Batch sorption dynamics and equilibrium for the removal of lead ions from aqueous phase using activated carbon developed from coffee residue activated with zinc chloride

Lignocellulosic materials are good precursors for the production of activated carbon. In this work, coffee residue has been used as raw material in the preparation of powder activated carbon by the method of chemical activation with zinc chloride for the sorption of Pb(II) from dilute aqueous solutions.The influence of impregnation ratio (ZnCl₂/coffee residue) on the physical and chemical properties of the prepared carbons was studied in order to optimize this parameter. The optimum experimental condition for preparing predominantly microporous activated carbons with high pore surface area (890 m²/g) and micropore volume (0.772 cm³/g) is an impregnation ratio of 100%. The developed activated carbon shows substantial capability to sorb lead(II) ions from aqueous solutions and for relative impregnation ratios of 75 and 100%, the maximum uptake is practically the same. Thus, 75% represents the optimal impregnation ratio.Batch experiments were conducted to study the effects of the main parameters such as contact time, initial concentration of Pb(II), solution pH, ionic strength and temperature. The maximum uptake of lead(II) at 25 °C was about 63 mg/g of adsorbent at pH 5.8, initial Pb(II) concentration of 10 mg/L, agitation speed of 200 rpm and ionic strength of 0.005 M. The kinetic data were fitted to the models of pseudo-first order and pseudo-second order, and follow closely the pseudo-second order model. Equilibrium sorption isotherms of Pb(II) were analyzed by the Langmuir, Freundlich and Temkin isotherm models. The Freundlich model gives a better fit than the others.Results from this study suggest that activated carbon produced from coffee residue is an effective adsorbent for the removal of lead from aqueous solutions and that ZnCl₂ is a suitable activating agent for the preparation of high-porosity carbons.     

Loofa egyptiaca as a novel adsorbent for removal of direct blue dye from aqueous solution

In this paper, Loofa egyptiaca (LE), an agricultural plant cultivated in Egypt, was used to prepare low-cost activated carbon (LE_C1 and LE_C2) adsorbents. The adsorbents (LE, LE_C1 and LE_C2) were evaluated for their ability to remove direct blue 106 dye from aqueous solutions. Batch mode experiments were conducted using various parameters such as pH, contact time, dye concentration and adsorbent concentration. The surface chemistry of LE, LE_C1 and LE_C2 was analyzed by scanning electron microscopy (SEM). The experimental data were examined using Langmuir, Freundlich, Temkin and Harkins–Jura isotherms. The results showed that the adsorption of direct blue 106 was maximal at the lowest value of pH (pH = 2). Removal efficiency was increased with an increase in dye concentration and a decrease in amount of adsorbent. Maximum adsorption capacity was found to be 57.14, 63.3 and 73.53 mg/g for LE, LE_C1 and LE_C2 respectively. Kinetics were also investigated using pseudo-first-order, pseudo-second-order and intra-particle diffusion models. The experimental data fitted very well with the pseudo-first-order and pseudo-second-order kinetic models. The results indicate that LE, LE_C1 and LE_C2 could be employed as adsorbents for the removal of direct blue dye from aqueous solutions.     

Investigating the phenol removal from aqueous media by photocatalytic magnetized graphene oxide nanocomposite

As a large and diverse group of secondary metabolites, phenolic compounds are one of the most common chemical pollutants present in water resources. these compounds can have toxic effects on ecosystems and humans. Therefore, their removal from water sources appears to be of great importance. In this study, a magnetic graphene oxide (MGO) photocatalyst was synthesized and used to remove phenol from water. The fabricated GO magnetic nanocomposites were determined by SEM and FTIR techniques. Afterward, these nanoparticles were used to remove phenol from aquatic media considering different operational parameters, including pH of the solution, initial concentration of phenol, contact time, and adsorbent dosage. The results showed that the magnetized GO nanoparticles could remove 90.83% of phenol molecules under the optimal conditions of solution pH = 3.0, initial phenol concentration of 20 mg/L, adsorbent concentration of 300 mg/L, and contact time of 120 min. additionally have compared the results of UV, Fe₃O₄/GO, and Fe₃O₄/GO/UV on the removal of phenol under optimum conditions. Accordingly, the phenol removal efficiencies for UV alone, Fe₃O₄/GO, and Fe₃O₄/GO/UV were obtained at 4.5, 65.73, and 90.83%, respectively. Based on the findings, the prepared magnetic GO nanoparticles have extended capabilities such as easy and rapid separation from sample and high potential in removing phenolic compounds, so, it can be introduced as an appropriate adsorbent for removal of this pollutant from water and wastewater.     

Equilibrium studies of copper ion adsorption onto palm kernel fibre

The equilibrium sorption of copper ions from aqueous solution using a new adsorbent, palm kernel fibre, has been studied. Palm kernel fibre is obtained in large amounts as a waste product of palm oil production. Batch equilibrium studies were carried out and system variables such as solution pH, sorbent dose, and sorption temperature were varied. The equilibrium sorption data was then analyzed using the Langmuir, Freundlich, Dubinin–Radushkevich (D–R) and Temkin isotherms. The fit of these isotherm models to the equilibrium sorption data was determined, using the linear coefficient of determination, r², and the non-linear Chi-square, χ² error analysis.The results revealed that sorption was pH dependent and increased with increasing solution pH above the pH_PZC of the palm kernel fibre with an optimum dose of 10 g/dm³. The equilibrium data were found to fit the Langmuir isotherm model best, with a monolayer capacity of 3.17 × 10^?4 mol/g at 339 K. The sorption equilibrium constant, K_a, increased with increasing temperature, indicating that bond strength between sorbate and sorbent increased with temperature and sorption was endothermic. This was confirmed by the increase in the values of the Temkin isotherm constant, B₁, with increasing temperature. The Dubinin–Radushkevich (D–R) isotherm parameter, free energy, E, was in the range of 15.7–16.7 kJ/mol suggesting that the sorption mechanism was ion exchange. Desorption studies showed that a high percentage of the copper was desorbed from the adsorbent using acid solutions (HCl, HNO₃ and CH₃COOH) and the desorption percentage increased with acid concentration. The thermodynamics of the copper ions/palm kernel fibre system indicate that the process is spontaneous and endothermic.     

Platinum (IV) recovery from chloride solution by functionalized acrylic copolymers

Two acrylic adsorbents with different morphological structures and bearing amidoethylenamine and thiol groups were obtained and used for platinum sorption from chloride solution by the batch method. Physico-chemical parameters that influence adsorption such as initial Pt(IV) concentration, stirring time, pH, and adsorbent amount were investigated. The thermodynamic parameters of Pt(IV) sorption on the synthesized adsorbent were also evaluated based on Langmuir and Freundlich isotherms. Thermodynamic parameters estimated from Langmuir constants indicated that the adsorption is spontaneous, exothermic and there is a disordered state at the molecular level. The models used to analyze the sorption rate led to the conclusion that the most important step in the sorption of Pt(IV) could be both particle diffusion and chemical reaction of [PtCl₆]⁻ with amine functional groups. Thus, both the ion exchange and complex formation mechanisms can occur via nitrogen atoms in the recovery of Pt(IV) on the studied adsorbent.     

Green coconut shells applied as adsorbent for removal of toxic metal ions using fixed-bed column technology

This study applies green coconut shells as adsorbent for the removal of toxic metal ions from aqueous effluents using column adsorption. The results show that a flow rate of 2 mL/min and a bed height of 10 cm are most feasible. Furthermore, larger amounts of effluent can be treated for removal of single ions. The breakthrough curves for multiple elements gave the order of adsorption capacity: Cu⁺² > Pb⁺² > Cd⁺² > Zn⁺² > Ni⁺². Real samples arising from the electroplating industry can be efficiently handled.     

Comparison of biosorbents with inorganic sorbents for removing copper(II) from aqueous solutions

In comparison with several other reported inorganic sorbents, Camellia tree leaf and primary sludge obtained from a settling tank as a pretreatment to the activated sludge system in a Hong Kong sewage treatment plant were evaluated for removing Cu(II) from aqueous solutions. Experimental data were modeled by the Langmuir isotherm equation to estimate the maximum sorption capacity (q_max). Results show that, at pH 5.6, biosorbents, Camellia tree leaf and primary sludge in particular, exert higher sorption capacities (q_max > 40 mg g⁻¹) than inorganic sorbents, Na-montmorillonite (q_max = 33.3 mg g⁻¹), fly ash (q_max = 18.8 mg g⁻¹), and goethite powder (10.3 mg g⁻¹). Furthermore, a pseudo second-order kinetic model was found to properly describe the experimental data for both bio- and inorganic sorbents. Sorption of Cu(II) on the Camellia tree leaf and primary sludge were much faster than that on the inorganic sorbents. In addition, desorption tests revealed that the desorption capacities of the two biomaterials are higher than the other selected materials; and much more Cu(II) can be retrieved from the Cu(II)-loaded biosorbents. Finally, increasing solution pH was found to greatly increase q_max and accelerate sorption processes.     

Treatment of municipal wastewater using a contact oxidation filtration separation integrated bioreactor

A new contact oxidation filtration separation integrated bioreactor (CFBR) was used to treat municipal wastewater. The CFBR was made up of a biofilm reactor (the upper part of the CFBR) and a gravitational filtration bed (the lower part of the CFBR). Polyacrylonitrile balls (50 mm diameter, 237 m²/m³ specific surface, 90% porosity, and 50.2% packing rate) were filled into the biofilm reactor as biofilm attaching materials and anthracite coal (particle size 1–2 mm, packing density 0.947 g/cm³, non-uniform coefficient (K₈₀ = d₈₀/d₁₀) < 2.0) was placed into the gravitational filtration bed as filter media. At an organic volumetric loading rate of 2.4 kg COD/(m³ d) and an initial filtration velocity of 5 m/h in the CFBR, the average removal efficiencies of COD, ammonia nitrogen, total nitrogen and turbidity were 90.6%, 81.4%, 64.6% and 96.7% respectively, but the treatment process seemed not to be effective in phosphorus removal. The average removal efficiency of total phosphorus was 60.1%. Additionally, the power consumption of the CFBR was less than 0.15 kWh/m³ of wastewater treated, and less than 1.5 kWh/kg BOD₅ removal.     

Removal of mercury from aqueous solutions using activated carbon prepared from agricultural by-product/waste

Removal of mercury from aqueous solutions using activated carbon prepared from Ceiba pentandra hulls, Phaseolus aureus hulls and Cicer arietinum waste was investigated. The influence of various parameters such as effect of pH, contact time, initial metal ion concentration and adsorbent dose for the removal of mercury was studied using a batch process. The experiments demonstrated that the adsorption process corresponds to the pseudo-second-order-kinetic models and the equilibrium adsorption data fit the Freundlich isotherm model well. The prepared adsorbents ACCPH, ACPAH and ACCAW had removal capacities of 25.88 mg/g, 23.66 mg/g and 22.88 mg/g, respectively, at an initial Hg(II) concentration of 40 mg/L. The order of Hg(II) removal capacities of these three adsorbents was ACCPH > ACPAH > ACCAW. The adsorption behavior of the activated carbon is explained on the basis of its chemical nature. The feasibility of regeneration of spent activated carbon adsorbents for recovery of Hg(II) and reuse of the adsorbent was determined using HCl solution.     

Optimization of activated carbon production from empty fruit bunch fibers in one-step steam pyrolysis for cadmium removal from aqueous solution

The fast growth of the palm oil industry in Malaysia is associated with various waste products, namely the empty fruit bunches (EFB), which have a negative impact on the environment. Therefore, these wastes were utilized as a cheap raw material for the production of activated carbon (AC) with less energy consumption. One-step steam pyrolysis was used to produce AC from oil palm empty fruit bunch fibers (EFBF) by varying the operating parameters of temperature, steam flow rate, and activation time using two-level full factorial experimental design (FFD). Ten samples of AC were prepared and the optimized production conditions were chosen based on the ability to adsorb and remove cadmium. Physical activation comprised of carbonization for 30 min using nitrogen gas (N₂), followed by activation with steam at different flow rates (2.0, 3.0, and 4.0 ml/min), temperatures (600, 750, and 900°C) and times (15, 30, and 45 min). The AC sample produced at an activation temperature of 900°C with a steam flow rate of 2.0 ml/min and activation time of 15 min was selected as the best adsorbent with a total yield of 21.7%. It had adsorbed more than 97% of total cadmium from aqueous solution within 2 min of the contact time. Characterization of EFBF-based AC by SEM and BET surface area analysis had shown a good-quality adsorbent with highly active sites and well-developed pores with BET surface area of 635.16 m²/g. Experimental results indicated that the prepared AC from EFBF provide a promising solution in water and wastewater treatment.     

Adsorption of methylene blue from aqueous solution by jackfruit (Artocarpus heteropyllus) leaf powder: A fixed-bed column study

Continuous fixed-bed studies were undertaken to evaluate the efficiency of jackfruit leaf powder (JLP) as an adsorbent for the removal of methylene blue (MB) from aqueous solution under the effect of various process parameters like bed depth (5–10 cm), flow rate (30–50 mL/min) and initial MB concentrations (100–300 mg/L). The pH at point of zero charge (pH_PZC) of the adsorbent was determined by the titration method and a value of 3.9 was obtained. A FTIR of the adsorbent was done before and after the adsorption to find the potential adsorption sites for interaction with methylene blue molecules. The results showed that the total adsorbed quantities and equilibrium uptake decreased with increasing flow rate and increased with increasing initial MB concentration. The longest breakthrough time and maximum MB adsorption were obtained at pH 10. The results showed that the column performed well at low flow rate. Also, breakthrough time and exhaustion time increased with increasing bed depth. The bed-depth service time (BDST) model and the Thomas model were applied to the adsorption of MB at different bed depths, flow rates, influent concentrations and pH to predict the breakthrough curves and to determine the characteristic parameters of the column that are useful for process design. The two model predictions were in very good agreement with the experimental results at all the process parameters studied indicating that they were very suitable for JLP column design.     

黄浦江上游原水强化处理选炭试验研究

以黄浦江上游水源为原水,通过煤质炭、竹质炭、椰壳炭等炭种筛选小试和中试试验,研究了黄浦江上游原水中有机污染物强化去除的最佳炭种及其最佳投加量。结果表明黄浦江上游原水中投加PAC能够改善处理后水质,提高原水中有机物的去除效果;并且随着PAC投加量的增加,原水中有机物去除效果增强;综合性价比、碳源等因素确定竹质炭较为经济合理;当竹质炭投加量为10～15mg/L时,处理后出水CODMn可达到3mg/L或以下。     

Removal of polycyclic aromatic hydrocarbons from aqueous solution on soybean stalk-based carbon

Soybean [ (L.) Merr.] stalk-based carbons were prepared by phosphoric acid activation at different carbonization temperatures. Characteristics of the prepared carbon, including specific surface area, iodine number, and amount of methylene blue sorption, were determined. Experiments on phenanthrene, naphthalene, and acenaphthene, as representatives of polycyclic aromatic hydrocarbons (PAHs), removal from aqueous solution by the prepared carbon were conducted at different levels of carbon addition. The results indicated that the specific surface area, iodine number, and amount of methylene blue sorption increased with an increase of carbonization temperature. The maximum values were observed at 700°C and were 287.63 m g, 508.99 mg g, and 90.14 mg g, respectively. The removal efficiencies of phenanthrene, naphthalene, and acenaphthene tended to increase with increasing carbon amounts and carbonization temperature. The optimal removal performance was obtained under the experimental conditions of carbon concentrations of 0.04 g 32 mL and carbonization temperature of 700°C, and the removal efficiencies of phenanthrene, naphthalene, and acenaphthene were 99.89, 100, and 95.64%, respectively. The performance of the prepared carbon was superior to that of commercial activated carbon. Additionally, for the same carbon concentrations, the removal efficiency of PAHs on prepared carbons followed the order: phenanthrene > naphthalene > acenaphthene. Results obtained from this work provide some insight into the reuse of an agricultural residue, and also provide a new application for the treatment of PAHs in contaminated water utilizing activated carbon prepared from agricultural residues.     

Land Use and Climate Variability Amplify Carbon,Nutrient, and Contaminant Pulses: A Review with Management Implications

Nonpoint source pollution from agriculture and urbanization is increasing globally at the same time climate extremes have increased in frequency and intensity. We review >200 studies of hydrologic and gaseous fluxes and show how the interaction between land use and climate variability alters magnitude and frequency of carbon, nutrient, and greenhouse gas pulses in watersheds. Agricultural and urban watersheds respond similarly to climate variability due to headwater alteration and loss of ecosystem services to buffer runoff and temperature changes. Organic carbon concentrations/exports increase and organic carbon quality changes with runoff. Nitrogen and phosphorus exports increase during floods (sometimes by an order of magnitude) and decrease during droughts. Relationships between annual runoff and nitrogen and phosphorus exports differ across land use. CH₄ and N₂O pulses in riparian zones/floodplains predominantly increase with: flooding, warming, low oxygen, nutrient enrichment, and organic carbon. CH₄, N₂O, and CO₂ pulses in streams/rivers increase due to similar factors but effects of floods are less known compared to base flow/droughts. Emerging questions include: (1) What factors influence lag times of contaminant pulses in response to extreme events? (2) What drives resistance/resilience to hydrologic and gaseous pulses? We conclude with eight recommendations for managing watershed pulses in response to interactive effects of land use and climate change.     

Biohythane production from pineapple peel using Methanosarcina mazei enhanced with palm oil mill effluent (POME) sludge in single-stage anaerobic digestion

Biohythane production via single-stage anaerobic digestion (AD) is an effective way for sustainable energy recovery from lignocellulosic biomass. In this paper, biohythane was produced through the AD process from pineapple peel waste substrate using purely cultured Methanosarcina mazei with the enhancement of palm oil mill effluent (POME) sludge as the inoculum. This study focuses on the effects of the lignocellulosic pre-treatment method, the addition of POME sludge into M. mazei culture medium as inoculum, and various operational conditions (food to microorganisms (F/M) ratios, temperature, pH) on gas production performances. The experimental results indicate that these parameters influenced the efficiency of biohythane production by producing the peak maximum biohythane production rate values (HPR_max) and (MPR_max), H₂:CH₄ = 1.93:0.67 L/L-d, and biohythane yield (HY) and (MY), H₂:CH₄ = 1.18:0.55 mL/L-substrate. This study demonstrates that biohythane gas (H₂ + CH₄ + CO₂) production from pineapple waste can be accelerated by M. mazei only with the enhancement of POME sludge through single-stage AD system under mesophilic batch process conditions.     

Effect of synthesis parameters on single gas permeation through T-type zeolite membranes

In this research, nanoporous zeolite T membranes were synthesized at three levels of synthesis temperature: 100, 120 and 140 °C and synthesis time: 15, 30 and 50 h and characterized by gas permeation. Effects of synthesis parameters on CO₂ and CH₄ permeances and CO₂/CH₄ ideal separation factors were studied. All experiments were conducted at 1 bar feed pressure and 30 °C module temperature. Normally, it is anticipated that increasing synthesis temperature and synthesis time increase gas permeances and consequently decrease ideal separation factor. This prediction was not observed in the case of synthesis temperature increase from 100 to 120 °C as well as synthesis time increase from 15 to 30 h, due to the dual effect of increasing synthesis temperature and synthesis time on gas permeances and ideal separation factor. More zeolites are deposited and larger crystals are formed at higher synthesis temperatures and times. Forming the larger crystals accelerates the rate of zeolite layer integration, which is responsible for gas separation, in one hand and reduces the density of deposited zeolite layer on the support, due to the formation of more voids, on the other hand. In terms of maximizing the CO₂/CH₄ ideal separation factor, medium synthesis temperature and synthesis time (120 °C and 30 h) can be selected, however, maximum gas permeances are obtained at low levels of synthesis temperature and time (100 °C and 15 h). According to the ranges of gas permeances (10⁻¹¹ to 10⁻⁶ mol/m² s Pa) and CO₂/CH₄ ideal separation factors (1.4–70.3), it is concluded that the zeolite T membranes synthesized at optimum conditions can be employed for membrane separation of CO₂/CH₄ mixtures.     

Novel lithium-based sorbents from fly ashes for CO2 capture at high temperatures

In this work several Li₄SiO₄-based sorbents from fly ashes for CO₂ capture at high temperatures have been developed. Three fly ash samples were collected and subjected to calcination at 950 °C in the presence of Li₂CO₃. Both pure Li₄SiO₄ and fly ash-based sorbents were characterised and tested for CO₂ sorption at different temperatures between 400 and 650 °C and adding different amounts of K₂CO₃ (0–40 mol%). To examine the sorbents performance, multiple CO₂ sorption/desorption cycles were carried out. The temperature and the presence of K₂CO₃ strongly affect the CO₂ sorption capacity for the sorbents prepared from fly ashes. When the sorption temperature increases by up to 600 °C both the CO₂ sorption capacity and the sorption rate increase significantly. Moreover when the amount of K₂CO₃ increases, the CO₂ sorption capacity also increases. At optimal experimental conditions (600 °C and 40 mol% K₂CO₃), the maximum CO₂ sorption capacity for the sorbent derived from fly ash was 107 mg CO₂/g sorbent. The Li₄SiO₄-based sorbents can maintain its original capacity during 10 cycle processes and reach the plateau of maximum capture capacity in less than 15 min, while pure Li₄SiO₄ presents a continual upward tendency for the 15 min of the capture step and attains no equilibrium capacity.     

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.     

Operating experience with chemical looping combustion in a 120 kW dual circulating fluidized bed (DCFB) unit

This study presents first operating experience with a 120 kW chemical looping pilot rig. The dual circulating fluidized bed reactor system and its auxiliary units are discussed. Two different oxygen carriers, i.e. ilmenite, which is a natural iron titanium ore, and a designed Ni-based particle, are tested in the CLC unit. The pilot rig is fueled with H₂, CO and CH₄ respectively at a fuel power of 65–145 kW. High solids circulation, very low solids residence time and low solids inventory are observed during operation. Owing to the scalability of the design concept, these characteristics should be quite similar to those of commercial CLC power plants. Ilmenite shows a high potential for the combustion of H₂-rich gases (e.g. from coal gasification with steam). The H₂ conversion is quite high but there is still a high potential for further improvement. The Ni-based oxygen carrier achieves the thermodynamic maximum H₂ and CO conversion and also very high CH₄ conversion. A variation of the air/fuel ratio and the reaction temperature indicates that the Ni/NiO ratio of the particle has an influence on the performance of the chemical looping combustor. Generally, low solids conversion in air and fuel reactors is observed in almost any conditions. Despite a very low H₂O/CH₄ molar ratio, no carbon formation is observed.