Oscar Fernando Herrera Adarme

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.

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.

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

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 (nCOOH), 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 nCOOH of 94.5% and 6.81mmolg(-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 1.001mmolg(-1) for Co(2+), Cu(2+) and Ni(2+), respectively. The adsorption mechanism was investigated by using isothermal titration calorimetry. The values of ΔadsH° were in the range from 5.36 to 8.09kJmol(-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.

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.

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 ± 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.

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.

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.