry weight.