Adsorption of urea onto granular activated alumina: A comparative study with granular activated carbon

ABSTRACT

This study investigated the ability of granular activated alumina to remove urea from wastewater through adsorption, and compared its performance with granular activated carbon. XRF, EDX, XRD, and TGA were used to investigate the adsorbents. The removal of urea as a function of pH value was studied. The point of zero charge for activated alumina was found to be 8.8, while that for activated carbon was found to be 7.1. The experimental data of the adsorption process were explored by fitting to different kinetic models to determine the adsorption kinetics and mechanisms. Then, the equilibrium data were examined by fitting to various two-parameter and three-parameter isotherm models. Results showed that the removal efficiency increased with the increasing pH value. The maximum removal efficiencies were 24% and 31% for granular activated alumina and granular activated carbon, respectively, at pH?=?9.0. Kinetic studies showed that adsorption of urea onto both activated alumina and activated carbon can be expressed by pseudo second order kinetics. Equilibrium studies showed that the adsorption isotherms could be expressed by the Redlich-Peterson isotherm and Temkin isotherm for activated alumina and activated carbon, respectively. Adsorbents were investigated using FTIR and SEM, and results showed the occurrence of adsorption.     

Kinetic,isothermal and thermodynamic studies on Th(IV) adsorption by different modified activated carbons

In this study, the performance of modified adsorbents obtained from activated carbon for the adsorption of thorium(IV) ions from aqueous media was investigated. The analytical and spectroscopic methods such as FT-IR, BET, SEM and UV–Vis were used to examine the properties of the modified materials. According to the analysis results, the both adsorbents had large surface areas after modification. Then, temperature, pH, mixing time and solution concentration parameters were observed to determine optimum thorium adsorption conditions on modified materials. The obtained results from the experiments were applied different three kinetic models and adsorption isotherms and thermodynamic parameters were calculated and then all of the results were interpreted. The adsorption process for both adsorption systems was observed to be compatible with the pseudo-second-order kinetic model. The adsorption equilibrium data were best described by the Langmuir model for modified adsorbent with KMnO₄ and by the Freundlich model for modified adsorbent with NaOH. Furthermore, the calculated thermodynamic parameters (ΔG°, ΔH° and ΔS°) showed that the both adsorption processes were endothermic and spontaneous. The data show that modified adsorbents can be used as influential and low-cost adsorbents to remove thorium ion. Modified new adsorbents were highly selective for thorium ion in competitive adsorption studies.

     

Preparation of manganese dioxide loaded activated carbon adsorbents and their desulfurization performance

Manganese dioxide loaded activated carbon adsorbents (MnO₂/AC) were prepared and characterized by N₂ adsorption-desorption, BET method, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectrometry (FT-IR) and scanning electron microscopy (SEM). Effects of preparation conditions and adsorption conditions on desulfurization performance of the adsorbents were studied in a fixed-bed adsorption apparatus. Experimental results show that the surface area and pore volume of MnO₂/AC decreased compared with the unmodified activated carbon, but the adsorption capacity to H₂S was improved greatly. A suitable H₂S removal activity was obtained with manganese dioxide to activated carbon ratio of 1.1: 1 and the calcination temperature of 250°C. At the adsorption temperature of 40°C and gas flow rate of 20 mL/min, the H₂S saturation capacity and H₂S removal rate reached up to 713.25 mg/g and 89.9%, respectively.     

Adsorption dynamics of hydrogen sulfide in impregnated activated carbon bed

Potassium iodide (KI) impregnated activated carbons were prepared and applied for the removal of hydrogen sulfide. The adsorption dynamics of the prepared adsorbents were investigated in fixed-bed column as functions of the concentration of hydrogen sulfide and oxygen, and relative humidity. It was found that the adsorption capacity was highly dependent on the oxygen concentration because of the chemical adsorption of hydrogen sulfide on KI impregnated activated carbon. The adsorbents before and after adsorption of hydrogen sulfide were characterized by BET, SEM and EDS analysis.     

Heavy metals and adsorbents effects on activated sludge microorganisms

The sorption of Cu(II) and Cd(II) from synthetic solution by powdered activated carbon (PAC), biomass, rice husk (RH) and activated rice husk (ARH) were investigate under batch conditions. After activated by concentrated nitric acid for 15 hours at 60-65 degrees C, the adsorption capacity for RH was increased. The adsorbents arranged in the increasing order of adsorption capacities to the Langmuir Q degree parameter were biomass > PAC > ARH > RH. The addition of adsorbents in base mix solution had increased the specific oxygen uptake rate (SOUR) activated sludge microorganisms with and without the presence of metals. The increased of SOUR were due to the ability of PAC and RH in reducing the inhibitory effect of metals on microorganisms and provide a reaction site between activated sludge microorganisms and substrates.     

Adsorption kinetic and isotherm studies of Azure A on various activated carbons derived from agricultural wastes

The present study narrates the eminent role of agricultural wastes as adsorbents viz., Indian almond shell carbon (IASC), ground nut shell carbon (GSC), areca nut shell carbon (ASC), tamarind shell carbon (TSC) and cashew nut shell carbon (CSC) for the removal of Azure A (AA) dye from waste water. Different experimental parameters such as effect of initial concentration, contact time, dose, pH and particle size have been studied. The experimental results were analysed using Freundlich, Langmuir, Temkin, Redlich–Peterson and Dubinin–Radushkevich isotherm models. Different kinetic equations (first order, pseudo first order and pseudo second order) were applied to study the adsorption kinetics of AA on various activated carbons. Surface morphology of the adsorbents before and after adsorption is studied by Scanning Electron Microscopy (SEM). FT-IR studies revealed the presence of functional groups of dye on the adsorbents. It is inferred from the experimental result that the activated carbons (IASC, GSC, ASC, TSC and CSC) from agricultural wastes can be applied as an adsorbent substitute to commercial activated carbon (CAC) in the removal of AA dye from waste water.     

Dye and its removal from aqueous solution by adsorption: A review

In this review article the authors presented up to-date development on the application of adsorption in the removal of dyes from aqueous solution. This review article provides extensive literature information about dyes, its classification and toxicity, various treatment methods, and dye adsorption characteristics by various adsorbents. One of the objectives of this review article is to organise the scattered available information on various aspects on a wide range of potentially effective adsorbents in the removal of dyes. Therefore, an extensive list of various adsorbents such as natural materials, waste materials from industry, agricultural by-products, and biomass based activated carbon in the removal of various dyes has been compiled here. Dye bearing waste treatment by adsorption using low cost alternative adsorbent is a demanding area as it has double benefits i.e. water treatment and waste management. Further, activated carbon from biomass has the advantage of offering an effected low cost replacement for non-renewable coal based granular activated carbon provided that they have similar or better adsorption on efficiency. The effectiveness of various adsorbents under different physico-chemical process parameters and their comparative adsorption capacity towards dye adsorption has also been presented. This review paper also includes the affective adsorption factors of dye such as solution pH, initial dye concentration, adsorbent dosage, and temperature. The applicability of various adsorption kinetic models and isotherm models for dye removal by wide range of adsorbents is also reported here. Conclusions have been drawn from the literature reviewed and few suggestions for future research are proposed.     

Comparative study of acid yellow 119 adsorption onto activated carbon prepared from lemon wood and ZnO nanoparticles loaded on activated carbon

Activated carbon from lemon wood (AC) and ZnO nanoparticles loaded on activated carbon (ZnO‐NP‐AC) were prepared and their efficiency for effective acid yellow 199 (AY 199) removal under various operational conditions was investigated. The dependence of removal efficiency on variables such as AY 199 concentration, amount of adsorbent and contact time was optimized using response surface methodology and Design‐Expert. ZnO nanoparticles and ZnO‐NP‐AC were studied using various techniques such as scanning electron microscopy, X‐ray diffraction and energy‐dispersive X‐ray analysis. The optimum pH was studied using one‐at‐a‐time method to achieve maximum dye removal percentage. Small amounts of the proposed adsorbents (0.025 and 0.025 g) were sufficient for successful removal of AY 199 in short times (4.0 and 4.0 min) with high adsorption capacity (85.51 and 116.29 mg g^?1 for AC and ZnO‐NPs‐AC, respectively). Fitting the empirical equilibrium data to several conventional isotherm models at optimum conditions indicated the appropriateness of the Langmuir model with high correlation coefficient (0.999 and 0.978 for AC and ZnO‐NPs‐AC, respectively) for representation and explanation of experimental data. Kinetics evaluation of experiments at various time intervals revealed that adsorption processes can be well predicted and fitted by pseudo‐second‐order and Elovich models. This study revealed that the combination of ZnO nanoparticles and AC following simple loading led to significant improvement in the removal process in short adsorption time which was enhanced by mixing the media via sonication.     

Adsorbent usage for VOC removal in synthetic latices

In the synthetic latex industry, there is a trend towards lower VOC levels. This paper describes an alternative to the current steam stripping or chemicals injection processes, namely using adsorbents for VOC removal for a styrene‐butadiene latex. Both batch and continuous adsorption experiments were performed to screen adsorbents, experimental conditions and simulate plant scale‐up. The removal effect of the adsorbents was determined using gas chromatography (GC). It was found that activated carbon had the best VOC removal efficiency, and optimum operating conditions existed at a pH of 10.5, and ambient temperature. It was further found in the carbon bed experiments that the VOC level could be lowered down to 150 ppm, which was the minimum attainable. The regeneration of the spent carbon using solvent extraction was also investigated. Several solvents were tested, and toluene was found to be the most efficient.     

Effect of valence of copper on adsorption of dimethyl sulfide from liquid hydrocarbon streams on activated bentonite

Samples of activated bentonite and activated bentonite modified with CuCl and CuCl₂, separately, were tested as dimethyl sulfide (DMS) adsorbents. The adsorption and desorption behaviours of DMS on the adsorbents were studied systematically. The adsorbents were characterised by nitrogen adsorption, XRD, and DMS-TPD tests. The addition of CuCl and CuCl₂ to the activated carbon significantly enhanced the adsorption capacity of DMS, despite a notable decrease in the specific surface area and total pore volume of the activated bentonite. It is presumed that copper cation species may act as an adsorption site for DMS. The adsorption capacity of Cu(II)-bentonite was better than that of Cu(I)-bentonite. The DMS-TPD patterns indicate that the stronger electrophilicity of Cu(II) compared to that of Cu(I) caused it to interact with the DMS molecules more strongly, thus contributing to a better adsorptive performance. The Cu(II)-bentonite calcined at 150°C had the best DMS removal performance with a high sulphur capacity of 70.56 mg S g^?1 adsorbent. The DMS removal performance became much lower with the increase in the calcination temperature, which appeared to be due to the decrease in the CuCl₂·2H₂O phase and the formation of the monoclinic Cu(OH)Cl phase.     

Adsorption of cyanuric acid on activated carbon from aqueous solution: effect of carbon surface modification and thermodynamic characteristics

The performance of a conventional and two surface-modified activated carbon samples was investigated for the sorption of cyanuric acid from aqueous solution by varying the process parameters such as initial concentration, pH, temperature, dose of adsorbents, and agitation time. The modified carbon samples obtained by acid and ammonia treatment of the conventional sample had a higher BET surface area (989 and 1010 m2 g-1, respectively) and higher specific mesopore surface area (27.36 and 33.21 m2 g-1, respectively) compared to the untreated material (820 and 18.25 m2 g-1). The solute removal was found to be favored at lower solute concentration, increased agitation time, increased adsorbent dose, and lower temperature. The modified adsorbents outperformed the conventional activated carbon for sorption of cyanuric acid especially at higher pH (>7.5) and with increasing temperature. The Freundlich model appears to fit the isotherm data better than the Langmuir model. The thermodynamic parameters (DeltaG degrees ads, DeltaH degrees, and DeltaS degrees) were evaluated showing that the sorption process was thermodynamically favorable, spontaneous, and exothermic. The findings can be used for predictive modeling for analysis and design adsorption systems for removal of cyanuric acid and other polar atrazine degradation products from environmental aqueous samples.     

Elution and frontal dynamics of adsorption of organic substances on activated carbon

The elution dynamics of adsorption on activated carbon was studied at various carrier-gas flow rates for a series of organic substances. With the help of the model of the equilibrium adsorption layer that uses the adsorption isotherm described by the theory of volume filling of micropores the outlet curves for the elution and frontal dynamics of adsorption can be adequately predicted. The effective kinetic coefficient and the parameters of the adsorption isotherm were found to be constant for the elution curves calculated both in the elution and frontal regimes of the adsorption dynamics over the whole range of concentrations studied. The effective kinetic coefficient in the mathematical model employed for the systems with microporous adsorbents is independent in fact of the nature of an adsorptive and is mainly determined by the parameters of porous structure of activated carbon and the experimental conditions of a dynamic run.     

Microwave assisted preparation of efficient activated carbon from grapevine rhytidome for the removal of methyl violet from aqueous solution

Grapevine rhytidome (the outer layer of bark on trunk), as an abundant and low-cost precursor, was used to prepare granular activated carbon with high surface area for the removal of methyl violet from aqueous solution. Microwave heating source was used to reduce the treatment time and energy consumption. To optimize the preparation, the effects of the different parameters, such as phosphoric acid concentration, acid/precursor weight ratio, impregnation time, microwave power, radiation time, and oven heating time on the ability of the samples for removal of methyl violet were studied. The obtained activated carbon was characterized by N₂ adsorption/desorption, SAXS, TEM and SEM methods. The adsorption of methyl violet onto the activated carbon was studied from both equilibrium and kinetic point of view and the results were compared with the commercial granular activated carbon. The rate of adsorption onto the prepared activated carbon was faster than commercial activated carbon. Different kinetic models were used to analyze the experimental kinetic data. The obtained activated carbon showed higher adsorption capacity (more than twice) for the adsorption of methyl violet in comparison with the commercial one. The equilibrium data were analyzed using different isotherm models. Adsorption was found to be maximum in the pH range 7-9.     

CO2 adsorption on zeolite X/activated carbon composites

Two series of zeolite X/activated carbon composites with different ratios of zeolite and activated carbon were prepared through a combination process of CO₂ activation of the mixtures of elutrilithe and pitch and subsequent hydrothermal crystallization in alkaline solution. An additional surface modification was achieved in diluted NH₄Cl solution. CO₂ and N₂ uptakes on the composites before and after modification were determined for pressures up to 101?kPa at 273 and 298?K, respectively. Langmuir-Freundlich and Toth adsorption models were used to describe the adsorption isotherms of CO₂ and the corresponding heats of adsorption were estimated with the Clausius-Clapeyron equation. Both before and after modification, all composites exhibited a remarkable preferential adsorption of CO₂ compared to N₂, with the modified composites showing a higher adsorption selectivity to CO₂ over N₂ than the unmodified composites. With an increasing ratio of zeolite in the composites, adsorption capacity and adsorption heat of CO₂ on the composites increased simultaneously. Lower adsorption heat was observed both before and after modification especially at the low-loading region and when there was less energetic heterogeneity on the surface of the modified composites. The results may be attributed to the elimination of strong basic sites on the modified composites, which is favorable for desorption of CO₂ on the adsorbents and application in pressure swing adsorption processes.     

Adsorption of carbon disulfide on activated carbon modified by Cu and cobalt sulfonated phthalocyanine

A series of adsorbents were studied for removal efficiency of carbon disulfide (CS₂) under micro-oxygen conditions. It was found that activated carbon modified by Cu and cobalt sulfonated phthalocyanine (CoSPc) denoted as ACCu–CoSPc showed significantly enhanced adsorption ability. Reaction temperature was found to be a key factor for adsorption, and 20 °C seems to be optimal for CS₂ removal. Samples were analyzed by N₂-BET, XRD, XPS, SEM–EDS and CO₂-TPD. The characterization results demonstrated that large quantities of SO₄ ^2? anions were formed and adsorbed in the reaction process. SO₂, CS₂ and COS were detected in the effluent gas generated from the temperature programmed desorption of ACCu–CoSPc–CS₂. Therefore, it can be concluded that ACCu–CoSPc most likely acted as a catalyst in the adsorption/oxidation process on the surface of the impregnated sample. The generated sulfide and sulfur oxide can cover the active sites of adsorbents, resulting in pronounced reduction of adsorbent activity. Finally, the exhausted ACCu–CoSPc can be regenerated by thermal desorption.     

Equilibrium uptake and sorption dynamics for the removal of a basic dye (basic red) using low-cost adsorbents

Waste carbon slurries (generated in fertilizer plants) and blast furnace slag (generated in steel plants) have been converted into low-cost potential adsorbents. The adsorbents have been characterized and tried for the removal of the dye basic red from wastewater. Studies were performed at different pH to find the pH at which maximum adsorption occurs. Equilibrium isotherms were determined to assess the maximum adsorption capacity of the adsorbents. Adsorption capacities are compared for activated carbon developed from fertilizer waste and activated slag developed from blast furnace waste. The adsorption data are correlated with Freundlich and Langmuir isotherms in each system. The kinetics of adsorption depends on the adsorbate concentration and the physical and chemical characteristics of the adsorbent. Studies were conducted to delineate the effect of pH, temperature, initial absorbate concentration, particle size of the adsorbent, and solid-to-liquid ratio. The adsorption of basic red was found to be endothermic and first-order in nature.     

Adsorption of SO2 by typical carbonaceous material: a comparative study of carbon nanotubes and activated carbons

Applying activated carbons for SO₂ adsorption and conversion to H₂SO₄, as a dry process, has been considered the development direction of desulfurization technology. Coal-based activated carbon, coconut shell activated carbon, single wall carbon nanotube and multi-wall carbon nanotubes were used as typical carbonaceous materials to study the SO₂ adsorption mechanism. SEM, N₂ adsorption, XPS and fixed-bed reaction system were employed to study the morphology, pore structure, surface functional groups and SO₂ adsorption behaviors of the four adsorbents. The fixed-bed experiment was carried out at normal pressure and SO₂ concentration was set 1,000 ppm. According to SEM and N₂ adsorption results, hierarchical pore structure was an important characteristic of activated carbon. Aggregation was an important characteristic of CNTs. Mesopores and macropores took the dominance of pore structure in CNTs. According the SO₂ adsorption data and correlation analysis, it can be concluded that the dominant adsorption type on activated carbons does not alter with adsorption temperature changing. However, the adsorption type of SO₂ adsorption on CNTs changes with adsorption temperature varying. With adsorption temperature increasing, the dominant adsorption type transforms to chemisorption by physisorption. Higher-density π–π* in carbon nanotubes may be the active sites for the SO₂ chemical adsorption. Micropores with the diameter smaller than 0.7 nm were the best SO₂ adsorption place for both activated carbons and carbon nanotubes. The results provided a profound insight into the microstructure and SO₂ adsorption mechanism of the two kinds of carbonaceous materials.     

Boron Removal from Aqueous Solutions by Adsorption on Waste Sepiolite and Activated Waste Sepiolite Using Full Factorial Design

In the present paper, boron removal from aqueous solution by adsorption was investigated and 2³ full factorial design was applied. Non activated waste sepiolite (NAWS) and HCl activated waste sepiolite (AWS) were used as adsorbents. Regression equation formulated for boron adsorption was represented as a function of response variables. The results obtained from the study on parameters showed that as pH increased and temperature decreased boron removal by adsorption increased. Adsorbed boron amount on AWS was higher than that of NAWS. Maximum boron removal was obtained at pH 10 and 20°C for both adsorbents. Adsorption data obtained from batch adsorption experiments carried out with NAWS and AWS fitted to the Langmuir equation. The batch adsorption capacities were found in mg/g: 96.15 and 178.57 for NAWS and AWS, respectively. The capacity value for column study was obtained by graphical integration as 219.01 mg/g for AWS. The Thomas and the Yoon-Nelson models were applied to experimental data to predict the breakthrough curves and to determine the characteristic parameters of the column useful for process design.     

Removal of nickel (II) ions from aqueous solutions using modified activated carbon: A kinetic and equilibrium study

Removal nickel from the aquatic environment is a serious environmental problem in view of public health. The present article studies the applicability of activated carbon, obtained from graphite, as a source of adsorbents to remove nickel from the aqueous polluted water. Activated carbon was obtained by steam activation of graphite and then was oxidized by nitric acid followed by modification with Tetraethylenepentamine (TEPA). The applicability of graphite activated carbon (GAC), and modified activated carbon by Tetraethylenepentamine (GACA) to remove nickel ions Ni(II) from aqueous media was studied. The effect of pH, initial concentration, contact time, and the temperature was evaluated during Ni(II) removal operating in a batch process. Experimental results show that the studied activated carbon have a good adsorption capacity for Ni(II) ions and could reduce the concentrations of it in the groundwater. A maximum removal efficient of Ni(II) was observed at 55°C. The experimental data showed an endothermic and spontaneous process, which was fitted to Langmuir isotherm. Based on our results, we can conclude that it is possible to use GAC and GACA for removing Ni(II) effectively from groundwater.     

Changes of the porous structure of activated carbons applied in a filter bed pilot operation

The paper investigates the changes in porosity (i.e., in the accessible adsorption capacity of carbonaceous adsorbents for pollutants during filter bed maturation) of three activated carbons applied in a filter bed pilot operation. The results of this investigation may help to reduce operating costs, increase granular activated carbon bed life, maximize the useful life of biofilters, and understand the mechanism of water purification by carbon adsorbents. The analysis of the pore structure was limited to the first year of service of the beds, since this was when the largest decrease in the available pore capacity occurred. Low-temperature nitrogen adsorption isotherms were used to evaluate the structural parameters and pore size distributions (PSDs) of carbon samples (virgin (reference) and mature adsorbents for different periods of water treatment) on the basis of the Nguyen and Do (ND) method and density functional theory (DFT). These results were compared with small-angle X-ray scattering (SAXS) investigations (PSDs calculated by Glatter's indirect transformation method (ITP)). The results show that in general, the ND and ITP methods lead to almost the same qualitative distribution curve behavior. Moreover, the enthalpy of immersion in water, mercury porosimetry, densities (true and apparent), and the analysis of ash are reported and compared to explain the decrease in adsorptive capacity of the carbons investigated. On the other hand, the efficacy of TOC (total organic carbon, i.e., a quantity describing the complex matrix of organic material present in natural waters) removal and the bacteria count were analyzed to explain the role of adsorption in the elimination of contaminants from water. Finally, a mechanism of organic matter removal was suggested on the basis of the above-mentioned experimental data and compared with mechanisms reported by other authors.