Insights into the S-shaped sorption isotherms and their dimensionless forms

Isotherms are of paramount importance for the interpretation of adsorption and ion exchange mechanisms and the design of separation and catalytic processes. Although the literature on sorption isotherms is rich, most of experiments and models employed are limited to systems that obey simple equilibrium isotherms, such as linear, favorable (convex-upward) or unfavorable (concave-upward). This paper deals with the rather overlooked S-shaped isotherms and their dimensionless forms, which are of great importance for the modeling of separation processes and interpretation of equilibrium data. A review on the physical significance and applications of S-shaped isotherms in adsorption and ion exchange process is also presented

Photochemical degradation of organic pollutants in wastewaters

In the present work, the photochemical treatment of a synthetic wastewater in a batch recycle photochemical reactor using ultraviolet irradiation (254 nm, 6 W), hydrogen peroxide and ferric ions was studied. Reactor volume was 250 mL with 55.8 mL of irradiated volume in the annular photoreactor. The synthetic wastewater was composed mainly of organic carbon. The effect of initial total carbon (136-1080 mg L-1), initial H2O2 amount (1332-5328 mg L-1), pH, and Fe(III) presence (2-40 ppm), on total carbon (TC) removal was studied. Each experiment lasted 120 min, and the process was attended via pH and TC concentration. Direct photolysis in the absence of any oxidant had practically no effect on TC removal. Regarding the effect of initial TC concentration in the wastewater keeping the same initial hydrogen peroxide concentration (2664 mg L-1), it was observed that for 136-271 mg L-1 TC, around 60% TC removal was achieved, while when initial TC was increased at 528 mg L-1, the TC removal observed decreased to 50%. For a further increase in TC at 1080 mg L-1, TC removal dropped to 14%. Initial pH adjustment of the wastewater resulted in slight variations of the TC removals achieved. Finally, adding Fe(III) in the process was beneficial in terms of TC removal obtained. Particularly, the addition of 40 ppm Fe(III) in the presence of 2664 mg L-1 H2O2 and initial TC equal to 528 mg L-1 increased the TC removal from 50% to 72%

Photocatalytic treatment of a synthetic wastewater

This work aimed at investigating the photocatalytic treatment of a synthetic wastewater using UV light (254 nm, 6 W), TiO2 catalyst and H2O2 in a batch recycle annular photoreactor. The total volume of the solution was 250 mL while the irradiated volume in the annular photoreactor with 55.8 mL. Each experiment lasted 120 min and samples were sent for Total Carbon and HPLC analysis. The stock wastewater had initial total carbon 1118 mg L-1. The effect of the presence of phenol in the wastewater on total carbon (TC) removal was also studied. It was shown that the photocatalytic treatment was effective only when initial TC was decreased to 32 mg L-1, whereas the optimum TiO2 concentration was 0.5 g L-1, leading to a TC removal up to 56%. For the same initial carbon load, the optimum H2O2 concentration was found to be 67 mg L-1 resulting in 55% TC removal. Combining, however, TiO2 and H2O2 did not lead to better performance, as 51% TC removal was observed. In contrast, when initial carbon in the wastewater was partially substituted by phenol, the combination of catalyst and hydrogen peroxide was beneficial. Specifically, when 10 ppm of phenol were added keeping the same initial TC concentration, UV/TiO2 treatment resulted in 46% TC removal and 98% phenol conversion, whereas using additionally H2O2 led to 100% phenol conversion after 45 minutes and 81% TC removal

Photocatalytic treatment of organic pollutants in a synthetic wastewater using UV light and combinations of TiO2, H2O2 and Fe(III)

In this study, the photocatalytic treatment of an organic wastewater with/without phenolic compounds by means of ultraviolet irradiation, titanium dioxide and hydrogen peroxide was examined in an annular photoreactor. Specifically, the effect of initial total carbon concentration, catalyst loading and H2O2 amount on the removal of total carbon was first examined in the case of a synthetic organic wastewater. The influence of partial carbon substitution by phenol, 2-chlorophenol, 2,4-discholophenol, trichlorophenol, and 4-nitrophenol on total carbon removal and target compounds’ conversion was studied keeping constant the initial organic carbon load. It was shown that the process applied was effective in treating the wastewater for initial total carbon 32 mg L-1, 0.5 g L-1 TiO2, and 66.6 mg L-1 H2O2. Applying UV/TiO2 and UV/H2O2, 58% and 53% total carbon removals were achieved, respectively, but combining TiO2 and H2O2 did not result in a better performance in the case of the synthetic wastewater without any phenolic compounds. In contrast, when a phenolic compound was added, the addition of H2O2 was beneficial, eliminating the differences observed from one phenolic compound to another. The total carbon removals observed were lower than the corresponding final conversions of the target phenolic compounds. Finally, the electric energy per order values were calculated and found to range in 52–248 kWh/m3/order, being dependent from the process applied and the phenolic compound present in the wastewater

TI2O3/TIO2-ASSISTED SOLAR PHOTOCATALYTIC DEGRADATION OF 4-TERT-BUTYLPHENOL IN WATER

Colored Ti2O3 and Ti2O3/TiO2 (mTiO) catalysts were prepared by the thermal treatment method. The effects of treatment temperature on the structure, surface area, morphology and optical properties of the as-prepared samples were investigated by XRD, BET, SEM, TEM, Raman and UV–VIS spectroscopies. Phase transformation from Ti2O3 to TiO2 rutile and TiO2 anatase to TiO2 rutile increased with increasing treatment temperatures. The photocatalytic activities of thermally treated Ti2O3 and mTiO were evaluated in the photodegradation of 4-tert-butylphenol (4-t-BP) under solar light irradiation. mTiO heated at 650 C exhibited the highest photocatalytic activity for the degradation and mineralization of 4-t-BP, being approximately 89.8% and 52.4%, respectively, after 150 min of irradiation. The effects of various water constituents, including anions (CO2 3 , NO3, Cl and HCO 3 ) and humic acid (HA), on the photocatalytic activity of mTiO-650 were evaluated. The results showed that the presence of carbonate and nitrate ions inhibited 4-t-BP photodegradation, while chloride and bicarbonate ions enhanced the photodegradation of 4-t-BP. As for HA, its effect on the degradation of 4-t-BP was dependent on the concentration. A low concentration of HA (1 mg/L) promoted the degradation of 4-t-BP from 89.8% to 92.4% by mTiO-650, but higher concentrations of HA (5 mg/L and 10 mg/L) had a negative effect

Effective photochemical treatment of a municipal solid waste landfill leachate

This work aimed at studying the photochemical treatment of a landfill leachate using ultraviolet light, hydrogen peroxide, and ferrous or ferric ions, in a batch recycle photoreactor. The effect of inorganic carbon presence, pH, initial H2O2 amount (0–9990 mg L-1) as well as Fe (II) (200–600 ppm) and Fe(III) (300–700 ppm) concentrations on the total carbon removal and color change was studied. Prior to the photochemical treatment, a pretreatment process was applied; inorganic nitrogen and inorganic carbon were removed by means of air stripping and initial pH regulation, respectively. The leachate sent subsequently for photochemical treatment was free of inorganic carbon and contained only organic carbon with concentration 1200±100 mg L-1 at pH 5.1–5.3. The most favorable concentrations of H2O2 and ferric ions for carbon removal were 6660 mg L-1 and 400 ppm, respectively. Adjusting the initial pH value in the range of 2.2–5.3 had a significant effect on the organic carbon removal. The photo-Fenton-like process was more advantageous than the photo-Fenton one for leachate treatment. By applying the most favorable operating conditions, 88.7% removal of total organic carbon, 100% removal of total inorganic carbon, 96.5% removal of total nitrogen, and 98.2% color removal were achieved

Catalytic oxidation of methylene blue by use of natural zeolite-based silver and magnetite nanocomposites

This work reports the synthesis of natural zeolite-based silver and magnetite nanocomposites and their application for the catalytic oxidation of methylene blue in water. The zeolite was impregnated with 5.5 wt.% Fe in the form of magnetite nanoparticles with size of 32 nm, and with 6.4 wt.% Ag in the form of silver oxide and metallic silver nanoparticles with sizes of 42 and 20 nm, respectively. The results showed that physical adsorption contributed to the removal of methylene blue by 25−36% and that Fe3O4@NZU is superior to Ag2O@NZU and Ag0@NZU, leading to 55% removal without oxidant and 97% in the presence of H2O2. However, there is no evidence of significant mineralization of methylene blue. The application of reaction rate models showed that the reaction order changes from zero to first and second order depending on the H2O2 concentration

Fixed-bed gasification and pyrolysis of organic fraction of MSW blended with coal samples

Buildup of vast quantities of municipal solid waste (MSW) including refuse derived fuel, organic fraction around the urban areas has negative environmental consequences. Gasification and pyrolysis of municipal solid waste could be an attractive option to utilize or convert to a valuable product. This study investigates the thermochemical properties of refuse derived fuel (RDF), organic fraction of MSW (Org MSW) and coal samples. Along with proximate and elemental analysis, calorific values were provided for RDF, MSW organic fraction, and coal samples. This followed by the thermogravimetric analysis of the same samples. In addition, Org MSW MSW and coal samples were blended in a proportion of 0.5/0.5 and 0.25/0.75 and then thermally treated in horizontal tube furnace both under air and inert gases to investigate the pyrolysis and gasification processes. TGA tests revealed that volatile content from Org MSW and RDF begin to be emitted at temperatures above 180-200 °C. Org MSW and RDF lose all their volatile contents at 500 °C and 700 °C. Pyrolysis experiments revealed that below 500 °C mostly tars are formed from Org MSW. Organic MSW and coal 0.5/0.5 blends yielded higher methane concentrations than coal or MSW alone, reaching 35-37 % at 800 °C. It could be concluded that both fixed bed and thermogravimetric method analysis have provided a good result to investigate the gasification and pyrolysis processes

Degradation and mineralization of 4-tert-butylphenol in water using Fe-doped TiO2 catalysts

In the present work, the photocatalytic degradation and mineralization of 4-tert-butylphenol in water was studied using Fe-doped TiO2 nanoparticles under UV light irradiation. Fe-doped TiO2 catalysts (0.5, 1, 2 and 4 wt.%) were prepared using wet impregnation and characterized via SEM/EDS, XRD, XRF and TEM, while their photocatalytic activity and stability was attended via total organic carbon, 4-tert-butyl phenol, acetic acid, formic acid and leached iron concentrations measurements. The effect of H2O2 addition was also examined. The 4% Fe/TiO2 demonstrated the highest photocatalytic efficiency in terms of total organic carbon removal (86%). The application of UV/H2O2 resulted in 31% total organic carbon removal and 100% 4-t-butylphenol conversion, however combining Fe/TiO2 catalysts with H2O2 under UV irradiation did not improve the photocatalytic performance. Increasing the content of iron on the catalyst from 0.5 to 4% considerably decreased the intermediates formed and increased the production of carbon dioxide. The photocatalytic degradation of 4-tert-butylphenol followed pseudo-second order kinetics. Leaching of iron was observed mainly in the case of 4% Fe/TiO2, but it was considered negligible taking into account the iron load on catalysts. The electric energy per order was found in the range of 28–147 kWh/m3/order and increased with increasing the iron content of the catalyst

PHOTOCATALYTIC DEGRADATION OF 4-TERT-BUTYLPHENOL USING SOLAR LIGHT RESPONSIVE AG2CO3

In this work, Ag2CO3 was prepared via a solution-based method and was further characterized by XRD, Raman spectroscopy, SEM/EDS analysis, and UV-VIS spectroscopy. SEM results revealed the formation of micro-sized particles with a rectangular shape. The photocatalytic activity of the catalyst was evaluated in the degradation of 4-tert-butylphenol (4-t-BP) under simulated solar light irradiation. The effects of 4-t-BP initial concentration (2.5–10 ppm), catalyst dosage (100–300 mg/L), different types of lamp sources, and water matrix were investigated. Complete 4-t-BP (5 ppm) degradation was achieved after 60 min by Ag2CO3 (200 mg/L). The effect of anions such as CO32−, HCO3−, NO3−, and Cl- in the concentration range of 100–300 mg/L was also studied. CO32− promoted the photocatalytic degradation process, while HCO3− and NO3− exhibited an inhibition effect, which was marked with increasing HCO3− and NO3− concentrations. The presence of Cl− at the concentration of 100 mg/L increased 4-t-BP degradation, but higher concentrations inhibited the photocatalytic reaction. Cyclic experiments showed that the catalyst practically retained its catalytic activity toward 4-t-BP degradation after three successive experimental runs. Keywords: 4-tert-butylphenol; degradation; heterogeneous photocatalysis; solar ligh