Kinetics and Equilibrium Sorption Studies of 4-Nitrophenol on pyrolyzed and activated oil shale residue

Sorption of the organic pollutant 4-nitrophenol (4-NP) by pyrolyzed and activated Jordanian oil-shale was studied. Pyrolyzed oil shale was prepared using a fluidized bed reactor at 520 °C in the presence of nitrogen. Physical activation was carried out by treating the pyrolyzed oil shale with CO₂ at 830 °C, while chemical activation was achieved by using KOH and ZnCl₂ as impregnating agents. Batch kinetics and isotherm studies were conducted to evaluate the sorption process. Effects of contact time, initial sorbate concentration, sorbent concentration, temperature, pH and inorganic salts (NaCl and KCl) on the sorption process by the different sorbents were considered. Chemically activated oil shale, pretreated with ZnCl₂, gave the highest uptake of 4-NP. The isotherm experimental data fit reasonably well to Langmuir, Freundlich and Redlich-Paterson models. Three kinetic models, namely the Morris-Weber, Lagergren, and Pseudo-Second-Order model (PSOM), were applied to represent the experimental results for both pyrolyzed and ZnCl₂-oil shale sorbents.     

Adsorption of copper and zinc by oil shale

 Oil shale is able to remove appreciable amounts of copper and zinc ions from aqueous solutions. It was noted that an increase in the adsorbent concentration with constant copper or zinc concentration resulted in greater metal removal from solution. An increase in the copper or zinc concentration with a constant sorbent concentration resulted in higher metal loading per unit weight of sorbent. For both metals, copper and zinc, equilibrium was attained after 24-h contact time. Increase in the initial pH or temperature of the metal solution resulted in an increase in the metal uptake per unit weight of the sorbent. Freundlich isotherm model was found to be applicable for the experimental data of Cu²⁺ and Zn²⁺. The results showed that oil shale could be used for the adsorption of the Cu²⁺ and Zn²⁺ with higher affinity toward Zn²⁺ ions. Addition of sodium salt to the metal solution influenced copper removal positively, but inhibited zinc removal. Received: 3 January 2000 · Accepted: 27 June 2000     

Removal of dyes from aqueous solutions using low-cost sorbents made of solid residues from olive-mill wastes (JEFT) and solid residues from refined Jordanian oil shale

The effectiveness of processed solid residue from olive-mill waste (JEFT) and solid residue of pyrolyzed oil shale in removing methylene blue as a cationic dye and methyl orange as an anionic dye from aqueous solutions has been investigated and compared with that of a commercial activated carbon, namely coconut-shell carbon. All three sorbents showed significant methylene-blue removal, but only the coconut granular-activated carbon showed notable methyl-orange removal. The oil-shale sorbent showed no removal and the olive carbon showed poor removal of methyl orange. The removal of both methylene blue and methyl orange increases with the lapse of time, and attains equilibrium in 100 min. Received: 12 May 1999 · Accepted: 1 November 1999     

Partial pyrolysis of olive wood to improve its sorption of chlorophenols and nitrophenols

Partial pyrolysis alters the chemical and textural properties of the lignocellulosic material. This work reports the effect of partial pyrolysis of olive wood on adsorption isotherms, kinetics and thermodynamics of chloro and nitrophenols. Shape of adsorption isotherms of the partially pyrolyzed sorbents was L3 for phenol; L2 for 2-nitrophenol and 2,4-dinitrophenol; H3 for 2-chlorophenol, 3-chlorophenol and 4-nitrophenol; and H2 for 4-chlorophenol. The pyrolyzed olive wood sorbents obeyed Langmuir and Freundlich models. Pyrolysis raised adsorption capacity, favorability and spontaneity; the adsorption became more exothermic; the randomness decreased. The adsorption was mainly physical; it occurred first by film diffusion then by pore-filling. Adsorption followed second-order rate kinetics. Adsorption of phenols on olive wood seemed to be governed by hydrophobic interaction. Washing the pyrolyzed olive wood with ethanol caused a decrease in adsorption capacity, favorability and spontaneity, and the adsorption became less exothermic. This indicated that pyrolysis produced species on the olive wood surface that played a significant role in phenols adsorption.     

Adsorption characteristics of phenol and heavy metals on biochar from <Emphasis Type="Italic">Hizikia fusiformis</Emphasis>

The objective of the present study is to evaluate the absorption efficacy of H. fusiformis biochar (HFB) for the removal of phenol and heavy metals from single and mixed solute systems of these species under different experimental conditions. The effects of contact time, pH change, initial phenol concentration, and heavy metal concentration on the adsorption capacity of HFB were investigated. The kinetics and equilibrium models of sorption of the components of the single and mixed solute systems on HFB were also studied. The experimental data were fitted to kinetic and equilibrium models. The batch experiments revealed that 360 min of contact time was sufficient to achieve equilibrium for the adsorption of both phenol and heavy metals. The adsorption of phenol and nickel by HFB followed the pseudo-second-order kinetic model, which was quite adequate for describing the adsorption mechanism. The equilibrium data for the adsorption of phenol and heavy metals fit well to the Langmuir model with regression coefficients of R ² > 0.819. The maximum Langmuir adsorption capacities were 10.39, 12.13, 22.25, 2.24, 2.89, and 22.03 mg/g for phenol, Ni²⁺, Zn²⁺, Cu²⁺, Pb²⁺, and Cd²⁺, respectively. Moreover, HFB exhibited optimal sorption under slightly acidic conditions at pH 6. The HFB used in the present study exhibited higher adsorption capacity for the removal of phenol and heavy metals from aqueous solutions compared to documented sorbents. These results demonstrate that HFB is potentially useful for alleviating the harmful effects of phenol and heavy metal in wastewater treatment systems.     

Sorption of lead by chemically modified rice bran

In this work, the effectiveness of native and chemically modified rice bran to remove heavy metal Pb(II) ions from aqueous solution was examined. Chemical modifications with some simple and low-cost chemicals resulted in enhancement of the adsorption capacities and had faster kinetics than native rice bran. Experiments were conducted in shake flasks to monitor the upshot of parameters over a range of pH, initial Pb(II) concentrations and contact times using a batch model study. The sorption capacities q (mg g^?1) increased in the following order: NaOH (147.78), Ca(OH)₂ (139.08), Al(OH)₃ (127.24), esterification (124.28), NaHCO₃ (118.08), methylation (118.88), Na₂CO₃ (117.12) and native (80.24). The utmost uptake capacity q (mg g^?1) was shown by NaOH-pretreated rice bran. The results showed that, using NaOH-modified rice bran, the chief removal of Pb(II) was 74.54 % at pH 5, primary Pb(II) concentration 100 mg L^?1 and contact time 240 min. Equilibrium isotherms for the Pb(II) adsorption were analyzed by Langmuir and Freundlich isotherm models. The Langmuir isotherm model, showing Pb(II) sorption as accessible through the high value of the correlation coefficient (R ² = 0.993), showed a q _max value of 416.61 mg g^?1. The kinetic model illustrated adsorption rates well, depicted by a second order, which gives an indication concerning the rate-limiting step. Thermodynamic evaluation of the metal ion ?G ^o was carried out and led to the observation that the adsorption reaction is spontaneous and endothermic in nature. NaOH chemically modified rice bran was a superb biosorbent for exclusion of Pb(II) and proved to be excellent for industrial applications.     

Phosphate removal from water by naturally occurring shale,sandstone, and laterite: The role of iron oxides and of soluble species

Aqueous phosphate removal by three geomaterials from Ivory Coast was evaluated to determine their potential application as low-cost phosphate adsorbents in wastewater treatment. Batch experiments showed that phosphate uptake strongly depended on pH. Laterite and sandstone dissolution was less pronounced compared to shale. A correlation between concentrations of aqueous cation species released from shale and phosphate uptake was observed. The kinetics were well described using the pseudo-second-order model. Isotherms displayed a saturation level on shale, while phosphate uptake continuously increased for laterite and sandstone. The removal efficiency decreased in the following ranking order: laterite > sandstone > shale. Laterite was also the most efficient adsorbent in column experiments. The high phosphate removal efficiency of laterite (8.3 mg PO₄ g^?1) was attributed to the presence of superparamagnetic low grain sizes of goethite. Laterite is a particularly promising material for further investigation in wastewater treatment technology such as constructed wetlands.     

Hydromechanical behavior of Tournemire argillites: Measurement of the poroelastic parameters and estimation of the intrinsic permeability by œdometric tests

Knowledge of shale poromechanical behavior is proven to be essential for various environmental issues such as deep geological storage of CO₂, high level radioactive waste storage, oil field abandonment and so forth… This paper sets out the key points of shale experimental characterization within the framework of Biot's mechanics of fluid saturated porous solids. Shales are well known to present a more or less transverse isotropy. This paper describes a full methodology for ?dometric tests on such sensitive and weakly permeable material. To illustrate this methodology, measurements carried out on Tournemire argillite are proposed. A transverse isotropic poroelastic model is also used to give a more in depth understanding of the hydromechanical coupling. Copyright © 2010 John Wiley & Sons, Ltd.     

Adsorption of hexavalent chromium onto activated carbon derived from <Emphasis Type="Italic">Leucaena leucocephala</Emphasis> waste sawdust: kinetics,equilibrium and thermodynamics

The adsorptive removal of Cr(VI) was studied using activated carbon derived from Leucaena leucocephala (ACLL). The physico-chemical properties of ACLL were determined using proximate analysis and N₂ BET surface area analysis. The N₂ BET surface area of ACLL was determined to be 1131 m² g^?1. The point of zero charge (pH_pzc) of 5.42 indicated that ACLL surface was positively charged for pH below the pH_PZC, attracting anions. The effect of experimental operating parameters such as time of contact, ACLL dose, pH, initial concentration and temperature was investigated. The optimum values of parameters such as concentration of 100 mg L^?1, 300 mg of ACLL dose, time of contact of 60 min, pH of 4 indicated the maximum Cr(VI) uptake of 13.85 mg g^?1. The pseudo-second-order kinetic model best fitted with the Cr(VI) adsorption data. Adsorptive removal of Cr(VI) onto ACLL satisfactorily fitted in the order of Redlich–Peterson > Freundlich > Langmuir > Temkin adsorption isotherm model. The thermodynamic parameters showed the adsorption of Cr(VI) onto ACLL was an endothermic and spontaneously occurred process.     

Influences of activated sludge surface properties on adsorption of aqueous fullerene C<Subscript>60</Subscript> nanoparticles

Rapid increases in the amounts of fullerene C₆₀ nanoparticles (nC₆₀) being produced and used will inevitably lead to increases in the amounts released into the aquatic environment. This will have implications for human and ecosystem health. Wastewater treatment plants are key barriers to nC₆₀ being released into aquatic systems, but little information is available on how adsorption processes in wastewater treatment plants affect the fates of nC₆₀. We investigated the effects of the surface properties of activated sludge on the adsorption of nC₆₀ and related mechanisms by modeling the adsorption kinetics and equilibrium process and performing correlation analyses. The adsorption of nC₆₀ closely followed the pseudo-second-order kinetic model (R > 0.983), the Freundlich isotherm model (R > 0.990), and the linear partitioning isotherm model (R > 0.966). Different adsorption coefficients, 1.070–4.623 for the Freundlich partitioning model and 1.788–6.148 for the linear partitioning model, were found for different types of activated sludge. The adsorption coefficients significantly positively correlated with the zeta (ζ) potential (R = 0.877) and hydrophobicity (R = 0.661) and negatively correlated with particle size (R = ?0.750). The results show that nC₆₀ adsorption is strongly affected by the surface properties of activated sludge because changes in surface properties cause changes in the electrostatic and hydrophobic interactions that occur.     

Adsorption of methyl tert-butyl ether using granular activated carbon: Equilibrium and kinetic analysis

The adsorption of methyl tert-butyl ether by granular activated carbon was investigated. The experimental data were analyzed using the Freundlich isotherm and the Langmuir isotherm. Although equilibrium data were found to follow Freundlich isotherm model, it were fitted better by the Langmuir model with a maximum adsorption capacity of 204.1 mg/g. The kinetic data obtained at different concentrations were analyzed to predict the constant rate of adsorption using three common kinetic models: pseudo-first-order, pseudo-second-order equation and intraparticle diffusion equation. The pseudo-second-order model was suitable for describing the adsorption kinetics for the removal of methyl tert-butyl ether from aqueous solution onto granular activated carbon. Both the Lagergren first-order rate constant k ₁ and pseudo-second-order rate constant k ₂ decrease with increasing initial concentrations of methyl tert-butyl ether and the intraparticle diffusion rate constant k _p shows the reverse characteristic. Analysis of sorption data using a boyd plot confirmed that external mass transfer is the main rate-limiting step at the initial stage of adsorption. Results illustrate that granular activated carbon is an effective adsorbent for methyl tert-butyl ether and also provide specific guidance into adsorption of methyl tert-butyl ether on granular activated carbon in contaminated groundwater.     

Activation and regeneration of a soil sorbent for defluoridation of drinking water

Geomaterials can be cost-effective sorbents for use in water treatment. In this study, a heavily-weathered Tertiary soil from Xinzhou, China was used as a sorbent for defluoridation of high-fluoride drinking water. The soil is composed of quartz, feldspar, illite and goethite, with an Fe oxide content of 6.75%. Batch and column experiments were done to characterize the F⁻ removal properties and to develop an optimal activation and regeneration procedure. The soil can be regenerated following a simple base-acid rinsing procedure. This can be performed in situ, i.e., by passing the rinsing solutions directly through the treatment column. The same regeneration procedure can be used to activate the pristine soil. Fluoride sorption is described by a Freundlich isotherm model and the bulk of the uptake occurs within 1.5 h. Iron oxide coatings on soil particles and perhaps ≡FeOH surface groups at particle edges of illite grains are likely responsible for the soil's F-sorption property. As collected in the field, the soil has a low permeability and is thus unsuitable for direct use in a flow-through column. Heat-treatment at 400–500°C for 2 h, however, produces a granular and permeable sorbent. Although the soil's sorption capacity (150 μg/g ) is about a quarter of the low end range of values reported for commercially-available activated alumina, the sorption for F⁻ is specific. A batch sorption experiment in the presence of Cl⁻, SO₄²⁻ and HCO₃⁻ shows little or no competition from these other anions.     

Optimization of ammonia removal by ion-exchange resin using response surface methodology

The ability of ion-exchange resin for ammonia removal from aqueous solution was studied. The results showed that Amberlite ion-exchange resin was effective in removing ammonia from aqueous solution. Factorial design and response surface methodology were applied to evaluate and optimize the effects of pH, resin dose, contact time, temperature and initial ammonia concentration. Low pH condition was preferred with the optimum pH found to be 6. High resin dose generated high removal rate and low exchange capacity. Results of factorial design and response surface methodology showed that temperature was not a significant parameter. The model prediction was in good agreement with observed data (R ² = 0.957). The optimum Q _e was 28.78 mg/g achieved at pH = 6 and initial TAN concentration of 3000 mg/L. The kinetics followed the pseudo-second-order kinetic model (R ² = 0.999). Equilibrium data were fitted to Langmuir and Freundlich isotherm models with Langmuir model providing a slightly better predication (R ² = 0.996). The resin was completely regenerated by 2 N H₂SO₄.     

<Emphasis Type="Italic">Vitis vinifera</Emphasis> leaf litter for biosorptive removal of nitrophenols

Vitis vinifera (grape) leaf litter, an abundant agricultural waste in South Africa was chemically modified with H₃PO₄ and carbonized for use as biosorbent. Characterization and the potential application of the adsorbent in simultaneous removal of 4-nitrophenol and 2-nitrophenol from aqueous solutions were investigated. The adsorbent was characterized using FTIR, SEM and EDX elemental microanalysis. The EDX and FTIR analysis revealed the presence of surface oxygen moieties capable of binding to adsorbate molecules while the SEM micrographs showed the development of pores and cavities in the adsorbent. Batch adsorption experiments were conducted at a varying contact time, adsorbent dosage, pH and initial adsorbate concentration to investigate optimal conditions. The maximum adsorption capacity of the adsorbent was 103.09 and 103.10 mg/g for 4-nitrophenol and 2-nitrophenol, respectively. The adsorption process was best fitted into Freundlich isotherm while the adsorption kinetics followed a pseudo-second-order model. Liquid film and intra-particle diffusion contributed to the adsorption process. Thermodynamic parameters of ΔG°, ΔH° and ΔS° were evaluated. The adsorption was exothermic, feasible and spontaneous. The results suggest a possible application of grape leaf litter as a precursor for activated carbon and for cheaper wastewater treatment technologies.     

Changes in the composition of bitumen extracts and chemical structure of kerogen during hydrous pyrolysis

The paper presents data on the composition of biomarkers from bitumen extracts and the chemical structure of kerogen from C_org-rich sedimentary rocks before and after hydrothermal treatment in an autoclave at 300°C. Samples selected for this study are kukersite and Ordovician Dictyonema shale from the Baltics, Domanik oil shale from the Ukhta region, Upper Permian brown coal from the Pre-Ural foredeep, carbonaceous shale from the Oxfordian horizon of the Russian plate, and Upper Jurassic oil shales from the Sysola oil shale bearing region. The rocks contain type I, II, III, and II-S kerogens. The highest yield of extractable bitumen is achieved for Type II-S kerogen, whereas Type III kerogen produces the lowest amount of bitumen. The stages of organic matter thermal maturation achieved during the experiments correspond to a transition from PC_2–3 to MC_1–2. The ¹³C NMR data on kerogen indicate that the aromatic structures of geopolymers underwent significant changes.     

Investigating CO<Subscript>2</Subscript>-enhanced oil recovery potential for a mature oil field: a case study based on Ankleshwar oil field,Cambay Basin,India

CO₂-enhanced oil recovery (EOR) is an upcoming technology in India. At present, no Indian field is under CO₂-EOR and implementation of this technique to a mature oil field needs a rigorous study. In the present work, we made an attempt to investigate the CO₂-EOR potential of a mature oil field, situated in Cambay Basin, India. The field was put on production in 1961, and it has produced approximately 65.36 MMt oil during massive water flooding, leading to residual oil reserves of 6.49 MMt. The operator of the field is interested in incremental oil recovery from this field by injecting CO₂. This requires estimation of incremental oil recovery potential of the field by carrying out systematic study. We, therefore, developed a conceptual model inspired by Ankleshwar oil field of Cambay Basin using available information provided by the field operator and carried out systematic studies to establish an optimized strategy for CO₂ injection. To achieve this goal, we investigated the effect of various operational parameters on oil recovery efficiency of our conceptual model and selected optimum parameters for reservoir simulations. Simulation results clearly indicate that the field can be a good candidate for CO₂-EOR, and an additional oil recovery of 10.4% of hydrocarbon pore volume is feasible. Major outcome of the study is an optimized black-oil simulation model, which is in good agreement with the fine grid compositional model of high accuracy. The proposed black-oil model can easily be implemented and updated compared with compute intensive finer compositional simulation model.     

Kinetic and equilibrium study of Ni(II) sorption from aqueous solutions onto Peganum harmala-L

In this study, the adsorption behavior of Ni(II) in an aqueous solution system using natural adsorbent Peganum harmala-L was measured via batch mode. The prepared sorbent was characterized by scanning electron microscope, Fourier transform infrared spectroscopy, N₂ adsorption–desorption and pH_zpc. Adsorption experiments were carried out by varying several conditions such as contact time, metal ion concentration and pH to assess kinetic and equilibrium parameters. The equilibrium data were analyzed based on the Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherms. Kinetic data were analyzed using the pseudo-first-order, pseudo-second-order and intra-particular diffusion models. Experimental data showed that at contact time 60 min, metal ion concentration 50 mg/L and pH 6, a maximum amount of Ni(II) ions can be removed. The experimental data were best described by the Langmuir isotherm model as is evident from the high R ² value of 0.988. The adsorption capacity (q _m) obtained was 68.02 mg/g at an initial pH of 6 and a temperature of 25 °C. Kinetic studies of the adsorption showed that equilibrium was reached within 60 min of contact and the adsorption process followed the pseudo-first-order model. The obtained results show that P. harmala-L can be used as an effective and a natural low-cost adsorbent for the removal of Ni(II) from aqueous solutions.     

Nonlinear kinetic analysis of phenol adsorption onto peat soil

Phenolic compounds are considered as a serious organic pollutant containing in many industrial effluents particularly vulnerable when the plant discharge is disposed on land. In the present study, the phenol removal potential of peat soil as adsorption media was investigated as the adsorption process are gaining popular for polishing treatment of toxic materials in industrial wastewater. Batch experiments were performed in the laboratory to determine the adsorption isotherms of initial concentrations for 5, 8, 10, 15, and 20 mg/L and predetermined quantity of peat soil with size ranges between 425 and 200 μm poured into different containers. The effects of various parameters like initial phenol concentration, adsorbent quantity, pH, and contact time were also investigated. From experimental results, it was found that 42 % of phenol removal took place with optimized initial phenol concentration of 10 mg/L, adsorbent dose of 200 g/L, solution pH 6.0 for the equilibrium contact time of 6 h. The result exhibits that pseudo-first-order (R ² = 0.99) and Langmuir isotherm models are fitted reasonably (R ² = 0.91). Adams–Bohart, Thomas, Yoon–Nelson, and Wolborska models were also investigated to the column experimental data of different bed heights to predict the breakthrough curves and to determine the kinetic coefficient of the models using nonlinear regression analysis. It was found that the Thomas model is the best fitted model to predict the experimental breakthrough curves with the highest coefficient of determination, R ² = 0.99 and lowest root mean square error and mean absolute performance error values.     

Biosorption of fluoride by water lettuce (<Emphasis Type="Italic">Pistia stratiotes</Emphasis>) from contaminated water

Phytoremediation is a proven low-cost and sustainable method for the removal of toxic pollutants from water. This green technology has been practiced for the past several years all over the world. In the present study, the interaction of fluoride on the surface of the floating aquatic plant water lettuce (Pistia stratiotes) during fluoride removal was investigated. Batch kinetic studies were performed to examine the fluoride uptake capacity of the plant with different initial fluoride concentrations such as 3, 5, 10, and 20 mg/L. The effects of various process parameters on fluoride uptake dynamics such as pH, plant biomass, initial fluoride concentration, and time were examined. Freundlich’s isotherm model was found to (R ² = 0.957) fit well to the experimental data. The nature of reaction order followed pseudo-first-order kinetics, when the initial fluoride level in the solution was 5 mg/L. The experimental findings showed that the removal mechanism was driven by biosorption phenomenon. High fluoride concentration in the solution reduced the growth ratio of P. stratiotes. The lowest growth ratio of this aquatic macrophyte was found to be 76.80 ± 3.73% at 20 mg/L fluoride concentration. At lower fluoride concentrations such as 3 and 5 mg/L, the growth ratio of the plant was not reduced significantly.     

Adsorption isotherms, kinetics and mechanism for the adsorption of cationic and anionic dyes onto carbonaceous particles prepared from Juglans regia shell biomass

In the present study, Juglans regia shells were used to prepare activated carbon by acid treatment method. J. regia shell-based activated carbon was used for the adsorption of two synthetic dyes namely, a basic dye malachite green and an acid dye amido black 10B. The prepared adsorbent was crushed and sieved to three different mesh sizes 100, 600 and 1,000 μm. The adsorbent was characterized by scanning electron microscopy, surface acidity and zero-point charge. Batch experiments were carried out by varying the parameters like initial aqueous phase pH, adsorbent dosage and initial dye concentration. The equilibrium data were tested with Langmuir, Freundlich, Redlich–Peterson and Sips isotherm at three different temperatures 293, 300 and 313 K and it was found that the Freundlich isotherm best fitted the adsorption of both the dyes. Kinetic data were tested with pseudo first-order model and pseudo second-order model. The mechanism for the adsorption of both the dyes onto the adsorbent was studied by fitting the kinetic data with intraparticle diffusion model and Boyd plot. External mass transfer was found to be the rate-determining step. Based on the ionic nature of the adsorbates, the extent of film diffusion and intraparticle diffusion varied; both being system specific. Thermodynamic parameters were also calculated. Finally, the process parameters of each adsorption system were compared to develop the understanding of the best suitable system.