Application of Sorption and Advanced Oxidation Processes for Removal of Phenols from Aqueous Solutions

The removal of organic contaminants such as aliphatic and aromatic hydrocarbons, phenols and related compounds, halogenated compounds, polycyclic aromatic hydrocarbons, aldehydes, ketones, acids, detergents, fats, dyes etc. from water and sewage is still an interesting and significant problem in environmental engineering. Both household and industrial waste is a source of organic contaminants in the environment. Higher and higher requirements regarding treated waste that is directed to water or the ground require constant development of the waste treatment process. The literature data and implemented solutions indicate that more and more attention is now paid to the use of sorption and advanced oxidation processes for the removal of organic compounds. The highest significance and application among available sorbents has activated carbon. The sorption properties of activated carbon are dependent on its porous structure, produced by the system of interconnected macro-, meso- and micropores as well as the chemical composition of the surface resulting from the presence of oxygen functional groups. Activated carbon is especially useful as sorbents of phenol and chlorophenol. It has been shown that the adsorption ability of activated carbon depends on the specific surface area, porosity and surface chemical composition. High affinity of phenol to the surface of activated carbon is related to the creation of donor-acceptor complexes between alkaline locations on the sorbent’s surface and the aromatic ring. Oxidation of activated carbon’s surface leading to increased acidity lowers the sorption capacity of activated carbon. While the presence of metals increases the sorption capacity of activated carbon in relation to phenol due to the donor-acceptor interaction of metal-electrons of π aromatic ring in the phenol particle. Another method of successful oxidation of phenols is their oxidation especially with the AOP methods (Advanced Oxidation Processe)s. A characteristic feature of these methods is oxidation of generally all organic compounds to CO2, H2O and inorganic compounds with the use of the hydroxyl radical OH* (generated in the solution) of extremely high oxidising potential of 2,8 V. Phenols and the related compounds quite easily undergo oxidation, especially with Fenton and photo-Fenton reactions. Both sorption and oxidation of organic compounds (including phenols) with AOP methods have advantages (high output and efficiency) and disadvantages (treatment of used sorbents, significant use of oxidants and increased sewage volume). In order to focus on the advantages of sorption and advanced oxidation while limiting their disadvantageous effect a combination of these two processes is considered. In this case the removal of contaminants is arranged as a two- or one-stage process. In the first one the removal of organic compounds covers sorption and then oxidation of the adsorbed substances with the use of AOP, which leads to a simultaneous regeneration of activated carbon. While in the latter case simultaneous sorption and oxidation of organic compounds is considered. In these both cases activated carbon acts as a sorbent of organic compounds and catalyst in the production of hydroxyl radicals OH* which are responsible for oxidation of organic compounds both in the solution and adsorbed on the activated carbon. It has been proven that in the presence of activated carbon in the environment of hydrogen peroxide, oxidation occurs of such organic compounds that do not undergo oxidation with the same oxidant in the aqueous solution. The applicability of activated carbon for the simultaneous removal of organic compounds is dependent on both their sorption and catalytic properties. Activated carbon should be alkaline, have high specific volume, pores’ volume, iodine number and significant dechlorination ability.The applicability of oxidation of organic compounds with the use of hydroxyl radicals created on the surface of activated carbon for regeneration of the used sorbents has also been proven

Analiza elementarna osadów pochodzących z miejskiej kanalizacji deszczowej w zależności od frakcji granulometrycznych

This is an investigation of the physical and chemical properties of sediments from the urban storm water drainage to determine the relationship between its quality and particle size. The catchment area of 85 ha is located in the center of the city with the main thoroughfares. The study included: granulometric analysis, content of mineral and organic substances, elemental composition and Scanning Electron Microscope (SEM) analysis. The results showed presence of eleven particular fractions, content of mineral substances on the level 80.46%. and organic substances on the level 19.54%. Article presents also the results of studies of elemental composition and SEM analysis in the sediments depending on the factions to confirm significant part of minerals

Adsorption of 2,4,6-Trichlorophenol onto Activated Carbon from Water-methanol Solutions

W pracy zbadano adsorpcję 2,4,6-trichlorofenolu na węglu aktywnym Norit R3-ex z wody, metanolu oraz roztworów woda/metanol o różnym składzie procentowym. Rozpatrywano zarówno kinetykę procesu, jak i adsorpcję w stanie równowagi. Badania kinetyczne pokazały, że 2,4,6-trichlorofenol adsorbował się szybciej z metanolu niż z wody, równowaga ustalała się odpowiednio po 3 i 5 godzinach. Kinetyka przebiegała zgodnie z modelem pseudo II rzędu, o czym świadczą wyższe wartości współczynników korelacji (> 0,99). Zbadano również adsorpcję w stanie równowagi z wody, metanolu oraz roztworów wodno- -metanolowych, zawierających 25, 50 i 75% rozpuszczalnika organicznego. Izotermy adsorpcji były dobrze opisane równaniem Freundlicha. Wartości stałych Freundlicha KF zmniejszały się wraz ze wzrostem zawartości metanolu w roztworze (od 1,533 dla wody do 0,288 dla czystego metanolu). Pokazuje to, że metanol wpływa negatywnie na adsorpcję 2,4,6-trichlorofenolu na węglu aktywnym. Zwiększenie zawartości rozpuszczalnika organicznego w roztworze powoduje pogorszenie adsorpcji.Adsorption of chlorophenols on activated carbon is one of the most popular methods for their removal from water. The adsorption process is affected by the adsorbate and adsorbent properties, temperature, and solution properties (e.g. ionic strength, pH). The influence of these parameters on the adsorption of chlorophenols on activated carbon is well documented, but to our knowledge there is no information on the effect of organic solvents. The purpose of this study was to examine the adsorption of the 2,4,6-trichlorophenol on activated carbon Norit R3-ex from water, methanol, and from water/methanol mixtures of different composition (25/75, 50/50 and 75/25%). Both, the kinetics and adsorption equilibria were investigated. The adsorbate concentrations in the solutions were measured by high- -performance liquid chromatography with ultraviolet detection. The kinetic studies were conducted for initial concentration of chlorophenol 0.25 mmol/dm3 from water and methanol. It was observed that 2,4,6-trichlorophenol was adsorbed more rapidly from the methanol than from the water, but nevertheless effective adsorption was much worse (41 vs. 93%). Adsorption equilibrium was achieved after 5 hours for water and after about 3 hours for methanol, respectively. In order to investigate the kinetics of adsorption the constant of adsorption were determined in terms of the pseudo-first-order and pseudo-second-order equations. The results showed that the pseudo-first-order model gives poor fitting with low R2 values, whereas the pseudo-second order model fits the experimental data quite well with correlation coefficients better than 0.99. Adsorption equilibrium data were also analyzed and were fitted well using Freundlich isotherm in the studied concentration range (from 0.05 to 0.5 mmol/dm3). The values of KF determined from the Freundlich plots decreased with increasing amount of methanol in a solution (from 1.533 for water to 0.288 for pure methanol). This suggests that methanol has a negative effect on the adsorption on activated carbon. Increasing of the methanol concentration in the solution results in deterioration of the 2,4,6-trichlorophenol adsorption

Adsorption of phenols from aqueous solutions on powdered activated carbons

The adsorption process by solid adsorbents is one of the most efficient methods for the removal of organic pollutants from water. Adsorption is attractive for its relative flexibility and simplicity of design, low cost, ease of operation and regeneration. Activated carbons are now the most commonly used adsorbents of proven adsorption efficiency for organic compounds due to their physicochemical properties including specific surface area, pore volume, pore size distribution and surface chemistry. For water treatment on a commercial scale granular activated carbon is most commonly used. In this paper the adsorption of phenol (Ph) and 4-cresol (4K) from aqueous solutions on powdered activated carbons (PAC) was studied. As adsorbents, two activated carbons L2S and SX2 with similar physicochemical properties were used. The adsorption was studied in a batch adsorption system, including both kinetics and equilibrium. The kinetics was fitted with the pseudo-first order and pseudo- second order models. The adsorption kinetics was found to follow the pseudo-second order model with the coefficient of determination values greater than 0.99. The adsorption isotherms were determined and modeled with the Freundlich and Langmuir equations. The equilibrium data obtained for both adsorbates were better described by the Langmuir model than by the Freundlich isotherm model. It was found that the 4K was adsorbed better than Ph on both adsorbents. The adsorption capacities of the L2S and SX2 activated carbons towards phenols were comparable. The values of the Langmuir adsorption capacity qm for phenol were 1.634 and 1.591 mmol/dm3 for the L2S and SX2 activated carbons, respectively. The qm values for 4-cresol were 1.885 and 1.844 mmol/dm3 for the L2S and SX2, respectively. The influence of solution pH on the adsorption was also investigated. The adsorption of the Ph and 4K was almost constant from the pH 2 to 8, and decreased significantly with further increase in the pH (above the pKa of the adsorbates and pHPZC of the adsorbents).W pracy porównano właściwości adsorpcyjne dwóch pylistych węgli aktywnych (L2S i SX2) o zbliżonych właściwościach fizykochemicznych jako adsorbentów do usuwania fenolu i 4-krezolu z roztworów wodnych. Zbadano kinetykę adsorpcji, adsorpcję w warunkach równowagowych oraz wpływ pH roztworu. Adsorpcja obydwu adsorbatów przebiegała zgodnie z modelem kinetycznym pseudo 2. rzędu, a w warunkach równowagowych była dobrze opisana równaniem izotermy Langmuira. W każdym przypadku 4-krezol adsorbował się szybciej i z większą wydajnością niż fenol. Różnice w pojemnościach adsorpcyjnych poszczególnych pylistych węgli aktywnych były niewielkie. Adsorpcja utrzymywała się na stałym poziomie w środowisku o pH od 2 do 8, jej znaczny spadek był obserwowany w wysokich wartościach pH (> 8), powyżej wartości pKa adsorbatów i pHPZC adsorbentów

Adsorption of phenol and copper(ii) ions on spherical activated carbon oxidized with ammonium persulfate

Zbadano adsorpcję fenolu i jonów miedzi(II) z modelowych roztworów wodnych na sferycznym węglu aktywnym utlenianym nadtlenodisiarczanem(VI) diamonu w różnych warunkach. Do oceny stopnia modyfikacji węgla wykorzystano analizę elementarną oraz izotermy adsorpcji pary wodnej i benzenu. Wykazano, że adsorpcję fenolu i jonów Cu(II) z roztworów wodnych można dobrze opisać modelami izoterm Freundlicha i Langmuira. Stwierdzono, że adsorpcja fenolu zmniejszała się wraz ze wzrostem stopnia utlenienia węgla i spadkiem jego powierzchni właściwej. Adsorpcja jonów Cu(II) zwiększała się wraz ze wzrostem stopnia utlenienia powierzchni węgla aktywnego, wykazując dużą rolę kwasowych grup tlenowych w adsorpcji jonów metalu na drodze wymiany jonowej. Wykazano również, że nadtlenodisiarczan(VI) diamonu okazał się bardzo skutecznym utleniaczem, gdyż nawet utlenianie węgla w najbardziej łagodnych warunkach (stężenie 0,1 mol/dm3, czas 30 min) dało znaczące zwiększenie ilości związanego tlenu (ok. 3,4-krotne) oraz znaczące zwiększenie ilości adsorbowanych jonów miedzi(II), przy stosunkowo niedużym zmniejszeniu ilości adsorbowanego fenolu.Adsorption of phenol and copper(II) ions from model aqueous solutions on spherical activated carbon oxidized with ammonium persulfate under various conditions was investigated. Elemental analysis and adsorption isotherms of water and benzene vapors were employed to assess the extent of modifications of the activated carbon surface. It was demonstrated that adsorption of phenol and Cu(II) ions from aqueous solutions could be well described by the Freundlich and Langmuir isotherm models. Adsorption of phenol decreased with the increasing degree of carbon oxidation as well as its decreasing specific surface area. Adsorption of the Cu(II) ions increased with the increasing degree of carbon surface oxidation indicating an important role of acidic groups in adsorption of metal ions by ion-exchange mechanism. Furthermore, ammonium persulfate was demonstrated to be an efficient oxidizing agent as carbon oxidation under even the mildest conditions (0.1 mol/dm3, 30 min) led to a significant increase in the oxygen bound (about 3-4 times) as well as the Cu(II) ions adsorbed. The amount of the adsorbed phenol decreased only slightly

Sensitivity and uncertainty analysis of hydrodynamic model (SWMM) for storm water runoff forecasting in an urban basin – a case study

Modelowanie ilości ścieków oraz napełnień przewodów sieci kanalizacyjnej stanowi istotny element umożliwiający ocenę funkcjonowania systemów odprowadzania wód opadowych z terenu zlewni. Złożoność procesów fizycznych, które są symulowane oraz ograniczona liczba danych dostępnych do kalibracji powoduje dużą niepewność uzyskanych wyników. W artykule przedstawiono przykład zastosowania techniki GSA-GLUE do analizy wrażliwości i probabilistycznej identyfikacji parametrów (szerokość drogi spływu, wysokość retencji terenowej powierzchni uszczelnionych i nieuszczelnionych, udział powierzchni uszczelnionej, współczynnik szorstkości kanałów, spadek podłużny zlewni) w przypadku modelu zlewni zurbanizowanej wykonanego w programie SWMM (storm water management model). Do kalibracji i walidacji modelu zlewni wykorzystano wyniki pomiarów wysokości opadów oraz przepływów ścieków deszczowych wykonanych w latach 2009–2011. Przeprowadzone obliczenia wykazały, że największy wpływ na kształt hydrogramu odpływu wód opadowych ze zlewni zurbanizowanej w opracowanym modelu hydrodynamicznym miały współczynnik szorstkości ścian kanałów oraz wysokość retencji terenów uszczelnionych. Uzyskane wyniki przeprowadzonej symulacji potwierdziły, że zastosowane w pracy metody oceny wrażliwości i identyfikacji parametrów mogą być pomocne przy kalibracji modeli hydrodynamicznych zlewni zurbanizowanych.Modeling of sewage volume and sewer system filling-ups is an important element that allows performance assessment of a rainfall drainage system from a basin area. The complex nature of physical processes being simulated and limited amount of observation data available for calibration make the model outcomes highly uncertain. The presented case study demonstrates an application of the GSA-GLUE technique (global sensitivity – generalized uncertainty estimation) to the sensitivity analysis and probabilistic identification of parameters (surface runoff width, water capacity of impervious and pervious surfaces, impervious surface fraction, the Manning roughness coefficient of channels and longitudinal basin slope) for the urban catchment model designed with the SWMM software. Measurement data of rainfall intensity and rain water flow from the period of 2009 to 2011 was used for calibration and validation of the basin model. The numerical experiments revealed that the channel roughness coefficient and water capacity measures of impervious surfaces had the highest impact on shape of the calculated hydrograph for storm water runoff in an urban basin. The simulation results confirmed that the sensitivity analysis and parameter identification methods applied might be useful in calibration of urbanized basin hydrodynamic models

Removal of 2,4,6-trichlorophenol from aqueous solutions using agricultural waste as low-cost adsorbents

Agricultural waste products including sunflower seed hulls, pumpkin seed shells, walnut shells and peanut shells were used as low-cost adsorbents for the removal of 2,4,6-trichlorophenol (TCP) from aqueous solutions. The effects of adsorbent dosage, pH and ionic strength on the adsorption of TCP were investigated. The results showed that the adsorption of TCP was pH dependent and increased upon increasing the ionic strength of the solution. The adsorption kinetics was found to follow a pseudo-second order kinetics. The equilibrium adsorption data were fitted to the Langmuir, Freundlich and Sips isotherms and the best results were achieved with the Freundlich model. The desorption of TCP using deionized water, water/methanol mixture or 5% sodium hydroxide was also studied. The results suggest that the tested materials may be used as an effective adsorbents without any treatment or any other modification for removal of TCP from the aqueous medium