Removal of copper (II) from aqueous solution by adsorption onto low-cost adsorbents

The use of low-cost adsorbents was investigated as a replacement for current costly methods of removing metals from aqueous solution. Removal of copper (II) from aqueous solution by different adsorbents such as shells of lentil (LS), wheat (WS), and rice (RS) was investigated. The equilibrium adsorption level was determined as a function of the solution pH, temperature, contact time, initial adsorbate concentration and adsorbent doses. Adsorption isotherms of Cu (II) on adsorbents were determined and correlated with common isotherm equations such as Langmuir and Freundlich models. The maximum adsorption capacities for Cu (II) on LS, WS and RS adsorbents at 293, 313 and 333 K temperature were found to be 8.977, 9.510, and 9.588; 7.391, 16.077, and 17.422; 1.854, 2.314, and 2.954 mg g(-1), respectively. The thermodynamic parameters such as free energy (delta G0), enthalpy (delta H0) and entropy changes (delta S0) for the adsorption of Cu (II) were computed to predict the nature of adsorption process. The kinetics and the factors controlling the adsorption process were also studied. Locally available adsorbents were found to be low-cost and promising for the removal of Cu (II) from aqueous solution.     

Exploring chemical analysis of vermicompost of various oil palm fibre wastes

The aim of this work was to study the physical and chemical properties of different oil palm wastes, viz. empty fruit bunch (EFB), oil palm frond (OPF) and oil palm trunk (OPT). A study (84 days duration) was conducted to evaluate the efficiency of an exotic earthworm species (epigeic-African Nightcrawler (Eudrilus euginae)) for the decomposition of different types of oil palm wastes (EFB, OPT and OPF) into valuable vermicompost. The decrease in earthworm’s biomass gain for EFB, OPT and OPF may be due to exhaustion of worm feed in vermicomposters. The percentage of nitrogen, phosphorous and potassium in vermicompost was found to increase while pH and total organic carbon declined as a function of the vermicomposting period. The vermicompost obtained showed an increase in heavy metal content for all the reactors, but levels were still in the range of nutrient in the vermicompost. The data reveal that vermicomposting (using African Nightcrawler) is a suitable technology for the decomposition of oil palm wastes, especially EFB into value-added material.     

Performance of oil palm kernel shell gasification using a medium-scale downdraft gasifier

This article focused on the performance of oil palm kernel shell (PKS) gasification using a medium-scale downdraft gasifier with a feedstock capacity of 500 kg at a temperature range of 399–700°C and at a feed rate of 177 kg/h. This article is important for evaluating the reliability of PKS gasification for commercial power generation activities from biomass. The process performance was evaluated based on the syngas calorific value (CV), syngas flow rate, and its cold gas efficiency (CGE). The syngas flow rates and CVs were measured using a gas flow meter and a gas analyzer in real time. The data obtained were then analyzed to evaluate the performance of the process. The results showed that the CGE of the process was moderately high (51%) at 681°C, with a high syngas CV (4.45–4.89 MJ/Nm³) which was ideal for gas engine applications. The PKS gasification performance increased when the reactor temperature increased. Projections were made for the CGE and the syngas CV for the PKS gasification with increased reactor temperatures and it was found that these values could be increased up to 80% and 5.2 MJ/Nm^3, respectively at a reactor temperature of 900°C. In addition, the estimated power that could be generated was about 600 kW_e at a maximum operation of 500 kg/h of feed rate. Based on the analysis, a medium-scale PKS gasification is observed to be a promising process for power generation from biomass due to the favorable performance of the process.     

Molecular docking analysis on antifungal properties of acid condensate produced from palm kernel shell

The rise in the number of fungi that resisted antifungal action is of serious concern nowadays. In this study, the potential of acid condensate (AC) produced from microwave-assisted pyrolysis of palm kernel shell (PKS) was investigated for its antifungal properties through molecular docking evaluation. The phenolic-rich AC was determined for its chemical compositions using the GC–MS analysis where compounds with the highest phenolics content were further evaluated (using the Autodock Tools 1.5.7) for its potential enzymes/protein binding properties. From the GC–MS analysis, catechol, guaiacol and syringol were present at highest percentages. This directly correlates with results obtained from the molecular docking works where all these ligands managed to bind (indicated by H-bond, π-stacking, hydrophobic interaction) with some of the amino acid at the active sites which indicate its potential to inhibit substrate binding of this enzyme. As a conclusion, this study demonstrated the potential use of AC from agricultural biomass such as PKS as a natural-based antifungal agent that can reduce environmental and health impacts.     

Removal of phenol from aqueous solution by adsorption onto OTMAC-modified attapulgite

The potential of octodecyl trimethyl ammonium chloride (OTMAC)-modified attapulgite (AT) for phenol adsorption from aqueous solutions was studied. The comparison of natural AT and modified AT showed that it is possible to utilize the sonication-modified OTMAC-AT in the treatment of phenol-contaminated wastewaters. Batch sorption studies were carried out to evaluate the effect of contact time, shaking frequency, temperature and the amount of AT. The results showed that in a lab-scale reactor, at room temperature, with an amount of the modified AT added (2.5 g), and a shaking frequency of 140 rev/min, the adsorption rate of phenol could be 60.4% for a duration of 60 min. The sorption kinetics were described by a pseudo-second-order model, and the values of k and q(e) were 1.367 mg/ig min and 0.7901 ig/mg, respectively. The analysis of equilibrium data showed that the Freundlich isotherms were found to be applicable for the adsorption equilibrium data. K and 1/n were estimated to be 14.53 and 0.8438, respectively.     

Upgrading of bio-oil from palm kernel shell by catalytic cracking in the presence of HZSM-5

Upgrading of bio-oil extracted from palm kernel shell (PKS) was performed using a lab-scale fixed-bed reactor with HZSM-5 as a catalyst. The catalytic cracking was carried out at optimized conditions: 0.3-MPa pressure, temperature of 500°C, and oil to catalyst ratio of 1:5. One of the challenges in upgrading bio-oil by catalytic cracking is deactivation of catalyst due to coke formation on catalyst surface. To overcome coke deposition, the upgrading process was carried out at 0.3-MPa pressure. Characterization of raw and upgraded bio-oil obtained through catalytic cracking was discussed in detail, indicating improvement in its physical properties. The distribution of products after cracking of bio-oil includes 58.89 wt% of organic liquid product, 15.63 wt% of aqueous fraction, 7.84 wt% of coke, and 17.64 wt% of gases. The degree of deoxygenation and calorific value of organic liquid product is 43.74% and 31.65 MJ/kg respectively. Organic liquid product obtained comprises 17.55% of hydrocarbons within the gasoline range. Hence, HZSM-5 proved its effectiveness for upgrading the bio-oil in a continuous mode.     

Equilibrium and kinetic studies on biosorption of Hg(II), Cd(II) and Pb(II) ions onto microalgae Chlamydomonas reinhardtii

The microalgae Chlamydomonas reinhardtii was used for the biosorption of Hg(II), Cd(II) and Pb(II) ions. The maximum adsorption of Hg(II) and Cd(II) ions on Chlamydomonas reinhardtii biomass was observed at pH 6.0 and the corresponding value for Pb(II) ions was 5.0. The biosorption of Hg(II), Cd(II) and Pb(II) ions by microalgae biomass increased as the initial concentration of Hg(II), Cd(II) and Pb(II) ions increased in the biosorption medium. The maximum biosorption capacities of microalgae for Hg(II), Cd(II) and Pb(II) ions were 72.2+/-0.67, 42.6+/-0.54 and 96.3+/-0.86 mg/g dry biomass, respectively. The affinity order for algal biomass was Pb(II)>Hg(II)>Cd(II). FT-IR analysis of algal biomass revealed the presence of amino, carboxyl, hydroxyl and carbonyl groups, which were responsible for biosorption of metal ions. Biosorption equilibrium was established in about 60 min and the equilibrium was well described by the Freundlich biosorption isotherms. Temperature change in the range of 5-35 degrees C did not affect the biosorption capacity. The microalgae could be regenerated using 0.1 M HCl, with up to 98% recovery, which allowed the reuse of the biomass in six biosorption-desorption cycles without any considerable loss of biosorption capacity.     

Adsorption studies of hazardous malachite green onto treated ginger waste

Adsorption of malachite green (MG) from aqueous solution onto treated ginger waste (TGW) was investigated by batch and column methods. The effect of various factors such as initial dye concentration, contact time, pH and temperature were studied. The maximum adsorption of MG was observed at pH 9. Langmuir and Freundlich isotherms were employed to describe the MG adsorption equilibrium. The monolayer adsorption capacities were found to be 84.03, 163.9 and 188.6 mg/g at 30, 40 and 50 °C, respectively. The values of thermodynamic parameters like ΔG°, ΔH° and ΔS° indicated that adsorption was spontaneous and endothermic in nature. The pseudo second order kinetic model fitted well in correlation to the experimental results. Rechienberg's equation was employed to determine the mechanism of adsorption. The results indicated that film diffusion was a major mode of adsorption. The breakthrough capacities were also investigated.     

Kinetic and equilibrium characterization of uranium(VI) adsorption onto carboxylate-functionalized poly(hydroxyethylmethacrylate)-grafted lignocellulosics

This study investigated the feasibility of using a new adsorbent prepared from coconut coir pith, CP (a coir industry-based lignocellulosic residue), for the removal of uranium [U(VI)] from aqueous solutions. The adsorbent (PGCP-COOH) having a carboxylate functional group at the chain end was synthesized by grafting poly(hydroxyethylmethacrylate) onto CP using potassium peroxydisulphate-sodium thiosulphite as a redox initiator and in the presence of N,N'-methylenebisacrylamide as a crosslinking agent. IR spectroscopy results confirm the graft copolymer formation and carboxylate functionalization. XRD studies confirm the decrease of crystallinity in PGCP-COOH compared to CP, and it favors the protrusion of the functional group into the aqueous medium. The thermal stability of the samples was studied using thermogravimetry (TG). Surface charge density of the samples as a function of pH was determined using potentiometric titration. The ability of PGCP-COOH to remove U(VI) from aqueous solutions was assessed using a batch adsorption technique. The maximum adsorption capacity was observed at the pH range 4.0-6.0. Maximum removal of 99.2% was observed for an initial concentration of 25mg/L at pH 6.0 and an adsorbent dose of 2g/L. Equilibrium was achieved in approximately 3h. The experimental kinetic data were analyzed using a first-order kinetic model. The temperature dependence indicates an endothermic process. U(VI) adsorption was found to decrease with an increase in ionic strength due to the formation of outer-sphere surface complexes on PGCP-COOH. Equilibrium data were best modeled by the Langmuir isotherm. The thermodynamic parameters such as DeltaG(0), DeltaH(0) and DeltaS(0) were derived to predict the nature of adsorption. Adsorption experiments were also conducted using a commercial cation exchanger, Ceralite IRC-50, with carboxylate functionality for comparison. Utility of the adsorbent was tested by removing U(VI) from simulated nuclear industry wastewater. Adsorbed U(VI) ions were desorbed effectively (about 96.2+/-3.3%) by 0.1M HCl. The adsorbent was suitable for repeated use (more than four cycles) without any noticeable loss of capacity.     

Biosorption of copper(II) and lead(II) onto potassium hydroxide treated pine cone powder

Pine cone powder surface was treated with potassium hydroxide and applied for copper(II) and lead(II) removal from solution. Isotherm experiments and desorption tests were conducted and kinetic analysis was performed with increasing temperatures.As solution pH increased, the biosorption capacity and the change in hydrogen ion concentration in solution increased. The change in hydrogen ion concentration for lead(II) biosorption was slightly higher than for copper(II) biosorption. The results revealed that ion-exchange is the main mechanism for biosorption for both metal ions. The pseudo-first order kinetic model was unable to describe the biosorption process throughout the effective biosorption period while the modified pseudo-first order kinetics gave a better fit but could not predict the experimentally observed equilibrium capacities. The pseudo-second order kinetics gave a better fit to the experimental data over the temperature range from 291 to 347 K and the equilibrium capacity increased from 15.73 to 19.22 mg g^?1 for copper(II) and from 23.74 to 26.27 for lead(II).Activation energy was higher for lead(II) (22.40 kJ mol^?1) than for copper(II) (20.36 kJ mol^?1). The free energy of activation was higher for lead(II) than for copper(II) and the values of ΔH* and ΔS* indicate that the contribution of reorientation to the activation stage is higher for lead(II) than copper(II). This implies that lead(II) biosorption is more spontaneous than copper(II) biosorption.Equilibrium studies showed that the Langmuir isotherm gave a better fit for the equilibrium data indicating monolayer coverage of the biosorbent surface. There was only a small interaction between metal ions when simultaneously biosorbed and cation competition was higher for the Cu-Pb system than for the Pb-Cu system. Desorption studies and the Dubinin–Radushkevich isotherm and energy parameter, E, also support the ion-exchange mechanism.     

Removal of Fe(II) from the wastewater of a galvanized pipe manufacturing industry by adsorption onto bentonite clay

Bentonite clay has been used for the adsorption of Fe(II) from aqueous solutions over a concentration range of 80-200 mg/l, shaking time of 1-60 min, adsorbent dosage from 0.02 to 2 g and pH of 3. The process of uptake follows both the Langmuir and Freundlich isotherm models and also the first-order kinetics. The maximum removal (>98%) was observed at pH of 3 with initial concentration of 100 mg/l and 0.5 g of bentonite. The efficiency of Fe(II) removal was also tested using wastewater from a galvanized pipe manufacturing industry. More than 90% of Fe(II) can be effectively removed from the wastewater by using 2.0 g of the bentonite. The effect of cations (i.e. zinc, manganese, lead, cadmium, nickel, cobalt, chromium and copper) on the removal of Fe(II) was studied in the concentration range of 10-500 mg/l. All the added cations reduced the adsorption of Fe(II) at high concentrations except Zn. Column studies have also been carried out using a certain concentration of wastewater. More than 99% recovery has been achieved by using 5 g of the bentonite with 3M nitric acid solution.     

不同交联度PP-g-4VP离子交换纤维的制备及对水溶液中铬离子吸附的研究

通过控制交联剂(DVB)及单体(4-VP)浓度等工艺,研制了不同交联度的聚丙烯接枝4乙烯基吡啶离子交换纤维(PP-g-4VP),旨在改善纤维的结构及其再生吸附和重复使用性能。实验结果表明,随着DVB含量增大,纤维的接枝率下降,交联度增加,而吸水率下降。所制的PP-g-4VP和PP-g-4VP-季铵盐纤维对Cr~(6+)静态吸附量大,分别达约6.5mmol/g和4mmol/g。交联度低时,纤维对Cr~(6+)吸附速度越快,穿透点前流出液浓度较低。纤维吸附Cr~(6+)后用1N NH_3·H_2O能完全洗脱,再生吸附性能良好。     

A comparative study on the properties,mechanisms and process designs for the adsorption of non-ionic or anionic dyes onto cationic-polymer/bentonite

The adsorption properties and mechanisms of a cationic-polymer/bentonite complex (EPI-DMA/bentonite), prepared from polyepicholorohydrin-dimethylamine and bentonite, for non-ionic dyes (Disperse Blue SBL and Vat Scarlet R) and anionic dyes (Reactive Violet K-3R and Acid Dark Blue 2G) were investigated in this study. The solution pH, presence of salt and surfactant can significantly affect the dye removal efficiency. The equilibrium data were analyzed using the Langmuir and Freundlich models. The Langmuir model is the most suitable to describe non-ionic dye adsorption, but for anionic dyes the Freundlich model is best. The kinetic data for the adsorption of different dyes were analyzed using pseudo first- and second-order equations, and the experimental data conformed to the pseudo second-order kinetic model better. The possibility of intraparticle diffusion was also examined by using the intraparticle diffusion equation. The single-stage batch adsorber design for the adsorption of both types of dyes onto EPI-DMA/bentonite was studied based on the Langmuir isotherm model for non-ionic dyes and the Freundlich isotherm model for anionic dyes. The results showed that the required amount of EPI-DMA/bentonite for 95% dye removal in 5 L dye solution with a concentration of 50 mg/L is 378.0 g for DB SBL, 126.5 g for VS R, 9.7 g for RV K-3R and 15.5 g for ADB 2G.     

Determination of model parameters for zinc (II) ion biosorption onto powdered waste sludge (PWS) in a fed-batch system

Biosorption of zinc (II) ions onto pre-treated powdered waste sludge (PWS) was investigated using a completely mixed tank operating in fed-batch mode instead of an adsorption column. Experiments with variable feed flow rate (0.05-0.5 L h(-1)), feed Zn(II) ion concentrations (37.5-275 mg L(-1)) and amount of adsorbent (1-6 g PWS) were performed using fed-batch operation at pH 5 and room temperature (20-25 degrees C). Break-through curves describing variations of aqueous (effluent) zinc ion concentrations with time were determined for different operating conditions. Percent zinc removal from the aqueous phase decreased, but the biosorbed (solid phase) zinc ion concentration increased with increasing feed flow rate and zinc concentration. A modified Bohart-Adams equation was used to determine the biosorption capacity of PWS (q'(s)) and the rate constant (K) for zinc ion biosorption. Biosorption capacity (q'(s)=57.7 g Zn kg(-1) PWS) of PWS in fed-batch operation was found to be comparable with powdered activated carbon (PAC) in column operations. However, the adsorption rate constant (K=9.17 m(3) kg(-1) h(-1)) in fed-batch operation was an order of magnitude larger than those obtained in adsorption columns because of elimination of mass transfer limitations encountered in the column operations. Therefore, a completely mixed tank operated in fed-batch mode was proven to be more advantageous as compared to adsorption columns due to better contact between the phases yielding faster adsorption rates.     

Kinetic studies on the adsorption of phenol, 4-chlorophenol,and 2,4-dichlorophenol from water using activated carbons

This study uses rate parameters in pseudo-first-order (PFO) and pseudo-second-order (PSO) equations (k₁ and k₂q_e, respectively) to judge the extent for approaching equilibrium in an adsorption process. Out of fifty-six systems collected from the literature, the adsorption processes with a k₂q_e value between 0.1 and 0.8 min^?1 account for as much as 70% of the total. These are classified as fast processes. This work compares the validity of PFO and PSO equations for the adsorption of phenol, 4-chlorophenol (4-CP), and 2,4-dichlorophenol (2,4-DCP) on activated carbons prepared from pistachio shells at different NaOH/char ratios. The activated carbons, recognized as microporous materials, had a surface area ranging from 939 to 1936 m²/g. Findings show that the adsorption of phenol, 4-CP, and 2,4-DCP on activated carbons had a k₂q_e value of 0.15–0.58 min^?1, reflecting the fast process. Evaluating the operating time by rate parameters revealed that k₂q_e was 1.6–1.8 times larger than k₁. These findings demonstrate the significance of using an appropriate kinetic equation for adsorption process design.     

Removal of direct red 12B and methylene blue from water by adsorption onto Fe (III)/Cr (III) hydroxide, an industrial solid waste

Removal of direct red 12B and methylene blue by adsorption onto Fe (III)/Cr (III) hydroxide was studied using various parameters such as agitation time, dye concentration, adsorbent dose and pH. Equilibrium adsorption data followed both Langmuir and Freundlich isotherms. Adsorption followed second-order rate kinetics. The Langmuir adsorption capacity (Qo) was found to be 5.0 and 22.8 mg dye per g of the adsorbent for direct red 12B and methylene blue, respectively. Acidic pH was favorable for the adsorption of direct red 12B and basic pH for methylene blue. Desorption studies showed that chemisorption seems to be the major mode of adsorption.     

Adsorption characterization of Pb(II) and Cu(II) ions onto chitosan-tripolyphosphate beads: Kinetic,equilibrium and thermodynamic studies

Chitosan-tripolyphosphate (CTPP) beads were synthesized, characterized and were used for the adsorption of Pb(II) and Cu(II) ions from aqueous solution. The effects of initial pH, agitation period, adsorbent dosage, different initial concentrations of heavy metal ions and temperature were studied. The experimental data were correlated with the Langmuir, Freundlich and Dubinin-Radushkevich isotherm models. The maximum adsorption capacities of Pb(II) and Cu(II) ions in a single metal system based on the Langmuir isotherm model were 57.33 and 26.06 mg/g, respectively. However, the beads showed higher selectivity towards Cu(II) over Pb(II) ions in the binary metal system. Various thermodynamic parameters such as enthalpy (ΔH°), Gibbs free energy (ΔG°) and entropy (ΔS°) changes were computed and the results showed that the adsorption of both heavy metal ions onto CTPP beads was spontaneous and endothermic in nature. The kinetic data were evaluated based on the pseudo-first and -second order kinetic and intraparticle diffusion models. Infrared spectra were used to elucidate the mechanism of Pb(II) and Cu(II) ions adsorption onto CTPP beads.     

Utilization of waste product (tamarind seeds) for the removal of Cr(VI) from aqueous solutions: Equilibrium, kinetics, and regeneration studies

In the present study, an adsorbent was prepared from tamarind seeds and used after activation for the removal of Cr(VI) from aqueous solutions. The tamarind seeds were activated by treating them with concentrated sulfuric acid (98% w/w) at a temperature of 150 °C. The adsorption of Cr(VI) was found to be maximum at low values of initial pH in the range of 1–3. The adsorption process of Cr(VI) was tested with Langmuir, Freundlich, Redlich–Peterson, Koble–Corrigan, Tempkin, Dubinin–Radushkevich and Generalized isotherm models. Application of the Langmuir isotherm to the system yielded a maximum adsorption capacity of 29.7 mg/g at an equilibrium pH value ranging from 1.12 to 1.46. The adsorption process followed second-order kinetics and the corresponding rate constants obtained were 2.605 × 10⁻³, 0.818 × 10⁻³, 0.557 × 10⁻³ and 0.811 × 10⁻³ g/mg min⁻¹ for 50, 200, 300 and 400 mg/L of initial Cr(VI) concentration, respectively. The regenerated activated tamarind seeds showed more than 95% Cr(VI) removal of that obtained using the fresh activated tamarind seeds. A feasible solution is proposed for the disposal of the contaminants (acid and base solutions) containing high concentrations of Cr(VI) obtained during the regeneration (desorption) process.