Adsorption of dyes and humic acid from water using chitosan‐encapsulated activated carbon

The adsorption isotherms and rates of two dyes and humic acid from aqueous solutions onto chitosan‐encapsulated activated carbon (CEAC) beads were measured at 30 °C. Such beads were prepared by mixing different weight percents of cuttlefish‐based chitosan (100%, 80%, 67%, and 55%) and rice‐based activated carbons. It was shown that the isotherms of dyes and humic acid were well fitted by the Freundlich equation. The adsorption capacity and rate could be enhanced when activated carbon was encapsulated with chitosan. Four simplified kinetic models including the pseudo‐first‐order equation, pseudo‐second‐order equation, intraparticle diffusion model, and the Elovich equation were tested to follow the adsorption processes. The adsorption of dyes was best described by the Elovich equation, but that of humic acid was best described by the intraparticle diffusion model. The kinetic parameters of each best‐fit model were calculated and are discussed in this paper. © 2002 Society of Chemical Industry     

Synthetic carbons activated with phosphoric acid III. Carbons prepared in air

Synthetic activated carbons were prepared by phosphoric acid activation of a styrene-divinylbenzene copolymer in an air atmosphere at various temperatures in the 400-900 °C interval. The carbons were characterized by elemental analysis, cation-exchange capacity measurement, infrared spectroscopy, potentiometric titration, copper adsorption from solution and physical adsorption of N₂ at −196 °C and CO₂ at 0 °C. It was shown that, similarly to synthetic phosphoric acid activated carbons obtained in argon, the synthetic carbons activated with phosphoric acid in air possess an acidic character and show considerable cation-exchange properties. The contribution of oxygen-containing surface groups along with phosphorus-containing groups to CEC is higher for carbons obtained in air. Three types of surface groups were identified on carbons prepared at temperatures up to 600 °C, and four types on carbons prepared at higher temperatures. These groups were assigned to ‘super-acidic’ (pK<0), phosphorus-containing (pK=1.1-1.2), carboxylic (pK=4.7-6.0) and phenolic (pK=8.1-9.4) groups. The cation-exchange capacity was at a maximum for the carbon prepared at 800 °C. Copper adsorption by synthetic phosphoric acid activated carbons obtained in air at temperatures lower than 800 °C is higher than for similar carbons obtained in argon. The increase is due to additional formation of oxygen-containing surface groups. Calculated copper binding constants revealed the importance of phosphorus-containing and carboxylic groups for adsorption of copper from aqueous solution. All carbons show a multimodal pore size distribution including simultaneously micropores and mesopores, but the porous texture is not a prime factor in determining the cation-exchange capacities of these carbons. Synthetic phosphoric acid activated carbons show a greater development of porosity when obtained in air as compared to carbons carbonized in argon.     

Oxygen and phosphorus enriched carbons from lignocellulosic material

Activated carbons were prepared by phosphoric acid activation of fruit stones in air at temperatures 400-1000 °C. The surface chemistry was investigated by elemental analysis, cation exchange capacity, infrared spectroscopy and potentiometric titration. The porous structure was analyzed from adsorption isotherms (N₂ at 77 K and CO₂ at 273 K). It was demonstrated that all carbons show considerable cation exchange capacity, the maximum (2.2 mmol g⁻¹) being attained at 700 °C, which coincides with the maximum contents of phosphorus and oxygen. The use of air instead of argon during thermal treatment increased the amount of cation exchangeable surface groups for carbons obtained at 400-700 °C. Proton affinity distributions of all carbons show the presence of three types of surface groups with pK 1.8-3.1 (carboxylic and polyphosphates), 4.8-6.3 (second dissociation of carboxylic, weak acid in polyphosphates and enol structures) and 8.1-9.7 (phenols and enol structures). Carbons obtained in air at 400-600 °C show enhanced copper adsorption from 0.001 mol L⁻¹ Cu(NO₃)₂ in acidic solutions as compared to carbons obtained in argon. Carbons obtained in air show well-developed porous structure that is equivalent or higher as compared with carbons obtained in argon; the difference being progressively increased with increasing treatment temperature.     

Synthetic carbons activated with phosphoric acid: II. Porous structure

Synthetic activated carbons were prepared by H₃PO₄ activation of a chloromethylated and sulfonated copolymer of styrene and divinylbenzene, using an impregnation weight ratio of 0.75 and carbonization temperatures in the 400-1000 °C range. Other impregnation ratios (0.93 and 1.11) were also used at a carbonization temperature of 800 °C. The porous texture of the resulting carbons was characterized by N₂ adsorption at −196 °C and CO₂ adsorption at 0 °C. All carbons exhibited a multimodal pore size distribution with maxima in the micropore and meso/macropore regions. Maxima in pore volume were attained at 900 °C for micropores and at 500 and 900 °C for mesopores. The mesopore volume was less sensitive than the micropore volume to changes in the impregnation ratio. It is concluded that the porous texture is not a prime factor in determining the outstanding cation exchange capacities of these carbons.     

Adsorption of Hg(II) ions from aqueous chloride solutions using powdered activated carbons

Activated carbons were developed from Casurina equisetifolia leaves, by chemically treating with sulfuric acid (1:1) or zinc chloride (25%), at low (425 °C) and high (825 °C) temperatures. The resulting powdered activated carbons were applied for removing mercuric ions from aqueous solution at different agitation times and mercuric ion concentrations. The equilibrium data fitted well the Langmuir adsorption isotherm. The Langmuir adsorption capacities were 12.3 and 20.3 mg g⁻¹ for low temperature carbons and 43.9 and 38.5 mg g⁻¹ for high temperature carbons impregnated with H₂SO₄ and ZnCl₂, respectively. Studies of the effects of carbon dosage, NaCl concentrations and solution pH values were carried out for the more effective, high temperature carbons. Increasing NaCl concentration resulted in a significant decrease in the adsorption efficiency. Adsorption was high from solutions with low and neutral pH values and lower for solutions with alkaline pH values for the high temperature carbons.     

Tubular structured ordered mesoporous carbon as an efficient sorbent for the removal of dyes from aqueous solutions

Tubular structured ordered mesoporous carbon CMK-5 was investigated for the adsorption of the industrial dyes reactive blue 19, acid red 57 and fuchsin basic in aqueous solutions at room temperature. It was found that CMK-5 exhibits an ultrahigh adsorption rate and superior adsorption capacities for these dyes. Its maximum adsorption capacities for reactive blue 19, acid red 57 and fuchsin basic were 733, 1131 and 1403 mg g⁻¹, respectively, and significantly greater than other literature reported results on porous carbons. Following adsorption of reactive blue 19, CMK-5 carbon could be regenerated by either ethanol extraction or thermal annealing at 600 °C, reaching ∼51% and ∼77%, respectively of the adsorption capacity of the original carbon. For comparison, ordered mesoporous carbon CMK-3 (rod structure), polymer based disordered mesoporous carbon, and steam and CO₂ activated commercial coconut carbons were investigated for the adsorption of reactive blue 19. The fast adsorption rate of CMK-5 carbon is due to its unique properties of tubular mesostructure, bimodal mesopore system and high surface area. In the case of requiring emergency removal of large amount of dyes in aqueous solution, CMK-5 would be an ideal choice.     

Production of fibrous activated carbons from natural cellulose (jute, coconut) fibers for water treatment applications

Different fibrous activated carbons were prepared from natural precursors (jute and coconut fibers) by physical and chemical activation. Physical activation consisted of the thermal treatment of raw fibers at 950 °C in an inert atmosphere followed by an activation step with CO₂ at the same temperature. In chemical activation, the raw fibers were impregnated in a solution of phosphoric acid and heated at 900 °C in an inert atmosphere. The characteristics of the fibrous activated carbons were determined in the following terms: elemental analysis, pore characteristics, SEM observation of the porous surface, and surface chemistry. As the objective of this study was the reuse of waste for industrial wastewater treatment, the adsorption properties of the activated carbons were tested towards pollutants representative of industrial effluents: phenol, the dye Acid Red 27 and Cu²⁺ ions. Chemical activation by phosphoric acid seems the most suitable process to produce fibrous activated carbon from cellulose fiber. This method leads to an interesting porosity (S_BET up to 1500 m² g⁻¹), which enables a high adsorption capacity for micropollutants like phenol (reaching 181 mg g⁻¹). Moreover, it produces numerous acidic surface groups, which are involved in the adsorption mechanisms of dyes and metal ions.     

Surface chemistry of phosphorus-containing carbons of lignocellulosic origin

Activated carbon adsorbents were prepared by phosphoric acid activation of fruit stones in an argon atmosphere at various temperatures in the 400-1000 °C range and at different acid/precursor impregnation ratios (0.63-1.02). The surface chemistry of the carbons was investigated by elemental analysis, cation exchange capacity (CEC, measured by neutralization of NaOH with acidic surface groups), infrared spectroscopy and potentiometric titration. Porous structure was derived from adsorption isotherms (N₂ at −196 °C and CO₂ at 0 °C). It was demonstrated that all carbons show considerable cation exchange capacity, the maximum (CEC = 2.2 mmol g⁻¹) being attained at 800 °C, which coincides with the maximum contents of phosphorus and oxygen. The cation exchange properties of phosphoric acid activated carbons from fruit stones are chemically stable in very acidic and basic solutions. Proton affinity distributions of all carbons show the presence of three types of surface groups with pK at 2.0-3.3, 4.6-5.9 and 7.6-9.1. These pK ranges were ascribed primarily to: (a) phosphorus-containing and carboxylic groups; (b) lactonic groups, and (c) phenolic groups, respectively. Phosphoric acid activated carbons are microporous with a relatively small contribution of mesopores. A maximum BET surface area of 1740 m² g⁻¹ was attained at 400 °C.     

Removal of basic dyes from aqueous solution by low-cost adsorbent: Wood apple shell (Feronia acidissima)

The adsorption of two basic dyes, methylene blue (MB) and crystal violet (CV) on wood apple shell (WAS) were investigated using a batch adsorption technique. A series of experiments were undertaken in an agitated batch adsorber to assess the effect of the system variables such as solution pH, dye concentration and temperature. Removal of dyes was observed to be most effective at higher pH. Freundlich and Langmuir isotherm models were applied to the equilibrium data. The results showed that Langmuir equation fits better than the Freundlich equation. It was observed that the WAS adsorbent showed higher adsorption capacity for crystal violet (130 mg/g) than methylene blue (95.2 mg/g). The FTIR studies indicate that the interaction of dye and WAS surface is via the nitrogen atoms of the adsorbate and oxygen groups of the adsorbent. The adsorption of dyes onto WAS proceeds according to a pseudo-second-order model. Thermodynamic parameters such as free energy (ΔG°), enthalpy (ΔH°) and entropy (ΔS°) were also calculated. The studies show that WAS, a lignocellulosic inexpensive material, can be an alternative to other expensive adsorbents used for dye removal in wastewater treatment.     

Preparation of microporous sorbents from cedar nutshells and hydrolytic lignin

Carbon nutshells and hydrolytic lignin were used as starting materials for the preparation of microporous active carbons. Optimum parameters for cedar nutshell carbonization have been selected (temperature of carbonization 700-800 °C, rate of heating less than 3 °C/min) for the preparation of microporous carbons (average pore width 0.56 nm). The textural characteristics of microporous carbons made from nutshell are similar to those of a ‘Coconut’ carbon molecular sieve, but the latter has both a higher CO₂ adsorption capacity and a higher coefficient of N₂/O₂ separation. The influence of carbonization and steam-activation parameters on the microtexture and molecular-sieve properties of granular carbons made from hydrolytic lignin was also investigated. A low rate of heating (less 3 °C/min) promotes the formation of micropores with average sizes around 0.56-0.58 nm at carbonization temperature 700 °C. At the same carbonization temperature the average sizes of micropores were 0.7-0.78 nm at rates of heating more than 3 °C/min. The activation of lignin-char with steam at 800 °C resulted in the formation of active carbons with more developed micropore volume (0.3-0.35 cm³ g⁻¹) and with micropores of widths around 0.6-0.66 nm which are able to separate He from a He-CH₄ mixture. The size of the micropores was varied as a function of burn off value.     

Equilibrium and kinetic modelling of the adsorption of Cd ions onto chestnut shell

A study on the removal of Cd²⁺ ions from aqueous solutions by acid formaldehyde pretreated chestnut (Castanea sativa) shell was conducted in batch conditions. The influence of different parameters: adsorption time, temperature (15, 25 and 35 °C) and initial concentration of Cd²⁺ ions (15.3, 50.5 and 87.3 mg L^− 1), on cadmium uptake was analysed. Cadmium free and cadmium loaded chestnut shell were characterized by FTIR spectroscopy, which evidenced the functional groups involved in cadmium uptake. Cadmium adsorption equilibrium could be described by the Freundlich adsorption model at all the temperatures essayed, which predicted shell heterogeneity. The Cd²⁺ adsorption process by chestnut shell followed the pseudo second order kinetic model. Cadmium sorption capacity increased with decreasing temperature at an initial concentration of 15.3 mg L^− 1 and with increasing initial cadmium concentration at a temperature of 25 °C. The second order kinetic constant, which increased with increasing temperature, was used to calculate the energy of adsorption as equal to 19.2 kJ mol^− 1.     

Determination of EMC isotherms and appropriate mathematical models for canola

Canola seed needs to be dried to minimize damage during subsequent unit operations. In order to optimize the drying and storage processes of seeds it is necessary to know the equilibrium moisture content at different air equilibrium relative humidities and temperatures. In the present work adsorption equilibrium moisture content isotherms were determined for a specific local canola variety at 25, 40 and 55 °C and seven air relative humidifies within the range of 11-90%. Experimental data were used to model the adsorption isotherm process using non-linear regression analysis. Thirteen available mathematical and semi empirical models were employed to find the best fit isotherm curve model. The Halsey model showed the best results at 25 and 40 °C and the values of coefficient of determination (R²), chi-square (χ²) and root of mean square error (RMSE) were 0.993, 0.122 and 0.295 at 25 °C and 0.994, 0.042 and 0.174 at 40 °C. Another best fit mode was the GAB model at 55 °C which resulted in the values of 0.997, 0.023 and 0.120 for R², χ² and RMSE respectively. The adsorption monolayer moisture content (m₀) was also evaluated using BET equation. The m₀ values at 25 °C, 40 °C and 55 °C were 0.017, 0.016 and 0.015 g H₂O/g solid and the corresponding constant values of the BET equation were found to be −4.733, −5.129 and −10.299 respectively.     

Comparisons of pore properties and adsorption performance of KOH-activated and steam-activated carbons

Carbonaceous adsorbents with controllable pore sizes derived from carbonized pistachio shells (i.e., char) were prepared by the KOH activation and steam activation methods in this work. The pore properties including the BET surface area, pore volume, pore size distribution, and pore diameter of these activated carbons were characterized by the t-plot method based on N₂ adsorption isotherms. Through varying the KOH/char ratios from 0.5 to 3, the KOH-activated carbons exhibited BET surface areas ranging from 731 to 1687 m²/g with a similar micropore content (80–92%). The carbons activated by steam at 830 °C for 2 h had a BET surface area of 821 m²/g with the micropore content of 42%. The micropore/total pore volume ratio (V_micro/V_pore) and average pore size (D_pore) were independent of the KOH/char ratio, revealing that KOH activation is a powerful method in developing and controlling the number of micropores with a very similar pore size distribution. The adsorption equilibria and kinetics of methylene blue, basic brown 1, acid blue 74, 2,4-dichlorophenol, 4-chlorophenol, and phenol from water on all activated carbons at 30 °C were investigated to demonstrate the fact that adsorption of organics is not only dependent upon the BET surface area but is also determined by the relative size between pores and molecules. The adsorption isotherms were subjected to the model fitting according to Langmuir and Freudlich equations. By comparing the projected area of adsorbates, the surface coverage of phenols is about 3.6 times of that of dyes (based on unit gram of activated carbon). The Elovich equation was found to suitably describe the adsorption process of all KOH-activated carbons while the adsorption behavior on the steam-activated carbon was reasonably fitted with the intraparticle diffusion model.     

Synthetic carbons activated with phosphoric acid: I. Surface chemistry and ion binding properties

Synthetic activated carbons were prepared by phosphoric acid activation of a styrene-divinylbenzene copolymer at various temperatures in the 400-1000 °C range. The resulting carbons were characterized by elemental analysis, cation-exchange capacity measurement, infrared spectroscopy, potentiometric titration with calculation of proton affinity spectra, and copper adsorption from solution. The results indicate that the synthetic carbons obtained possess acidic character and show cation-exchange properties similar to those of oxidized carbons. However, the acidic compounds arising from treatment with phosphoric acid are tightly bound to the carbon lattice and are chemically and thermally more stable than those introduced by oxidative treatments. The largest amount of cation-exchange surface groups is introduced after activation at 800 °C. Infrared investigations showed that phosphorus compounds may be polyphosphates bound to the carbon lattice. Proton affinity distribution curves calculated from potentiometric titration experiments showed four types of surface groups on synthetic phosphoric acid activated carbons. Among them phosphorus-containing groups are the most important for the adsorption of heavy metal ions (copper) from acid solutions. Thus, carbons activated with phosphoric acid may be regarded as prospective cation-exchangers for the removal of heavy metals from water solutions.     

Dynamical adsorption and temperature-programmed desorption of VOCs (toluene, butyl acetate and butanol) on activated carbons

The elimination of solvent vapors from paint shop atmospheres and their recovery for possible re-use is a current environmental requirement. We have studied the dynamical adsorption at 23 °C of typical car paint solvents, i.e. toluene, butylacetate and butanol, on two microporous activated carbons, and the thermal regeneration of these carbons with hot air at 150 °C. A sequence of seven adsorption-desorption cycles with a mixture of these solvents left the carbons with some textural changes but the adsorption capacity remained virtually unaffected. Heavy volatile compounds, proceeding from the possibly unstabilized binder, are eliminated in the course of the first adsorption-desorption runs. Differential scanning calorimetry applied to the desorption in argon of pure solvents showed that the desorption enthalpies ΔH_des are close to, or slightly larger than, the evaporation enthalpies ΔH_vap except for butanol, which exhibited a particularly high ΔH_des value. Temperature-programmed desorption experiments, obtained with carbon samples heated in a helium flow containing oxygen traces, evidenced the desorption of numerous oxidation products. This finding may have consequences for hot air regeneration processes.     

Adsorption equilibrium of organic vapors on single-walled carbon nanotubes

Gravimetric techniques were employed to determine the adsorption capacities of commercially available purified electric arc and HiPco single-walled carbon nanotubes (SWNTs) for organic compounds (toluene, methyl ethyl ketone (MEK), hexane and cyclohexane) at relative pressures, p/p₀, ranging from 1 × 10⁻⁴ to 0.95 and at isothermal conditions of 25, 37 and 50 °C. The isotherms displayed both type I and type II characteristics. Adsorption isotherm modeling showed that SWNTs are heterogeneous adsorbents, and the Freundlich equation best describes the interaction between organic molecules and SWNTs. The heats of adsorption were 1-4 times the heats of vaporization, which is typical for physical adsorption of organic vapors on porous carbons.     

Adsorption behaviors of mercury from aqueous solution using sulfur-impregnated adsorbent developed from coal

Adsorption of mercury from aqueous solution on sulfur-impregnated adsorbent has been studied. Raw coal was mixed with K₂S powder, and then heated at 800-1000 °C for 30 min in nitrogen to produce sulfur-impregnated adsorbent. The sulfur content and specific surface area of the adsorbent were determined, and the ability of the adsorbent to adsorb mercury in aqueous solution was examined. With increasing temperature of sulfur-impregnation, specific surface area of the adsorbent increases, while sulfur content of the adsorbent is almost constant. The adsorbent obtained at 900 °C shows the highest and fastest adsorption of mercury from aqueous solution at 25 °C, and the elution extents of adsorbed mercury are negligible in distilled water and 10% in 0.1 M HCl solution, respectively. Adsorption kinetics was tested for pseudo-first order and pseudo-second order reactions, and the rate constants of adsorption for these kinetic models were calculated. Adsorption experiments demonstrate that the adsorption process corresponds to pseudo-second-order kinetic model than pseudo-first-order model. With increasing temperature of aqueous solution, the kinetics of adsorption becomes faster and the amount of mercury adsorbed on the adsorbent increases. The thermodynamic values, ΔG⁰, ΔH⁰ and ΔS⁰, indicated that adsorption was an endothermic and spontaneous process.     

A study of the characteristics of activated carbons produced by steam and carbon dioxide activation of waste tyre rubber

This paper presents a study into the effect of different activation conditions on the porosity and adsorption characteristics of carbon adsorbents produced from waste tyre rubber. For the purpose of this work, three carbon series were produced using different activation temperatures (between 925 and 1100 °C) and oxidising agents (steam or carbon dioxide). Carbons produced to different degrees of burn off were characterised using gas (nitrogen) and liquid phase (phenol, methylene blue and Procion Red H-E2B) adsorption. Total micropore volumes and BET surface areas increased almost linearly with the degree of activation to 0.554 ml/g and 1070 m²/g, respectively, while the development of external surface area was particularly rapid at degrees of activation above 50 wt% burn off. Steam was observed to generate a narrower but more extensive microporosity than carbon dioxide. However, carbon dioxide produced carbons of slightly larger external surface areas. Activation at higher temperatures resulted in pores of slightly larger dimensions, although this was only evident in highly activated samples. Porosity characteristics were reflected in the capacity of the carbons to adsorb species of different molecular size from solution. In this respect, steam-activated carbons presented greater capacities for the adsorption of smaller molecular size compounds (phenol), while carbon dioxide-activated carbons adsorbed larger textile dyes more effectively.     

Selective adsorption of organic sulfur in coal extract by using metal-loaded carbon

The objective of this study was to develop an efficient cleaning process for hydrocarbon resources. We investigated the removal of organic sulfur from coal extract by using metal-loaded carbons. Tetralin and tetralin/phenol mixture were used for thermal extraction of Illinois No. 6 coal at 375 °C with a holding time of 1 h, and we examined the effects of temperature on product yield and sulfur-removal behavior using metal-loaded carbons. A decrease in the n-hexane insoluble fraction was observed at a temperature range from 200 °C to 250 °C in the extracts of tetralin and tetralin/phenol mixture. The organic sulfur content in the n-hexane insoluble fraction drastically decreased with increasing temperature. The organic sulfur in the n-hexane insoluble fraction was reduced above 200 °C, while the sulfur content reached 30-35% at 375 °C for both tetralin and tetralin/phenol mixture extracts. We investigated the effect of holding time on the extent of the coal extract desulfurization using Ni-loaded carbon. The sulfur content in the coal extract decreased as the holding time increased. The rate of coal extract desulfurization using tetralin/phenol was slower than that obtained using tetralin. The coal extract obtained using the tetralin/phenol mixture contained a heavier polar fraction, which may have impeded the adsorption. All organic sulfur in the coal extract could be successfully removed Ni-loaded carbon at a treatment temperature of 350 °C and a holding time of 8 h. No appreciable changes were observed in the content of carbon, hydrogen, or nitrogen at any temperature or holding time in the ultimate analysis of the n-hexane insoluble fraction treated with Ni-loaded carbon. The results demonstrated that Ni-loaded carbon was much effective in removing organic sulfurs from the coal extract.     

Study of adsorption isotherms and kinetic models for Methylene Blue adsorption on activated carbon developed from Egyptian rice hull (Part II)

Adsorption of Methylene Blue (MB) from aqueous solutions on activated carbon prepared from Egyptian rice hulls (ERHA) is studied experimentally. Results obtained indicate that the removal efficiency of Methylene Blue at 25 °C exceeds 99% and that the adsorption process is highly pH-dependent. Results showed that the optimum pH lies between 5 and 9. The amount of Methylene Blue adsorbed form aqueous solution increases with the increase of the initial Methylene Blue concentration and temperature. Smaller adsorbent particle adds to increase the percentage removal of Methylene Blue.The results fit the BET model for adsorption of MB on ERHA, corroborating the assumption of that the adsorbate molecules could be adsorbed in more than one layer thick on the surface of the adsorbent.A comparison of kinetic models at different conditions (pH, Temperature, adsorbent particle size, adsorbent dose and adsorbate concentration) applied to the adsorption of Methylene Blue on the adsorbent was evaluated for the pseudo first-order, the pseudo second-order, Elovich and intraparticle diffusion kinetic models, respectively. Results showed that the pseudo second-order kinetic model correlate the experimental data well.