Effect of surface properties of activated carbons on surfactant adsorption kinetics

This research investigates the adsorption properties of three activated carbons (AC) derived from coconut, coal, and wood origin. A linear relationship exists between the number of water molecules adsorbed onto each AC and the oxygen content determined elemental analysis and XPS. An inverse linear relationship exists between the plateau amount of dodecanoic acid anionic surfactant and the oxygen content on the surface of ACs. The surface charge on each AC’s surface had a linear relationship with the plateau amount of dodecanoic acid. A plug-flow heterogeneous surface diffusion model (PFHSDM) for a fixed-bed adsorption process was developed to describe the adsorption kinetics in a fixed-bed column. The model represents axially dispersed plug-flow, external mass transfer, adsorption equilibrium on the fluid-particle interface, and intraparticle diffusion. The larger molecular dimension of the dodecanoic acid as a more hydrophobic entity than octanoic acid led to a faster external mass transfer rate but a slower surface diffusion rate as estimated from the PFHSDM. The interaction between the organic moiety of surfactant and the AC surface chemistry such as surface oxygen content and surface charge contributes to the adsorption performance in both to the adsorption equilibrium and kinetics.     

Effect of carbon-oxygen and carbon-sulphur surface complexes on the adsorption of mercuric chloride in aqueous solutions by activated carbons

Several activated carbons obtained from commercial sources have been tested for their ability to remove mercuric chloride (HgCl₂) from aqueous solutions. The chemical nature of the surface of the activated carbons was changed by introducing carbon-oxygen and carbon-sulphur surface complexes. The influence of these types of complexes on the adsorption of HgCl₂ by the activated carbons has been studied. It seems that the existence of hydroquinonic, phenolic and hydrosulphide groups on the surface of the carbon reduces Hg(II) to Hg(I). However, there was an increase in the adsorption of Hg(II) when sulphide or hydrosulphide groups were present on the surface of the carbon. The effect of the pH of the solutions on HgCl₂ adsorption was also studied; when the pH was changed from 1 to 7 there was an enhancement of the adsorption of HgCl₂ by the activated carbons.     

Effect of the porous texture and surface chemistry of activated carbons on the adsorption of a germanium complex from dilute aqueous solutions

The effect of the adsorption properties and surface chemistry of activated carbons on the adsorption of germanium (IV) from dilute aqueous solutions (50 ppm) was investigated. A large number of activated carbons were obtained by activating three precursors, one coal and two lignocellulosic chars, with alkaline hydroxides, NaOH and KOH, and different activating agent/precursor ratios (from 1/1 to 5/1). The characterization of their textural properties, assessed by N₂ and CO₂ isotherms, and their oxygen surface chemistry, assessed by temperature-programmed desorption experiments, confirm that a large variety of materials with different surface areas, pore size distributions and surface chemistries are available for this study. To increase the Ge adsorption, an organic compound (catechol) was used as a ligand in order to form a germanium complex. Such a complex works very well, allowing its good adsorption on the activated carbons. The results showed that to achieve the highest Ge adsorption, the activated carbon should show a high apparent surface area, a wide microporosity and a moderate oxygen surface content that may assure the wettability of the solution but that does not produce large repulsive interactions.     

二种估算苯酚在改性活性炭上脱附活化能模型

应用程序升温吸附(TPD)技术分别测定了苯酚在空白活性炭以及负载Fe3+,Ag+的活性炭上TPD曲线,并采用理想TPD模型和改进的TPD模型估算苯酚在这些吸附材料上的脱附活化能,讨论了吸附材料表面负载Fe3+,Ag+对苯酚脱附活化能的影响。结果表明:采用改进的TPD模型估算得到的脱附活化能要低于理想TPD模型估算得到的活化能4.9%—5.9%,这是由于理想TPD模型忽略了脱附过程中可能出现的吸附质被再吸附现象。苯酚从负载硬酸Fe3+活性炭表面上脱附活化能大于其从原始活性炭表面脱附的活化能,而它从负载属于软酸的Ag+的活性炭表面上脱附所需的活化能小于其从空白活性炭表面脱附的活化能。     

Adsorption of benzoic acid and phenol from aqueous solution by activated carbons—effect of surface acidity

Effect of surface acidic groups of activated carbons on their adsorption characteristics for substrates from aqueous solutions were studied. Six kinds of carbons obtained commercially and their heat-treated products were used. Pore-size distribution, BET surface area and surface acidity were measured. Adsorption isotherms for benzoic acid and phenol from aqueous solutions (single or double components) were obtained. Substitution adsorption, i.e. substrate adsorbed preliminarily is substituted by another substrate, was also carried out. It was found that adsorption of benzoic acid is scarcely affected by surface acidity of carbons and the amount adsorbed is almost entirely controlled by the specific surface area of carbons. On the contrary, adsorption of phenol is retarded considerably by the acidity of carbons. In the case of solution of double components, benzoic acid is adsorbed predominatedly. The phenol adsorbed preliminarily is easily substituted by benzoic acid, but the substitution of benzoic acid by phenol scarcely proceeds.     

Study of cobalt adsorption from aqueous solution on activated carbons from almond shells

The adsorption of cobalt from aqueous solutions in a series of activated carbons obtained from almond shells has been studied. The chemical nature and textural characteristics of those activated carbons were investigated. Both surface basicity and porosity increase with increasing activation time. The cobalt uptake on those activated carbons also increases with the activation time. A great enhancement of the cobalt uptake was found when those activated carbons were treated with concentrated nitric acid. The influence of the pH on the cobalt adsorption process was also studied.     

Modified activated carbons with amino groups and their copper adsorption properties in aqueous solution

Activated carbons were prepared by two chemical methods and the adsorption of Cu (II) on activated carbons from aqueous solution containing amino groups was studied. The first method involved the chlorination of activated carbon following by substitution of chloride groups with amino groups, and the second involved the nitrilation of activated carbon with reduction of nitro groups to amino groups. Resultant activated carbons were characterized in terms of porous structure, elemental analysis, FTIR spectroscopy, XPS, Boehm titration, and pHzpc. Kinetic and equilibrium tests were performed for copper adsorption in the batch mode. Also, adsorption mechanism and effect of pH on the adsorption of Cu (II) ions were discussed. Adsorption study shows enhanced adsorption for copper on the modified activated carbons, mainly by the presence of amino groups, and the Freundlich model is applicable for the activated carbons. It is suggested that binding of nitrogen atoms with Cu (II) ions is stronger than that with H+ions due to relatively higher divalent charge or stronger electrostatic force.     

Studies on the adsorption of caesium,thallium, strontium and cobalt radionuclides on activated carbons from aqueous solutions

Individual adsorption studies of Cs⁺, Tl⁺, Sr²⁺ and Co²⁺ on activated carbons from aqueous solutions are reported. The carbon samples were characterised using different techniques. The surface area and the micro-, meso- and macropore volumes of all samples have been calculated. The chemical nature of the surface of the activated carbons was also studied. Optimal conditions for the adsorption of the metal ions have been identified. The adsorption of these cations by the carbon samples was also determined in the presence of a number of different anions. The data suggest the possible use of activated carbons for the preconcentration and separation of some cations.     

Study of the kinetics of the adsorption by activated carbons of 2,4,5-trichlorophenoxyacetic acid from aqueous solution

The kinetics of the adsorption of 2,4,5-trichlorophenoxyacetic acid by activated carbons from an aqueous solution has been studied at several temperatures (10°C to 50°C). The activated carbons used were Merck (No. 2514) and one prepared from almond shells (C-A-14). The adsorption process seems to be of the order two and the desorption of the order one. The thermodynamic functions for the formation of the activated complex have also been calculated.     

Importance of activated carbon's oxygen surface functional groups on elemental mercury adsorption

The effect of varying physical and chemical properties of activated carbons on adsorption of elemental mercury (Hg⁰) was studied by treating two activated carbons to modify their surface functional groups and pore structures. Heat treatment (1200 K) in nitrogen (N₂), air oxidation (693 K), and nitric acid (6N HNO₃) treatment of two activated carbons (BPL, WPL) were conducted to vary their surface oxygen functional groups. Adsorption experiments of Hg⁰ by the activated carbons were conducted using a fixed-bed reactor at a temperature of 398 K and under N₂ atmosphere. The pore structures of the samples were characterized by N₂ and carbon dioxide (CO₂) adsorption. Temperature-programmed desorption (TPD) and base-acid titration experiments were conducted to determine the chemical characteristics of the carbon samples. Characterization of the physical and chemical properties of activated carbons in relation to their Hg⁰ adsorption capacity provides important mechanistic information on Hg⁰ adsorption. Results suggest that oxygen surface complexes, possibly lactone and carbonyl groups, are the active sites for Hg⁰ capture. The carbons that have a lower carbon monoxide (CO)/CO₂ ratio and a low phenol group concentration tend to have a higher Hg⁰ adsorption capacity, suggesting that phenol groups may inhibit Hg⁰ adsorption. The high Hg⁰ adsorption capacity of a carbon sample is also found to be associated with a low ratio of the phenol/carbonyl groups. A possible Hg⁰ adsorption mechanism, which is likely to involve an electron transfer process during Hg⁰ adsorption in which the carbon surfaces may act as an electrode for Hg⁰ oxidation, is also discussed.     

Influence of activated carbons porous structure on iopamidol adsorption

In the present study the adsorption of iopamidol (a pharmaceutical compound used in soft tissues diagnostic imaging based on X-ray radiography) onto activated carbons was assessed, since this is an effective technology to remove pharmaceutical compounds that fail to be degraded in conventional wastewater treatments. Three sisal-based carbons prepared by chemical activation with KOH, and two commercial carbons, were selected in order to understand the role of the porous structure in the removal of iopamidol from aqueous phase. The kinetic and equilibrium adsorption results indicate that iopamidol is adsorbed in mesopores and also in larger micropores (supermicropores). The adsorption isotherms reflect a complex mechanism originating unusual two-step isotherms, which highlights the influence of the porous structure. As proven using conductivity measurements and computational calculations, iopamidol can be adsorbed as a single molecule or in the form of aggregates, filling either small or much larger pores in a discontinuous way. By conjugating the molecular dimensions of the iopamidol species and the micropore size distribution of the samples, it was demonstrated that the unusual two-step isotherms are related with the absence of pores with width between 1.2 and 2.0 nm.     

Adsorption of cadmium ions from aqueous solutions by activated carbon with oxygen-containing functional groups

The adsorption of aqueous cadmium ions (Cd(II)) have been investigated for modified activated carbon (AC-T) with oxygen-containing functional groups. The oxygen-containing groups of AC-T play an important role in Cd(II) ion adsorption onto AC-T. The modified activated carbon is characterized by scanning electron microscopy, Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The results of batch experiments indicate that the maximal adsorption could be achieved over the broad pH range of 4.5 to 6.5. Adsorption isotherms and kinetic study suggest that the sorption of Cd(II) onto AC-T produces monolayer coverage and that adsorption is controlled by chemical adsorption. And the adsorbent has a good reusability. According to the FT-IR and XPS analyses, electrostatic attraction and cation exchange between Cd(II) and oxygen-containing functional groups on AC-T are dominant mechanisms for Cd(II) adsorption.     

The influence of porosity and surface oxygen groups of peat-based activated carbons on benzene adsorption from dry and humid air

Activated carbons (ACs) prepared from peat were used for benzene adsorption (5 ppmv) from dry and humid (relative humidity (RH) 70%) air streams. Benzene uptake by the ACs was lower in the presence of water vapor due to competition between benzene and water molecules for the adsorption sites. Adsorption of benzene from dry and humid air on the ACs with low content of surface oxygen groups was attributed to the presence of narrow micropores (size <0.7 nm). A linear correlation between the amount of adsorbed benzene and micropore volume calculated from CO₂ adsorption isotherms was found. The coefficients of determination R² were 0.87 for benzene adsorption in the absence of water vapor and 0.83 for adsorption at relative humidity 70%. It was shown that the presence of surface groups in the ACs reduces benzene uptake more profoundly in the presence of moisture than in the dry conditions.     

Kinetics of zirconium ions adsorption on activated charcoal from aqueous solutions

The batch kinetics of adsorption of the zirconium ions from aqueous solutions on activated charcoal has been investigated over a wide range of concentration of zirconium ions (1.0–5.0 g/l) and temperatures (10–50°C). The adsorption process of zirconium ions proceeds via two stages; the first stage is rather fast, followed by a much slower one. The Bangham equation was used to study the kinetics of the zirconium ions' adsorption on activated charcoal. It is observed that the diffusion of zirconium ions into the pores of the activated charcoal controls the kinetics of the adsorption process. Moreover, zirconium ion adsorption obeys the Freundlich and Langmuir isotherms in the concentration range studied. The adsorption equilibrium constant (k_c) values for zirconium ions adsorption on activated charcoal have also been calculated at different temperatures. Various thermodynamic quantities, ΔG, ΔH, and ΔS were computed from k_c values. The results showed that the adsorption of zirconium ions on activated charcoal is an endothermic process.     

Removal of phenol from aqueous solutions by adsorption onto polymeric adsorbents

Phenolic compounds are one of the most representative pollutants in industrial wastewater, and efficient removals of them have attracted significant concerns. In this study, several commercial and new synthetic polymers (acrylonitrile, 1,3‐butadiene, and styrene copolymer (ABS), styrene, acrylonitrile copolymer (SAN), poly(vinyl chloride) (PVC), poly(methyl methacrylate) (PMMA), poly(tert‐butyl acrylate) (ptBA)) with special functionalities were evaluated for their ability to remove phenol from an aqueous solution. Equilibrium studies were conducted in the range of 20–100 mg/L initial phenol concentrations, 3–11 pH solutions, and a temperature range of 25–65°C. The results showed that (styrene, 1,3‐butadiene) copolymer (SAN) gave the best adsorption capacity among all of the polymers tested. The solution temperature, phenol concentration, and agitation rate played a significant role in influencing the capacity of the adsorbents toward phenol molecules. An increase in solution temperature led to a significant increase in the adsorption capacity of SAN. The percentage of adsorption decreased when initial concentration of phenol increased. However, the percentage removal of phenol was observed to increase with agitation. Removal of phenol using polymeric microbeads is difficult to investigate under high and low pH values because it requires a lot of acid or base to adjust the pH values in the adsorption media. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

活性炭纤维吸附石化废水中苯酚的吸附平衡及动力学

以活性炭纤维(ACF)为吸附剂,研究了ACF对石化废水中苯酚的吸附平衡及动力学。在25、40、55及65℃下测定了吸附平衡等温线,采用Langmuir、Freundlich和Redlich-Peterson等温方程对吸附平衡数据进行了拟合,结果表明吸附平衡数据更符合Langmuir与Redlich-Peterson方程。体系温度从25、40、55升高到65℃时,ACF对模拟废水中苯酚的吸附能力随温度升高而降低,而ACF对石化废水中苯酚的吸附能力并不完全随温度升高而降低。ACF对石化废水与模拟废水中苯酚的吸附过程均符合拟二级动力学方程。颗粒内扩散模型对吸附动力学实验数据的拟合结果表明,吸附初期吸附速率主要受颗粒内扩散控制且石化废水中苯酚吸附的k_id随温度升高而增大,吸附中后期吸附速率除了受颗粒内扩散控制外还受到外扩散的影响。热力学分析表明,石化废水中ACF吸附苯酚过程的ΔG<0,由于石油类物质对苯酚吸附的影响,温度升高ΔG的数值变化不大。     

Combined adsorption and electrochemical processes for the treatment of acidic aqueous phenol wastes

This paper describes a combined adsorption/electrochemical reaction device for the treatment of acidic aqueous phenol wastes. The system works in batch mode. In each operation cycle there are two stages: (i) treatment of waste, in which the organic matter contained in the waste is removed from the aqueous solution and (ii) activated carbon regeneration, in which adsorbed organics are removed from the system and converted into carbon dioxide. The system leads to successful treatment of these wastes and transforms the organics contained in the waste into carbon dioxide and electrocoagulated solids. The granular activated carbon (GAC) bed of the system achieves rapid removal of the organics, with treatment time shorter than those reported for conventional electrochemical treatments. The regeneration of the GAC is achieved by electrochemical means and efficiencies close to 80% are obtained. The energy consumption of this system is similar to those reported for other electrochemical technologies used to treat aqueous wastes.