Methylene Blue Adsorption on Natural and Modified Clays

Toxic methylene blue dye is removed from water by accumulating it on the surface of clay minerals. Clay adsorbents are obtained from kaolinite, montmorillonite, and their acid activated forms. The adsorption experiments are carried out in a batch process in environments of different pH, initial dye concentration, amount of clay, interaction time, and temperature. Adsorption of dye is best described by second order kinetics. In the temperature range of 303 to 333 K, the Langmuir monolayer capacity for three kaolinite species increased from 45.5 to 56.5 mg g^?1, 45.9 to 57.8 mg g^?1, 46.3 to 58.8 mg g^?1, and for three montmorillonites species from 163.9 to 181.8 mg g^?1, 166.7 to 188.8 mg g^?1, and 172.4 to 192.3 mg g^?1. The interaction is an endothermic process driven by entropy increase and spontaneous adsorptive accumulation is ensured by favorable Gibbs energy decrease. It is found that acid activation enhances the adsorption capacity of kaolinite and montmorillonite.     

Combined processes of glycerol polymerization/carbonization/activation to produce efficient adsorbents for organic contaminants

BACKGROUND: Glycerol was used to produce efficient adsorbents with a high surface area for organic contaminants by a combined process based on polymerization, carbonization and activation. RESULTS: Glycerol and sulfuric acid catalyst at concentrations of 0, 0.5, 1, 2 and 5 mol% were heated to 150 °C to form polyglycerol, which was then decomposed at 580 °C and activated with CO₂ at 850 °C. The resulting activated carbons had a high specific area (1630 m²g^?1) and high adsorption capacity of methylene blue used as a model organic contaminant. This process was also used to produce a special composite adsorbent based on expanded vermiculite (EV) coated with activated carbon. These composites were produced by impregnation of EV with glycerol followed by polymerization, thermal decomposition and activation with CO₂ to produce up to 25 wt% carbon and a surface area of 835 m²g^?1. CONCLUSIONS: The carbon layer present in the EV composite/activated carbon (GVE4CA2) produces a remarkable increase in the methylene blue adsorption capacity of the expanded vermiculite and strongly decreases undesirable water absorption. Copyright © 2012 Society of Chemical Industry     

Towards waste minimisation in WWTP: activated carbon from biological sludge and its application in liquid phase adsorption

Surplus sludge produced during the biological treatment of wastewater requires costly disposal procedures. With increasing environmental and legislative constraints, increasing sludge production and more limited disposal options, new recycling alternatives have to be found. The possibility of obtaining activated carbons from surplus biological sludge by chemical activation with H₂SO₄ has been investigated. Operational parameters such as the amount of H₂SO₄ added, the temperature, and activation time were modified to ascertain their influence on the quality of the activated carbon obtained. The quality of the sludge‐based activated carbons was evaluated by established characterisation parameters for adsorption from solution such as phenol value, iodine number, methylene blue number and tannin value and compared with commercial activated carbons. Activation at 700 °C for 30 min in the presence of 0.5 cm³ H₂SO₄ g^?1 dry solids in the sludge led to an activated carbon with a good capacity for iodine and tannic acid. The sludge‐derived activated carbon obtained is mesoporous in nature with a high presence of large macropores. Weak and moderate acidic surface functional groups were detected on the surface, which impart a hydrophilic nature to the solid. When compared with a commercial activated carbon, the sludge‐derived activated carbon performed better when removing dyes with a high presence of anionic solubilising groups and heavy metals. The results indicate that COD adsorption from a biologically‐treated effluent may also be an area for application. © 2002 Society of Chemical Industry     

Facile synthesis of amine-functionalized UiO-66 by microwave method and application for methylene blue adsorption

The metal–organic frameworks UiO-66 with amine functional groups were synthesized by microwave irradiation, their structures and properties were characterized. The results show that NH₂-UiO-66 can be prepared quickly and well-crystallized by microwave-assisted method within 15 min. The amine-functionalized UiO-66 was octahedral crystals of well defined sizes (500–900 nm) and had a high specific surface area about 924.37 m² g^?1 and micropore range from 2.0 to 11 nm. The amine-functionalized UiO-66 was thermally stable up to 540 °C stability and exhibited a good combination of methylene blue adsorption. The maximum adsorption capacity reached up to 203.95 mg g^?1. The kinetics and equilibrium of the adsorption process were found to follow the pseudo-second-order kinetic and Langmuir adsorption model, respectively.     

Activated carbons prepared from biogas residue: characterization and methylene blue adsorption capacity

BACKGROUND: In China, some biogas residue, which cannot be utilized by microbes in the anaerobic process, has been used as fertilizer. More has been deposited in biogas plants or on land around the plants. This has an effect on the environmental protection of the biogas plant, especially if the high lignin content in the biogas residue is not handled properly. RESULTS: In this study biogas residue has been used for the preparation of activated carbons by phosphoric acid activation. Textural characterization and feasibility of employing the prepared activated carbon to remove methylene blue (MB) from aqueous solution were investigated. The results show that the activated carbons have high surface area (1950 m² g^?1) and pore volume (1.232 cm³ g^?1). Equilibrium data were best described by the Langmuir isotherm model, with a maximum monolayer adsorption capacity of 344.83 mg g^?1 at 25 °C. Among the kinetic models studied, the pseudo‐first‐order model was found to be the most applicable to describe the adsorption of MB. CONCLUSIONS: The adsorption performance of activated carbons prepared from biogas residues (BR‐AC) was comparable with that of commercial material and other adsorbents reported in earlier studies and presents a high value added application for biogas residues. Copyright © 2010 Society of Chemical Industry     

Activated carbon production from synthetic crude coke

A two-step pyrolysis and activation process was used to study the production of activated carbon from oil sands coke. Steam was employed as the activating agent at atmospheric pressure and 850°C. The activation of raw coke was compared with the activation of coke treated with a potassium hydroxide catalyst. A high BET surface area of 318 m²g⁻¹ was obtained for untreated coke activated for 6 h. The addition of a catalyst increased activation rates but did not result in a higher surface area for the potassium-treated activated coke. Surface area generally increased with activation time but was sensitive to the percentage burnoff. The adsorptive capacities of the activated carbons were significantly higher than that of the raw coke. The untreated activated coke had a higher adsorptive capacity for methylene blue than activated potassium coke. The reverse was true for iodine adsorption.     

Solvothermal polycondensation of novolacs phenolic-resin to nanopowders and their derived activated nanocarbons as efficient adsorbents for water cleaning

Novolacs phenolic-resin (PF) was easily polycondensed into polymeric powders with sizes and morphologies ranging from microspheres to nanoparticles by a simple solvothermal process without adding any crosslinking agent. Activating the highly divided PF powders by CO₂ resulted in nanosize activated carbons with high specific surface area (2092 m² g^?1) and large pore volume (1.33 cm³ g^?1) while preserving a high carbon yield of about 38 wt%. As for adsorption tests, the micropore-dominated activated nanocarbons exhibited fast and high adsorption capabilities towards both Cr(VI) ions and bulky rhodamine B molecules due to their much improved external surface area and the greatly shortened intra-particle diffusion distance. The equilibrium adsorption amounts of Cr(VI) and RB on the activated nanocarbons as estimated by the Langmuir model were 200 and 990 mg g^?1, achieved within an adsorption time of 30 and 360 min, respectively.     

Applicability of Activated Carbon to Treatment of Waste Containing Iodine-Labeled Compounds

Abstract

A timber industry waste was transformed to activated carbon by a one-step chemical activation process using H₃PO₄ (H). The used activated carbon (SDH) was characterized by N₂ adsorption, FTIR, density, pH, point of zero charge pH_pzc, moisture and ash content. Methylene blue (MB) and the iodine number were calculated by adsorption from the solution. The applicability of the different activated carbon produced was carried out to treatment of aqueous waste contaminated with iodine-labeled prolactin (I-PRL) Treatment processes were performed under the varying conditions; contact time, temperature, carbon type, carbon dosage, and different particle size of the activated carbon (SDH). The results indicated that 5 hours are sufficient to reach a plateau, and the amount of I-PRL adsorbed on SDH activated carbons increase with the solution temperature with thermodynamic parameter of ΔG° = ?7.962 (kJ/mol), ΔH° = 28.869 (kJ/mol) and ΔS° = 109.94 (J/mol K). The optimum adsorption results were reached using carbon dose of 0.1 gm with particle size of <0.25 mm, and a batch factor (V/M) of 7.14 mlg^?1. First- and second-order equations, intraparticle diffusion equation, and the Elovich equation have been used to test experimental data. The experimental data was found to fit the second-order model and a chemisorptions mechanism. 0.7 M NaOH can be used for regeneration of spent SDH activated carbon with the efficiency of 99.6% and the regenerated carbon can be reused for five cycles effectively.     

Utilization of waste plastic pet bottles to prepare copper-1,4-benzenedicarboxylate metal-organic framework for methylene blue removal

ABSTRACT

The study aims to use waste plastic PET bottles to recover terephthalic acid for preparing copper-1,4-benzenedicarboxylate, which was then utilized as an adsorbent for removal of methylene blue (MB) from aqueous solutions after carefully characterizing by XRD, FTIR, TGA, SEM, and EDX. The optimum conditions were established as pH = 6, 25°C, adsorbent dose of 1 g L^?1, contact time of 20 min, and agitation speed of 150 rpm. The adsorption process was spontaneous, exothermic, fitting well to Langmuir isotherm model with the maximum adsorption capacity of 41.01 mg g^?1 and more suitable to be described by the pseudo first-order kinetic model. It was indicated that the physical adsorption plays a leading role in the adsorption process. The recycling study was also conducted to confirm the long-term use of the synthesized adsorbent.     

Adsorption behavior of methylene blue on amine-functionalized ordered mesoporous alumina

Amine-functionalized ordered mesoporous alumina (NH₂-OMA) was synthesized through a facile and reproducible method. Its organic dyes adsorption characteristics, including adsorption isotherms, adsorption kinetics, the stability and reusability of the adsorbents were investigated. This material exhibited strong affinity to methylene blue and extremely high adsorption capacity. The maximum adsorption capacity value reached 657.89 mg g^?1. Adsorption kinetics was best described by the pseudo-second-order model. Equilibrium data were well fitted to the Langmuir isotherm model.     

Starch/rice husk ash based superabsorbent composite: high methylene blue removal efficiency

Superabsorbent hydrogels composites based on the biopolymer starch (ST) and rice husk ash (RHA) were successfully developed and tested towards the removal of methylene blue (MB), a cationic dye. RHA content hit the morphology, mechanical and water uptake properties of the composite. Batch adsorption experiments, carried out under pH 5 at 33 °C and with 2000 mg L^?1 as the initial concentration of MB, showed that at 5 wt% RHA the composite exhibited a remarkable adsorption capacity reaching up to 1906.3 mg g^?1 within 60 min. The adsorption kinetics followed the pseudo-second-order model and intraparticle diffusion was involved in this process. The Langmuir adsorption isotherm suggested a monolayer formation and spontaneous process. Thermodynamic parameters confirmed the spontaneity of the adsorption and suggested electrostatic interaction among the cationic dye molecules and the anionic adsorption sites on the adsorbent surface. FTIR analysis confirmed the adsorption process occurs via electrostatic mechanism associated with hydrophobic interactions. The adsorbents showed reusability with slight loss of adsorption capacity in five consecutive adsorption/desorption cycles. These results demonstrate ST/RHA superabsorbent composite as a low-cost, eco-friendly, robust and powerful adsorbent material for wastewater remediation.     

ADSORPTION OF A LEATHER DYE ON MESOPOROUS STRUVITE OBTAINED FROM SWINE WASTEWATER

Struvite powder obtained from swine wastewater was used as adsorbent to remove an azo leather dye from aqueous solution. The material was characterized by X-ray diffraction, surface area, and atomic force microscopy. The sample presented a single phase having a mesoporous structure and surface area of 35.63 m² g^?1. Langmuir and Freundlich isotherm models were fitted to the adsorption data and both satisfactorily represented the process. The maximum adsorption capacity was 38.14 mg g^?1. From the analysis of thermodynamic parameters such as free energy of adsorption (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) it was verified that the adsorption process is very fast, spontaneous, and exothermic in nature, with weak forces acting.     

Multivariate Optimization and Adsorption Characterization of As(III) by Using Fraxinus Tree Leaves

This study introduces Fraxinus tree leaves as a new, efficient biosorbent of As(III). A suitable response surface was achieved by running a central composite design. Simultaneous optimization of both responses (R% and q) was carried out and 67% of the goal of desirability function was attained. The results obtained for simultaneous optimization are R = 70% and q = 80.6 mg g^?1 with 67% desirability in m = 600 mg L^?1 where s = 0.10 g and pH = 3.9. Langmuir and Freundlich isotherms model were applied in explaining the sorbent–sorbate equilibrium study, and maximum capacity uptake equals 99.97 mg g^?1 and K_L = 0.05 L mg^?1 has been obtained. Fourier Transfer Infra-Red (FT-IR) and kinetic results were considered to examine the functional groups involved and the adsorption mechanism.     

Competitive Separation of Lead,Cadmium, and Nickel from Aqueous Solutions Using Activated Carbon: Response Surface Modeling,Equilibrium, and Thermodynamic Studies

In this study, the competitive separation of lead, cadmium, and nickel ions from aqueous solutions using a commercial activated carbon (AC) has been investigated and optimized using response surface methodology (RSM). The optimal conditions to reach the highest adsorption capacity for these metals were found as follows: initial pH = 6.3, temperature = 56.8°C, and shaking speed = 308 rpm. Under these conditions, the sequence of adsorption capacity toward the metal ions was as follows: Pb (II): 9.44 mg g^?1 > Cd (II): 9.37 mg g^?1 > Ni (II): 4.52 mg g^?1. The effect of shaking speed on the adsorption capacity of AC was higher than the effects of the initial pH and temperature, indicating the more important role of physisorption than chemisorption in the adsorption of these metal ions. This was confirmed by the results of thermodynamic studies. The equilibrium adsorption data were fitted to the Freundlich, Langmuir adsorption isotherm models and the Dubinin–Radushkevich model parameters were evaluated. All the models were tested and all were shown to represent the experimental data satisfactorily. The thermodynamic parameters such as ΔH, ΔS, and ΔG were computed from the experimental data. These values show that the adsorption is endothermic and spontaneous. The positive value of ΔS° indicates increasing of randomness at the solid/liquid interface during the adsorption of metal ions on AC.     

Modeling of Adsorptive Filtration of a Leather Dye in a Fixed Bed Column

Abstract

Activated carbons offer an efficient option for the removal of organic and inorganic contaminants from water. However, due to its high costs and difficulty in the regeneration, other low cost adsorbents have been used. In this work, the adsorption capacity of an adsorbent carbon with high iron oxides concentration was compared with that of a commercial activated carbon in the removal of a leather dye from an aqueous solution. The adsorbents were characterized using SEM/EDAX analysis and BET surface area. The capacity of adsorption of the adsorbents was evaluated through the static method at 25°C. The results showed that the color removal was due to the adsorption and precipitation of the dye on the surface of the solids. The adsorption equilibrium was described according to the linear model for the adsorbent carbon and the equilibrium constant was 0.02 L g^?1. The equilibrium of adsorption on activated carbon exhibited a behavior typical of the Langmuir isotherm and the monolayer coverage was 24.33 mg g^?1. A mathematical model was proposed to describe the dynamics of the color removal using a fixed bed considering that the color removal is due to the adsorption and the precipitation of the dye on the adsorbent.     

Removal of Orange II by Phosphonium-modified Algerian Bentonites

An Algerian montmorillonite was modified with two organic surfactants, methyltriphenyl phosphonium bromide and n-hexyltriphenyl phosphonium bromide. The solids obtained were used as adsorbents to remove Orange II, an anionic dye from aqueous solutions. Batch experiments were conducted to study the effects of temperature (20–60°C), initial concentration of adsorbate (50–150 mg L^?1) and pH of solution 6.5 on dye adsorption. Due to their organophilic nature, exchanged montmorillonites were able to adsorb Orange II at a very high level. Adsorption of Orange II for B-NHTPB and B-MTPB at different pH show that the adsorption capacity clearly decreases with an increase in pH of the initial solution from 2 to 8, this decrease being dramatic for pH > 8. This may be due to hydrophobic interactions of the organic dye with both phosphonium molecules and the remaining non-covered portion of siloxane surface. The kinetics of the adsorption was discussed on the basis of three kinetic models, i.e., the pseudo-first-order, the pseudo-second-order, and the intraparticle diffusion models. Equilibrium is reached after 30 min and 60 min for B-MTPB and B-NHTPB, respectively; the pseudo-second-order kinetic model described very well the adsorption of Orange II on modified bentonites. The non-linear Langmuir model provided the best correlation of experimental data, maximum adsorption of Orange II is 53.78 mg g^?1 for B-NHTPB and 33.79 mg g^?1 for B-MTPB. The thermodynamic parameters, such as free energy of adsorption (ΔG°), enthalpy change (ΔH°), and entropy change (ΔS°) were also determined and evaluated. From thermodynamic studies, it was deduced that the adsorption was spontaneous and exothermic.     

CMK-3 nanostructured carbon: Effect of temperature and time carbonization on textural properties and H2 storage

Abstract

CMK-3 carbons were synthesized varying the carbonization conditions and studying the effect of the templates calcined at different temperatures. The textural characterization of different SBA-15 templates calcined at 350, 450, and 550?°C shows a variation of the specific surface area below 10%. Based on the results, the SBA-15 obtained at 350?°C (the more affordable condition) was used as the final template for the CMK-3 synthesis. The results show that varying the time (from 2 to 6?h) and the temperature (from 600 to 900?°C) on the carbonization step, the textural, structural, and morphological properties of the carbons do not vary in a meaningful way. Thus, a CMK-3 carbon synthesized (using as template an SBA-15 calcined at 350?°C) obtained at 600?°C during 2?h was chosen to be used as adsorbent in hydrogen storage in order to stablish the relationship between the textural properties and its performance. Regarding the hydrogen storage, capacities of 15?mg H₂ g^?1 (1.5% w/w), and up to 28?mg H₂ g^?1 (2.8% w/w) were obtained at 1 and 10?bar, respectively. At high pressure, an important influence of the large micropores and narrow mesopores on the hydrogen adsorption was found.     

高比表面积煤质活性炭的制备与活化机理

以煤为原料,采用KOH活化法制备了高比表面积活性炭,分别考察了活化温度、浸渍比和活化时间等工艺参数对活性炭吸附性能的影响;测试了高比表面积活性炭在-196℃对N₂的吸附等温线、比表面积和孔径分布。结果表明,当活化工艺参数为活化温度900℃,浸渍比4,活化时间1.5 h的条件下可以制得较好的高比表面积活性炭产品,其比表面积为3135 m²·g^-1,孔容为1.72 cm³·g^-1,碘吸附值为2657 mg·g^-1;采用扫描电子显微镜观察了高比表面积活性炭的微观结构,采用气体分析仪检测了活化过程中的尾气成分,提出了高比表面积活性炭的活化机理。     

Equilibrium Isotherms,Thermodynamics, and Kinetic Studies for the Adsorption of Food Azo Dyes onto Chitosan Films

The adsorption of FD&C red 2 and FD&C yellow 5 onto chitosan films (CFs) was evaluated by equilibrium isotherms, thermodynamics, and kinetic studies. The effects of temperature (298–328 K), initial dye concentration (50–300 mg L^?1), stirring rate (50–350 rpm), and contact time (0–120 min) were investigated at pH of 2.0 and 100 mg L^?1 of CFs. The dye concentration was determined by spectrophotometry. Freundlich and Langmuir models were used to represent the equilibrium data. The Langmuir model was the more adequate to represent the equilibrium data (R² > 0.99 and average relative error <2.50%) and the maximum adsorption capacities were 494.13 and 480.00 mg g^?1 for FD&C red 2 and FD&C yellow 5, respectively, obtained at 298 K. The R_L values ranged from 0.044 to 0.145. The adsorption was exothermic, spontaneous, and favorable. For the FD&C red 2, 90% of saturation was attained at 120 min and the Elovich model was the more appropriate. For the FD&C yellow 5, 95% of saturation was attained at 20 min and the pseudo first-order model was the more adequate to fit the kinetic data. CFs were easily separated from the liquid phase after the adsorption process, providing benefits for industrial applications, and its application range can be extended for azo dyes.     

Activated carbon from cherry stones by chemical activation: Influence of the impregnation method on porous structure

Cherry stones are utilized as a precursor for the preparation of activated carbons by chemical activation with phosphoric acid (H₃PO₄). The activation process typically consists of successive impregnation, carbonization, and washing stages. Here, several impregnation variables are comprehensively studied, including H₃PO₄ concentration, number of soaking steps, H₃PO₄ recycling, washing of the impregnated material, and previous semi-carbonization. The choice of a suitable impregnation methodology opens up additional possibilities for the preparation of a wide variety of activated carbons with high yields and tailored porous structures. Microporous activated carbons with specific surface areas of ～800 m² g^?1 are produced, in which > 60% of the total pore volume is due to micropores. High surface areas of ～1500 m² g^?1 can be also developed, with micropore volumes being a 26% of the total pore volume. Interestingly, using the same amount of H₃PO₄, either carbons with surface areas of 791 and 337 m² g^?1 or only one carbon with a surface area of 640 m² g^?1 can be prepared. The pore volumes range very widely between 0.07–0.55, 0.01–0.90, and 0.09–0.79 cm³ g^?1 for micropores, mesopores, and macropores, respectively.