Waste materials for activated carbon preparation and its use in aqueous-phase treatment: a review

Commercial activated carbon is a preferred adsorbent for the removal of micropollutants from the aqueous phase; however, its widespread use is restricted due to high associated costs. To decrease treatment costs, attempts have been made to find inexpensive alternative activated carbon (AC) precursors, such as waste materials. Some reviews report the use of waste materials for the preparation of AC; however, these studies are restricted to either type of wastes, preparation procedures, or specific aqueous-phase applications. The present work reviews and evaluates literature dedicated both to the preparation of AC by recycling different types of waste materials and also to its application in various aqueous-phase treatments. It is clear that conventional (from agriculture and wood industry) and non-conventional (from municipal and industrial activities) wastes can be used to prepare AC, that can be applied in various aqueous treatment processes, namely to remove organic pollutants, dyes, volatile organic compounds, and heavy metals. Moreover, high surface areas can be obtained using either physical or chemical activation; however, combined treatments might enhance the surface properties of the adsorbent, therefore increasing its adsorption capacity. It is evident from the revision made that AC prepared from both conventional and non-conventional wastes might effectively compete with the commercial ones. This happens mostly when the activation procedures are optimized considering both the raw material used to produce the carbons and the contaminants to be removed.     

Effect of biochar amendment on tylosin adsorption-desorption and transport in two different soils

The role of biochar as a soil amendment on the adsorption-desorption and transport of tylosin, a macrolide class of veterinary antibiotic, is little known. In this study, batch and column experiments were conducted to investigate the adsorption kinetics and transport of tylosin in forest and agricultural corn field soils amended with hardwood and softwood biochars. Tylosin adsorption was rapid at initial stages, followed by slow and continued adsorption. Amounts of adsorption increased as the biochar amendment rate increased from 1 to 10%. For soils with the hardwood biochar, tylosin adsorption was 10 to 18% higher than that when using the softwood biochar. Adsorption kinetics was well described by Elovich equation ( ≥ 0.921). As the percent of biochar was increased, the rates of initial reactions were generally increased, as indicated by increasing α value at low initial tylosin concentration, whereas the rates during extended reaction times were generally increased, as indicated by decreasing β value at high initial tylosin concentration. A considerably higher amount of tylosin remained after desorption in the corn field soil than in the forest soil regardless of the rate of biochar amendment, which was attributed to the high pH and silt content of the former. The breakthrough curves of tylosin showed that the two soils with biochar amendment had much greater retardation than those of soils without biochar. The CXTFIT model for the miscible displacement column study described well the peak arrival time as well as the maximum concentration of tylosin breakthrough curves but showed some underestimation at advanced stages of tylosin leaching, especially in the corn field soil. Overall, the results indicate that biochar amendments enhance the retention and reduce the transport of tylosin in soils.     

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.     

Application of 'waste' wood-shaving bottom ash for adsorption of azo reactive dye

The utilization of wood-shaving bottom ash (WBA) for the removal of Red Reactive 141 (RR141), an azo reactive dye, was investigated. WBA/H(2)O and WBA/H(2)SO(4) were made by treating WBA with water and 0.1M H(2)SO(4), respectively, to increase adsorption capacity. Adsorption of RR141 from reactive dye solution (RDS) and reactive dye wastewater (RDW) by WBA/H(2)O and WBA/H(2)SO(4) involved the BET surface area and pore size diameter. Properties of adsorbents, effect of contact time, initial pH of solution, dissolved metals and elution studies indicated that the decolorisation mechanism involved both chemical adsorption and precipitation with calcium ions. In addition, the WBA/H(2)SO(4) surface might contain sulphate-cation complexes that were specific to enhancing dye adsorption from RDW. The adsorption isotherm had a best fit by the Freundlich model. Freundlich parameters showed that WBA/H(2)O used more heterogeneous surface than WBA/H(2)SO(4) and activated carbon for RDW adsorption. A thermodynamic study indicated that RDW adsorption was an endothermic process. The maximum dye adsorption capacities of WBA/H(2)O, WBA/H(2)SO(4) and activated carbon obtained from a Langmuir model at 30 degrees C were 24.3, 29.9, and 41.5mgl(-1), respectively. In addition, WBA/H(2)O and WBA/H(2)SO(4) could reduce colour and high chemical oxygen demand (COD) of real textile wastewater. According to the difficulty in the elution study, it was an environmentally safe disposal of this waste. Therefore, WBA, a waste from combustion of wood shavings, was suitable to be used as an effective adsorbent for azo reactive dye removal.     

Adsorption of pesticides onto quartz, calcite, kaolinite, and alpha-alumina

The fate of pesticides in aquifers is influenced by the small but not insignificant adsorption of pesticides to mineral surfaces. Batch experiments with five pesticides and four minerals were conducted to quantify the contributions to adsorption from different mineral surfaces and compare adsorption characteristics of selected pesticides. Investigated mineral phases included quartz, calcite, kaolinite, and alpha-alumina. Selected pesticides comprised atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine), isoproturon [3-(4-isopropylphenyl)-1,1-dimethylurea)], mecoprop [(RS)-2-(4-chloro-2-methylphenoxy)propionic acid], 2,4-D (2,4-dichlorophenoxyacetic acid), and bentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4-(3H)-one 2,2-dioxide]. Specific surface area and mineral surface charge proved to be important for the adsorption of these pesticides. Detectable adsorption of the anionic pesticides (mecoprop, 2,4-D, and bentazone) was only measured when positive sites were present on the mineral surface. However, when CaCl2 was added as an electrolyte, a detectable adsorption of mecoprop and 2,4-D was also measured on kaolinite (which exhibits a negative surface charge), probably due to formation of Ca-pesticide--surface complexes. Adsorption of the uncharged pesticides (atrazine and isoproturon) was detected only on kaolinite. The lack of adsorption on alpha-alumina indicates that the uncharged pesticides have a greater affinity for the silanol surface sites (=SiOH) than for the aluminol surface sites (=AlOH) in kaolinite. No measurable effect of ionic strength was found for the uncharged pesticides. The results indicate that quartz and calcite play a smaller role than clay minerals.     

Enzyme-linked immunosorbent assay for ultratrace determination of antibiotics in aqueous samples

Two commercially available enzyme-linked immunosorbent assay (ELISA) kits that are commonly used for tylosin or tetracycline residues in meat and milk were adapted for ultratrace analysis of these antibiotics in surface and ground waters. These two antibiotics are commonly fed to swine, turkeys, and cattle at subtherapeutic doses for growth promotion purposes. Both ELISA techniques were found to be highly sensitive and selective for the respective antibiotics with detection limits of 0.10 and 0.05 microg L(-1) for tylosin and tetracycline, respectively. The recovery of both tylosin and tetracycline from spiked samples of lake waters, runoff samples, soil saturation extracts, and nanopure water was close to 100%. Tetracycline ELISA was highly specific for tetracycline and chlortetracycline but not for other forms of tetracycline (oxytetracycline, demeclocycline, and doxycycline). Analysis of a few liquid swine manure samples by liquid chromatography-mass spectrometry (LC-MS) showed lower concentrations for chlortetracycline as compared with concentrations obtained using ELISA. However, the concentrations of tylosin from ELISA were comparable with that of LC-MS. The lower concentrations of chlortetracycline obtained by LC-MS in manure samples indicate the presence of other similar or transformed compounds that were detected by ELISA but not determined by LC-MS. These results indicate that both ELISA kits can be useful tools for low-cost screening of tylosin, tetracycline, and chlortetracycline in environmental waters. Furthermore, both ELISA procedures are rapid, portable, and easily adaptable for testing of multiple samples simultaneously.     

Adsorption of carbon dioxide on alkali-modified zeolite 13X adsorbents

Shaped zeolite 13X adsorbent with kaolin as binder was hydrothermally modified in sodium hydroxide solution to improve its adsorption performance. The characterization of the product by XRD, N₂ adsorption–desorption and water vapour adsorption displayed that kaolin component in zeolite adsorbent can be converted into zeolite during the alkali treatment, resulting in the modified adsorbent consisting entirely of effectual adsorption composition. Compared with the unmodified adsorbent, the modified adsorbent exhibited higher adsorption capacity and uptake rate for carbon dioxide, because of the increase of effective adsorption surface and the decrease of diffusion resistance owing to conversion of kaolin binder into zeolite. The model parameters of isotherms and the isosteric heats calculated by the Clausius–Clapeyron equation for CO₂ adsorption showed the stronger interaction of adsorbate–adsorbent and the higher degree of heterogeneity of adsorption centers in modified than unmodified adsorbents.     

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.     

Preparation and characterization of activated carbon from a new raw lignocellulosic material: Flamboyant (Delonix regia) pods

Activated carbons were prepared from flamboyant pods by NaOH activation at three different NaOH:char ratios: 1:1 (AC-1), 2:1 (AC-2), and 3:1 (AC-3). The properties of these carbons, including BET surface area, pore volume, pore size distribution, and pore diameter, were characterized from N₂ adsorption isotherms. The activated carbons obtained were essentially microporous and had BET surface area ranging from 303 to 2463 m² g⁻¹.¹³C (CP/MAS and MAS) solid-state NMR shows that the lignocellulosic structures were completely transformed into a polycyclic material after activation process, thermogravimetry shows a high thermal resistance, Boehm titration and Fourier-transform infrared spectroscopy allowed characterizing the presence of functional groups on the surface of activated carbons. Scanning electron microscopy images showed a high pore development. The experimental results indicated the potential use of flamboyant pods as a precursor material in the preparation of activated carbon.     

Investigation of activated carbon/ethanol for low temperature adsorption cooling

Commercially available adsorption cooling systems use water/silica gel, water/zeolite and ammonia/ chloride salts working pairs. The water-based pairs are limited to work above 0°C due to the water high freezing temperature, while ammonia has the disadvantage of being toxic. Ethanol is a promising refrigerant due to its low freezing point (161 K), nontoxicity, zero ozone depletion, and low global warming potential. Activated carbon (AC) is a porous material with high degree of porosity (500–3000 m²/g) that has been used in wide range of applications. Using Dynamic Vapour Sorption (DVS) test facility, this work characterizes the ethanol adsorption of eleven commercially available activated carbon materials for cooling at low temperature of ?15°C. DVS adsorption results show that Maxsorb has the best performance in terms of ethanol uptake and adsorption kinetics compared to the other tested materials. The Maxsorb/ethanol adsorption process has been numerically modeled using computational fluid dynamics (CFD) and simulation results are validated using the DVS experimental measurements. The validated CFD simulation of the adsorption process is used to predict the effects of adsorbent layer thickness and packing density on cycle uptake for evaporating temperature of ?15°C. Simulation results show that as the thickness of the Maxsorb adsorbent layer increases, its uptake decreases. As for the packing density, the amount of ethanol adsorbed per plate increases with the packing density reaching maximum at 750 kg/m³. This work shows the potential of using Maxsorb/ethanol in producing low temperature cooling down to ?15°C with specific cooling energy reaching 400 kJ/kg.     

Development of activated carbon from Nerium oleander flower and their rapid adsorption of direct and reactive dyes

The present study investigates the thermally activated carbon derived from Nerium oleander flower which was used an adsorbent. Physicochemical properties of Nerium oleander flower carbon (NOFC) were characterized by scanning electron microscopy, X-ray diffraction, and Fourier transform infrared for the removal of DTB (Direct Turquoise Blue) and RR-HE7B (Reactive red–HE7B) dyes from aqueous solution. Adsorption studies were carried out with different pH, adsorbent dose, contact time, and initial concentration dye solution. Optimum conditions for maximum removal of DTB and RR-HE7B was achieved to be pH 2 for both dyes, adsorbent dose of 100 mg and equilibrium time of 35 and 60 min, respectively, for NOFC. The maximum adsorption capacity of NOFC was found to be 33.33 and 19.60 mg g^?1, respectively, for the removal of dye solution. The mechanism of adsorption was studied by using different kinetic models and isotherms. The results clearly showed that the NOFC adsorption was fitted to pseudo–first-order for DTB and pseudo–second-order for RR-HE7B. Equilibrium data were well fitted with both isotherm models. According to the results, NOFC can effectively remove DTB and RR-HE7B from aqueous solutions.     

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.     

炭基催化剂比表面积、孔径与硫容关系研究

取T12系列12种炭基催化剂,采用物理吸附仪测定其比表面积和孔径分布,并在相同条件下做脱硫实验测得硫容。对其比表面积、孔径与SO2吸附分子直径比值与脱硫效果的关系进行研究。结果表明:对于T12系列炭基催化剂,催化效果会随着比表面积和孔径的增加而变得更好,总比表面积超过720m2/g,孔径超过0.85nm以后,催化剂的脱硫效果反而降低。     

Antibacterial activity of soil-bound antibiotics

There is some concern that antibiotic residues in land-applied manure may promote the emergence of antibiotic resistant bacteria in the environment. The goal of this study was to determine whether or not soil bound antibiotics are still active against bacteria. The procedure involved sorbing various amounts of tetracycline or tylosin on two different textured soils (Webster clay loam [fine-loamy, mixed, superactive, mesic Typic Endoaquolls] and Hubbard loamy sand [sandy, mixed, frigid Entic Hapludolls]), incubating these soils with three different bacterial cultures (an antibiotic resistant strain of Salmonella sp. [Salmonella(R)], an antibiotic sensitive strain of Salmonella sp. [Salmonella(S)], and Escherichia coli ATCC 25922), and then enumerating the number of colony forming units relative to the control. Incubation was done under both static and dynamic conditions. Soil-adsorbed antibiotics were found to retain their antimicrobial properties since both antibiotics inhibited the growth of all three bacterial species. Averaged over all other factors, soil adsorbed antimicrobial activity was higher for Hubbard loamy sand than Webster clay loam, most likely due to higher affinity (higher clay content) of the Webster soil for antibiotics. Similarly, there was a greater decline in bacterial growth with tetracycline than tylsoin, likely due to greater amounts of soil-adsorbed tetracycline and also due to lower minimum inhibitory concentration of most bacteria for tetracycline than tylosin. The antimicrobial effect of tetracycline was also greater under dynamic than static growth conditions, possibly because agitation under dynamic growth conditions helped increase tetracycline desorption and/or increase contact between soil adsorbed tetracycline and bacteria. We conclude that even though antibiotics are tightly adsorbed by clay particles, they are still biologically active and may influence the selection of antibiotic resistant bacteria in the terrestrial environment.     

改性玉米秸秆吸附去除废水中四环素的研究

应用平衡吸附法，研究了不同投加量（改性玉米秸秆）、温度及pH条件下，改性玉米秸秆对水体中四环素的吸附作用，并利用等温曲线及吸附动力学方程对试验结果进行了拟合。结果表明：在吸附剂用量0．4g，温度30℃，振荡时间30min，pH值7的条件下，对水体中四环素浓度为50．136mg／L的吸附率可达93．4％。四环素废水吸附均符合Langmuir及Freundlich等温模式。但Langmuir方程拟合得较好，Elovich方程能更好地拟舍改性玉米秸秆对水体中四环素的吸附动力学曲线。     

水处理用活性炭改性研究

研究了锆（Zr）和十六烷基三甲基氯化铵（CTAC）联合改性活性炭的制备，并考察Zr-CTAC改性活性炭对水中硝酸盐和磷酸盐的吸附作用及相关吸附机制，着重论述了锆（Zr）和十六烷基三甲基氯化铵联合改性活性炭（Zr-CTAC-AC）对水中硝酸盐和磷酸盐的吸附去除作用，结果表明Zr-CTAC-AC对水中硝酸盐和磷酸盐均具备较好的吸附去除能力。     

Kinetic and equilibrium isotherm studies for the adsorptive removal of Brilliant Green dye from aqueous solution by rice husk ash

The present study deals with the adsorption of Brilliant Green (BG) on rice husk ash (RHA). RHA is a solid waste obtained from the particulate collection equipment attached to the flue gas lines of rice husk fired boilers. Batch studies were performed to evaluate the influences of various experimental parameters like initial pH (pH0), contact time, adsorbent dose and initial concentration (C0) on the removal of BG. Optimum conditions for BG removal were found to be pH0 approximately 3.0, adsorbent dose approximately 6 g L(-1) of solution and equilibrium time approximately 5 h for the C0 range of 50-300 mg L(-1). Adsorption of BG followed pseudo-second-order kinetics. Intra-particle diffusion does not seem to control the BG removal process. Equilibrium isotherms for the adsorption of BG on RHA were analyzed by Freundlich, Langmuir, Redlich-Peterson (R-P), Dubnin-Radushkevich (D-R), and Temkin isotherm models using a non-linear regression technique. Langmuir and R-P isotherms were found to best represent the data for BG adsorption onto RHA. Adsorption of BG on RHA is favourably influenced by an increase in the temperature of the operation. Values of the change in entropy (DeltaS0) and heat of adsorption (DeltaH0) for BG adsorption on RHA were positive. The high negative value of change in Gibbs free energy (DeltaG0) indicates the feasible and spontaneous adsorption of BG on RHA.     

Use of an activated carbon from antibiotic waste for the removal of Hg(II) from aqueous solution

Porous carbon has been prepared from waste antibiotic material by a chemical activation method using K(2)CO(3) as an activating reagent. Carbon was studied systematically by the adsorption of nitrogen and iodine. It was found that the process parameters such as activation temperature and activation time are crucial for preparing high-quality activated carbon. The proper choice of the preparation conditions allows to produce microporous activated carbon with a micropore volume up to 0.492 cm(3)/g and a BET surface area of 1260 m(2)/g. Adsorption of mercury(II) from an aqueous solution on antibiotic carbon was investigated under the varying conditions of agitation time, metal ion concentration and pH. The adsorption capacity of the carbon is 129 mg/g.     

Metal bioavailability and speciation in a wetland tailings repository amended with biosolids compost,wood ash,and sulfate

Lead poisoning of waterfowl from direct ingestion of wetland mine tailings has been reported at the Coeur d'Alene River basin in Idaho. A greenhouse study was conducted to evaluate the effects of surface applications of amendments on lead bioavailability in the tailings. Treatments included sediment only, and sediment with three different surface amendments: (i) biosolids compost plus wood ash, (ii) compost + wood ash + a low SO4(2-) addition as K2SO4, and (iii) compost + wood ash + a high SO4(2-) addition. Measured variables included growth and tissue Pb, Zn, and Cd concentration of arrowhead (Sagittaria latifolia Willd.) and cattail (Typha latifolia L.) and soil pH, redox potential (Eh), pore water Pb, Pb speciation by X-ray absorption spectroscopy, and in vitro Pb bioavailability. The compost + ash amendment alleviated phytotoxicity for both plant species. Bioavailability of Pb as measured by a rapid in vitro extract decreased by 24 to 34% (over control) in the tailings directly below the amendment layer in the compost + SO4 treatments. The ratio of acid volatile sulfide (AVS) to simultaneously extracted metals (SEM) also indicated a reduction in Pb bioavailability (1:40 control, 1:20 compost, 1:8 compost + low SO4, and 1:3 compost + high SO4). Extended X-ray adsorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopy data indicated that lead sulfide was greater after 99 d in the treatments that included additions of sulfate. These results indicated that, under reducing conditions, surface amendments of compost + wood ash (with or without sulfate) decreased the bioavailability of Pb in metal-contaminated mine tailings.     

The influence of different surface-modification treatments on biomass-based carbons and their effects on adsorption of carbon dioxide

Surface modification of biomass-based carbon with nitrogen-containing functional groups is performed by the different modification method, including the thermal and chemical methods. We also investigate the effect of the different reaction parameters on their pore structure using the Brunauer–Emmett–Teller surface area and adsorption performance based on methylene blue value. Fourier transforms infrared spectroscopy methods are performed to confirm the presence of N-containing groups. Based on above results, the comparison effect of different modification methods on physico-chemical propriety and adsorption properties of biomass-based carbon materials are carried out. In conclusion, all modification methods could enhance CO₂ adsorption capability. However, the carbon materials treated with ammonia using thermal method show the best performance.