19 resultados para Pseudo-second-order kinetic models

em Universidade Federal do Rio Grande do Norte(UFRN)


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Heavy metals are used in many industrial processestheirs discard can harm fel effects to the environment, becoming a serious problem. Many methods used for wastewater treatment have been reported in the literature, but many of them have high cost and low efficiency. The adsorption process has been used as effective for the metal remoal ions. This paper presents studies to evaluate the adsorption capacity of vermiculite as adsorbent for the heavy metals removal in a synthetic solution. The mineral vermiculite was characterized by differents techniques: specific surface area analysis by BET method, X-ray diffraction, raiosX fluorescence, spectroscopy in the infraredd region of, laser particle size analysis and specific gravity. The physical characteristics of the material presented was appropriate for the study of adsorption. The adsorption experiments weredriveal finite bath metod in synthetic solutions of copper, nickel, cadmium, lead and zinc. The results showed that the vermiculite has a high potential for adsorption, removing about 100% of ions and with removal capacity values about 85 ppm of metal in solution, 8.09 mg / g for cadmium, 8.39 mg/g for copper, 8.40 mg/g for lead, 8.26 mg/g for zinc and 8.38 mg/g of nickel. The experimental data fit in the Langmuir and Freundlich models. The kinetic datas showed a good correlation with the pseudo-second order model. It was conducteas a competition study among the metals using vermiculiti a adsorbent. Results showed that the presence of various metals in solution does not influence their removal at low concentrations, removing approximat wasely 100 % of all metals present in solutions

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Due to its physico-chemical and biological properties, related to the abundance and low cost of raw material, chitosan has been recognized as a material of wide application in various fields, such as in drug delivery systems. Many of these properties are associated with the presence of amino groups in its polymer chain. A proper determination of these amino groups is very important, in order to properly specify if a given chitosan sample can be used in a particular application. Thus, in this work, initially, a comparison between the determination of the deacetylation degree by conductometry and elemental analysis was carried out using a detailed analysis of error propagation. It was shown that the conductometric analysis resulted in a simple and safe method for the determining the degree of deacetylation of chitosan. Subsequently, experiments were performed to monitor and characterize the adsorption of tetracycline on chitosan particles through kinetic and equilibrium studies. The main models of kinetics and adsorption isotherms, widely used to describe the adsorption on wastewater treatment systems and the drug loading, were used to treat the experimental data. Firstly, it was shown that an apparent linear t/q(t) × t relationship did not imply in a pseudo-second-order adsorption kinetics, differently of what has been repeatedly reported in the literature. It was found that this misinterpretation can be avoided by using non-linear regression. Finally, the adsorption of tetracycline on chitosan particles was analyzed using insights obtained from theoretical analysis, and the parameters generated were used to analyze the kinetics of adsorption, the isotherm of adsorption and to ropose a mechanism of adsorption

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Heavy metals are used in many industrial processestheirs discard can harm fel effects to the environment, becoming a serious problem. Many methods used for wastewater treatment have been reported in the literature, but many of them have high cost and low efficiency. The adsorption process has been used as effective for the metal remoal ions. This paper presents studies to evaluate the adsorption capacity of vermiculite as adsorbent for the heavy metals removal in a synthetic solution. The mineral vermiculite was characterized by differents techniques: specific surface area analysis by BET method, X-ray diffraction, raiosX fluorescence, spectroscopy in the infraredd region of, laser particle size analysis and specific gravity. The physical characteristics of the material presented was appropriate for the study of adsorption. The adsorption experiments weredriveal finite bath metod in synthetic solutions of copper, nickel, cadmium, lead and zinc. The results showed that the vermiculite has a high potential for adsorption, removing about 100% of ions and with removal capacity values about 85 ppm of metal in solution, 8.09 mg / g for cadmium, 8.39 mg/g for copper, 8.40 mg/g for lead, 8.26 mg/g for zinc and 8.38 mg/g of nickel. The experimental data fit in the Langmuir and Freundlich models. The kinetic datas showed a good correlation with the pseudo-second order model. It was conducteas a competition study among the metals using vermiculiti a adsorbent. Results showed that the presence of various metals in solution does not influence their removal at low concentrations, removing approximat wasely 100 % of all metals present in solutions

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Produced water is the main effluent linked to the activity of extraction of oil and their caring management is necessary due to the large volume involved, to ensure to minimize the negative impacts of discharges of these waters in the environment. This study aimed to analyze the use of retorted shale, which is a reject from the pyrolysis of pirobituminous shale, as adsorbent for the removal of phenols in produced water. The material was characterized by different techniques (grain sized analysis, thermal analysis, BET, FRX, FT-IR, XRD and SEM), showing the heterogeneity in their composition, showing its potential for the removal of varied compounds, as well as the phenols and their derivatives. For the analysis of the efficiency of the oil shale for the adsorption process, assays of adsorption balance were carried through, and also kinetic studies and dynamics adsorption, in the ETE of the UTPF of Petrobras, in Guamaré-RN. The balance assays shown a bigger conformity with the model of Langmuir and the kinetic model more adjusted to describe the adsorption of phenols in retorted shale was of pseudo-second order. The retorted shale presented a low capacity of adsorption of phenols (1,3mg/g), when related to others conventional adsorbents, however it is enough to the removal of these composites in concentrations presented in the produced water of the UTPF of Guamaré. The assays of dynamics adsorption in field had shown that the concentration of phenol in the effluent was null until reaching its rupture (58 hours). The results showed the possibility of use of the reject for removal of phenols in the final operations of the treatment process, removing as well, satisfactorily, the color and turbidity of the produced water, with more than 90% of removal

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Actually, surveys have been developed for obtaining new materials and methodologies that aim to minimize environmental problems due to discharges of industrial effluents contaminated with heavy metals. The adsorption has been used as an alternative technology effectively, economically viable and potentially important for the reduction of metals, especially when using natural adsorbents such as certain types of clay. Chitosan, a polymer of natural origin, present in the shells of crustaceans and insects, has also been used for this purpose. Among the clays, vermiculite is distinguished by its good ion exchange capacity and in its expanded form enhances its properties by greatly increasing its specific surface. This study aimed to evaluate the functionality of the hybrid material obtained through the modification of expanded vermiculite with chitosan in the removal of lead ions (II) in aqueous solution. The material was characterized by infrared spectroscopy (IR) in order to evaluate the efficiency of modification of matrix, the vermiculite, the organic material, chitosan. The thermal stability of the material and the ratio clay / polymer was evaluated by thermogravimetry. To evaluate the surface of the material was used in scanning electron microscopy (SEM) and (BET). The BET analysis revealed a significant increase in surface area of vermiculite that after interaction with chitosan, was obtained a value of 21, 6156 m2 / g. Adsorption tests were performed according to the particle size, concentration and time. The results show that the capacity of removal of ions through the vermiculite was on average 88.4% for lead in concentrations ranging from 20-200 mg / L and 64.2% in the concentration range of 1000 mg / L. Regarding the particle size, there was an increase in adsorption with decreasing particle size. In fuction to the time of contact, was observed adsorption equilibrium in 60 minutes with adsorption capacity. The data of the isotherms were fitted to equation Freundlich. The kinetic study of adsorption showed that the pseudo second- order model best describes the adsorption adsorption, having been found following values K2=0,024 g. mg-1 min-1and Qmax=25,75 mg/g, value very close to the calculated Qe = 26.31 mg / g. From the results we can conclude that the material can be used in wastewater treatment systems as a source of metal ions adsorbent due to its high adsorption capacity

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Textile activity results in effluents with a variety of dyes. Among the several processes for dye-uptaking from these wastewaters, sorption is one of the most effective methods, chitosan being a very promising alternative for this end. The sorption of Methyl Orange by chitosan crosslinked particles was approached using equilibrium and kinetic analyses at different pH s. Besides the standard pseudo-order analysis normally effectuated (i.e. pseudo-first-order and pseudo-second-order), a novel approach involving a pseudo-nth-order kinetics was used, nbeing determined via non-linear regression, using the Levenberg-Marquardt method. Zeta potential measurements indicated that electrostatic interactions were important for the sorption process. Regarding equilibrium experiments, data were well fitted to a hybrid Langmuir-Freundlich isotherm, and estimated Gibbs free energy of adsorption as a function of mass of dye per area of chitosan showed that the process of adsorption becomes more homogeneous as the pH of the continuous phase decreased. Considering the kinetics of sorption, although a pseudo-nth-order description yielded good fits, a kinetic equation involving diffusion adsorption phenomena was found to be more consistent in terms of a physicochemical description of the sorption process

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Soil contamination by pesticides is an environmental problem that needs to be monitored and avoided. However, the lack of fast, accurate and low cost analytical methods for discovering residual pesticide in complex matrices, such as soil, is a problem still unresolved. This problem needs to be solved before we are able to assess the quality of environmental samples. The intensive use of pesticides has increased since the 60s, because the dependence of their use, causing biological imbalances and promoting resistance and recurrence of high populations of pests and pathogens (upwelling). This has contributed to the appearance of new pests that were previously under natural control. To develop analytical methods that are able to quantify residues pesticide in complex environment. It is still a challenge for many laboratories. The integration of two analytical methods one ecotoxicological and another chemical demonstrates the potential for environmental analysis of methamidophos. The aim of this study was to evaluate an ecotoxicological method as "screening" analytical methamidophos in the soil and perform analytical confirmation in the samples of the concentration of the analyte by chemical method LC-MS/MS In this work we tested two soils: a clayey and sandy, both in contact with the kinetic methamidophos model followed pseudo-second order. The clay soil showed higher absorption of methamidophos and followed the Freundlich model, while the sandy, the Langmuir model. The chemical method was validated LC-MS/MS satisfactory, showing all parameters of linearity, range, precision, accuracy, and sensitivity adequate. In chronic ecotoxicological tests with C. dubia, the NOEC was 4.93 and 3.24 for ng L-1 of methamidophos to elutriate assays of sandy and clay soils, respectively. The method for ecotoxicological levels was more sensitive than LC-MS/MS detection of methamidophos, loamy and sandy soils. However, decreasing the concentration of the standard for analytical methamidophos and adjusting for the validation conditions chemical acquires a limit of quantification (LOQ) in ng L-1, consistent with the provisions of ecotoxicological test. The methods described should be used as an analytical tool for methamidophos in soil, and the ecotoxicological analysis can be used as a "screening" and LC-MS/MS as confirmatory analysis of the analyte molecule, confirming the objectives of this work

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Contamination of groundwater by BTX has been featured in recent decades. This type of contamination is due to small and continuous leaks at gas stations, causing serious problems to public health and the environment. Based on these antecedents, the search for new alternatives for treating contaminated water is shown to be essential. Therefore, this study aimed to evaluate the efficiency of removal of BTX by adsorption processes employing commercial alumina (Al2O3) and alumina supported with iron (Fe/Al2O3) as adsorbents. It was prepared by a in a synthetic gasoline solution and distilled water to simulate an actual sample. Initially, the adsorbents were characterized by techniques XRD, TG / DTG, XRF, FTIR and SEM/EDS, several trials, where he was placed synthetic solution to react in the presence of Al2O3 and Fe/Al2O3 in a closed, mechanical stirring system were performed varying the catalyst concentration 2, 4 and 6 g.L-1 every 0, 10, 30 60, 90 and 120 min, aliquots were taken and brought to analysis by gas chromatography flame ionization with headspace extraction. The results indicated that the absorbent which has higher BTX removal capacity was the Fe/Al2O3 at a concentration of 6 g.L-1, pH = 4 and time of 90 minutes reaction, resulting in an efficiency, resulting in a 86,5% efficiency for benzene removal, for the 95,4% toluene, 90,8% for ɱ,ρ- xylene and 93.7% for the θ-xylenes. Subsequently, we performed a kinetic study of the reactions, the values of experimental adsorption capacity (qe) showed agreement with the values of the theoretical adsorption capacity (qc) to the pseudo-second-order model in the adsorption tests using 2 and 6 gL-1 of Al2O3 and assays using 2, 4 and 6 g.L-1 of Fe/Al2O3. A fact corroborated by the R2 values, thus indicating that the chemical interactions are present in the adsorption mechanisms of BTX.

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Produced water is the main effluent linked to the activity of extraction of oil and their caring management is necessary due to the large volume involved, to ensure to minimize the negative impacts of discharges of these waters in the environment. This study aimed to analyze the use of retorted shale, which is a reject from the pyrolysis of pirobituminous shale, as adsorbent for the removal of phenols in produced water. The material was characterized by different techniques (grain sized analysis, thermal analysis, BET, FRX, FT-IR, XRD and SEM), showing the heterogeneity in their composition, showing its potential for the removal of varied compounds, as well as the phenols and their derivatives. For the analysis of the efficiency of the oil shale for the adsorption process, assays of adsorption balance were carried through, and also kinetic studies and dynamics adsorption, in the ETE of the UTPF of Petrobras, in Guamaré-RN. The balance assays shown a bigger conformity with the model of Langmuir and the kinetic model more adjusted to describe the adsorption of phenols in retorted shale was of pseudo-second order. The retorted shale presented a low capacity of adsorption of phenols (1,3mg/g), when related to others conventional adsorbents, however it is enough to the removal of these composites in concentrations presented in the produced water of the UTPF of Guamaré. The assays of dynamics adsorption in field had shown that the concentration of phenol in the effluent was null until reaching its rupture (58 hours). The results showed the possibility of use of the reject for removal of phenols in the final operations of the treatment process, removing as well, satisfactorily, the color and turbidity of the produced water, with more than 90% of removal

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In this work, chitosan was used as a coating of pure perlite in order to increase the accessibility of the groups OH- e NH2+the adsorptionof ions Mn2+ e Zn2+.The characterization results of the expanded perlite classified as microporous and whose surface area 3,176 m2 g-1after the change resulted in 4,664 m2g-1.From the thermogravimetry(TG) it was found that the percentage of coating was34,3%.The infrared analysis can prove the presence of groups Si-OH, Si-O e Al-O-Siresulting from the perlite and C=O, NH2and OH characterization of chitosan. The experiments on experiments on the adsorption of Mn and Zn were performed in the concentration range of10 a 50 mgL-1and the adsorption capacity inpH 5,8 e 5,2 was 19,49 and 23,09 mgg-1to 25 oC,respectively.The adsorption data were best fitted to Langmuir adsorption model to Langmuir adsorption model for both metalionsisindicative of monolayer adsorption. The kinetics of adsorption were calculated from the equation of Lagergren fitting the model pseudo-second-order for all initial concentrations, suggesting that adsorption of ions Mn2+ and Zn2+ follows the kinetics of pseudo-second-order and whose constant Speedk2(g/mg.min) are 0,105 e 3,98 and capacity and maximum removal qe 4,326 e 3,348,respectively.In this study we used a square wave voltammetry cathodic stripping voltammetry to quantify the adsorbed ions, and the working electrode glassy carbon, reference electrode silver / silver chloride and a platinum auxiliary electrode. The attainment of the peaks corresponding to ions Mn2+ and Zn2+ was evaluated in and electrochemical cell with a capacity of 30 mL using a buffer system (Na2HPO4/NaH2PO4)at pH 4 and was adjusted with solutionsH3PO4 0,1molL-1and NaOH 0,1 molL-1and addition of the analyte has been a cathodic peak in- 0,873 Vand detection limit of2,55x10-6molL-1para Zn.The dough used for obtaining the adsorption isotherm was 150 mg and reached in 120 min time of equilibrium for both metal ions.The maximum adsorption for 120 min with Mn concentration 20 mgL-1 and Zn 10 mgL-1,was91, 09 e 94, 34%, respectively

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In this work a chitosan (CS) ionically crosslinked were manufactured by treatment with sulfuric acid solution for application in the treatment of wastewater from oil industry. Two crosslinking process were developed: homogeneous and heterogeneous. In the homogeneous process the ratio molar of SO42-/ NH3+ (1:6 and 1:4) were the variable analyzed, denominated CS16 and CS14 respectively. In the heterogeneous process the soaking time of the membranes in sulfuric acid solution were the variable studied, being used times of 5 (CS5) and 30 (CS30) minutes. FTIR-ATR results indicated no changes in the characteristics of chitosan after homogeneous crosslinking process, while heterogeneous crosslinking showed formation of ionic bonds between protonated groups from chitosan and the crosslinking agent sulfate ions. TG/DTG and XRD analysis confirmed the formation of these interactions, as also shown the new structure on the surface region of CS5 and CS30 membranes compared to CS, CS16 e CS14. Swelling test in aqueous medium have shown that crosslinking process reduced the membrane sorption capacity. Swelling test in acid medium demonstrated that CS16 and CS14 membranes increasing the adsorption capacity up to a maximum percentage of 140% approximately, whereas the CS5 e CS30 reached a maximum of 60%. The mechanical properties indicated the stiff and ductile behavior of crosslinked membrane. Adsorption experiments of CuCl2 results that CS16 membranes reached the efficiency maximum with 73% of copper removal at pH 5.0 and 87% at pH 4.0. The experiments with CuSO4 also obtained efficiency maximum to the CS16 membrane and 80% to the removal of Cu2+ ions. Also was verified that the increase of concentration and temperature cause a decrease in the adsorption capacity for all membranes. Kinetics study indicated that pseudo-second-order obtained characterized better the membranes. Equilibrium studies demonstrated that the CS, CS16 and CS14 follow the Langmuir model, whereas CS5 and CS30 follows Freundlich model. Filtration experiments results with rejection maximum to the CS16 and CS5 membranes, reaching 92 and 98% respectively.

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In this work a chitosan (CS) ionically crosslinked were manufactured by treatment with sulfuric acid solution for application in the treatment of wastewater from oil industry. Two crosslinking process were developed: homogeneous and heterogeneous. In the homogeneous process the ratio molar of SO42-/ NH3+ (1:6 and 1:4) were the variable analyzed, denominated CS16 and CS14 respectively. In the heterogeneous process the soaking time of the membranes in sulfuric acid solution were the variable studied, being used times of 5 (CS5) and 30 (CS30) minutes. FTIR-ATR results indicated no changes in the characteristics of chitosan after homogeneous crosslinking process, while heterogeneous crosslinking showed formation of ionic bonds between protonated groups from chitosan and the crosslinking agent sulfate ions. TG/DTG and XRD analysis confirmed the formation of these interactions, as also shown the new structure on the surface region of CS5 and CS30 membranes compared to CS, CS16 e CS14. Swelling test in aqueous medium have shown that crosslinking process reduced the membrane sorption capacity. Swelling test in acid medium demonstrated that CS16 and CS14 membranes increasing the adsorption capacity up to a maximum percentage of 140% approximately, whereas the CS5 e CS30 reached a maximum of 60%. The mechanical properties indicated the stiff and ductile behavior of crosslinked membrane. Adsorption experiments of CuCl2 results that CS16 membranes reached the efficiency maximum with 73% of copper removal at pH 5.0 and 87% at pH 4.0. The experiments with CuSO4 also obtained efficiency maximum to the CS16 membrane and 80% to the removal of Cu2+ ions. Also was verified that the increase of concentration and temperature cause a decrease in the adsorption capacity for all membranes. Kinetics study indicated that pseudo-second-order obtained characterized better the membranes. Equilibrium studies demonstrated that the CS, CS16 and CS14 follow the Langmuir model, whereas CS5 and CS30 follows Freundlich model. Filtration experiments results with rejection maximum to the CS16 and CS5 membranes, reaching 92 and 98% respectively.

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The destructive impact of improper disposal of heavy metals in the environment increases as a direct result of population explosion, urbanization and industrial expansion and technological developments. Argil are potential materials for adsorption of inorganic and the pelletization of it is required for use in adsorptive columns of fixed bed. The low cost and the possibility of regeneration makes these materials attractive for use in the purification process, capable of removing inorganic compounds in contaminated aquatic environments. In this work was made pellets of a mixture of dolomite and montmorillonite by wet agglomeration, in different percentages. The removal of Pb (II) was investigated through experimental studies, and was modeled by kinetic models and isotherms of adsorption. The materials were characterized using the techniques of XRD, TG / DTA, FT-IR, and surface area by BET method. The results showed the adsorption efficiency of the contaminant by the composite material studied in synthetic solution. The study found that the adsorption follows the Langmuir model, and the kinetics of adsorption follows the model of pseudosecond order

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In the Einstein s theory of General Relativity the field equations relate the geometry of space-time with the content of matter and energy, sources of the gravitational field. This content is described by a second order tensor, known as energy-momentum tensor. On the other hand, the energy-momentum tensors that have physical meaning are not specified by this theory. In the 700s, Hawking and Ellis set a couple of conditions, considered feasible from a physical point of view, in order to limit the arbitrariness of these tensors. These conditions, which became known as Hawking-Ellis energy conditions, play important roles in the gravitation scenario. They are widely used as powerful tools for analysis; from the demonstration of important theorems concerning to the behavior of gravitational fields and geometries associated, the gravity quantum behavior, to the analysis of cosmological models. In this dissertation we present a rigorous deduction of the several energy conditions currently in vogue in the scientific literature, such as: the Null Energy Condition (NEC), Weak Energy Condition (WEC), the Strong Energy Condition (SEC), the Dominant Energy Condition (DEC) and Null Dominant Energy Condition (NDEC). Bearing in mind the most trivial applications in Cosmology and Gravitation, the deductions were initially made for an energy-momentum tensor of a generalized perfect fluid and then extended to scalar fields with minimal and non-minimal coupling to the gravitational field. We also present a study about the possible violations of some of these energy conditions. Aiming the study of the single nature of some exact solutions of Einstein s General Relativity, in 1955 the Indian physicist Raychaudhuri derived an equation that is today considered fundamental to the study of the gravitational attraction of matter, which became known as the Raychaudhuri equation. This famous equation is fundamental for to understanding of gravitational attraction in Astrophysics and Cosmology and for the comprehension of the singularity theorems, such as, the Hawking and Penrose theorem about the singularity of the gravitational collapse. In this dissertation we derive the Raychaudhuri equation, the Frobenius theorem and the Focusing theorem for congruences time-like and null congruences of a pseudo-riemannian manifold. We discuss the geometric and physical meaning of this equation, its connections with the energy conditions, and some of its several aplications.

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The destructive impact of improper disposal of heavy metals in the environment increases as a direct result of population explosion, urbanization and industrial expansion and technological developments. Argil are potential materials for adsorption of inorganic and the pelletization of it is required for use in adsorptive columns of fixed bed. The low cost and the possibility of regeneration makes these materials attractive for use in the purification process, capable of removing inorganic compounds in contaminated aquatic environments. In this work was made pellets of a mixture of dolomite and montmorillonite by wet agglomeration, in different percentages. The removal of Pb (II) was investigated through experimental studies, and was modeled by kinetic models and isotherms of adsorption. The materials were characterized using the techniques of XRD, TG / DTA, FT-IR, and surface area by BET method. The results showed the adsorption efficiency of the contaminant by the composite material studied in synthetic solution. The study found that the adsorption follows the Langmuir model, and the kinetics of adsorption follows the model of pseudosecond order