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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]

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]

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]

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]

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]

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 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]