Performance of Granular Activated Carbon (GAC) Adsorption and Biofiltration in the Treatment of Biologically Treated Sewage Effluent

Abstract

In this study, the performance of GAC adsorption and biofiltration systems in treating biological treated sewage effluent (BTSE) was evaluated in terms of organic removal efficiency, organic fractions, and molecular weight distribution (MW) of organic matter (OM) removed. The GAC biofilter removed 23.5% and 61% of the hydrophobic fractions and hydrophilic fractions of OM in the BTSE respectively. MW distribution studies of GAC filter and GAC adsorption revealed the following: Hydrophobic fraction of the effluent showed a peak at 345 dalton after GAC biofiltration and 256 dalton after GAC adsorption, whereas, with hydrophilic fractions, peaks at 46,178 and 345 daltons were observed after GAC biofiltration and peaks at 46,178 and 256 daltons after GAC adsorption. Transphilic fraction showed the peaks at 12,783 dalton with GAC biofiltration, and 1,463 dalton with GAC adsorption. The performance of the GAC biofilter was successfully mathematically modelled.     

Effects of O3, O3/H2O2 and Coagulation on Natural Organic Matter and Arsenic Removal from Typical Northern Serbia Source Water

The objectives of this study were to investigate the effects of ozone and the O₃/H₂O₂ process on FeCl₃ coagulation efficiency for the removal of the high content of natural organic matter (NOM) and arsenic (As) from groundwater (DOC = 9.27 ± 0.92 mg/L; 51.7 ± 16.4 µg As/L). Arsenic and NOM removal mechanisms during coagulation/flocculation are well investigated. However, data concerning arsenic removal in the presence of NOM, which is the subject of this article, are still insufficient. Laboratory and pilot plant test results have shown that the competition of NOM and As for adsorption sites on the coagulant surface have great influence on coagulation/flocculation efficiency for their removal. With both oxidation pre-treatments, arsenic content after the coagulation process was less than 2.0 µg/L in treated water. Application of ozone has a lower influence on coagulation efficacy in terms of DOC reduction, compared to the O₃/H₂O₂ process with the same ozone dose.     

Degradation of dye wastewater in a thin-film photoelectrocatalytic (PEC) reactor with slant-placed TiO2/Ti anode

A thin-film photoelectrocatalytic (PEC) reactor with slant-placed TiO₂/Ti anode was developed and successfully applied to degrade Rhodamine B (RhB) and textile effluent. Using a 5–150 mg L⁻¹ RhB solution as the model system, thin-film PEC removed total color and TOC by 99–28% and 78–15%, respectively, in 1 h, which is much higher than 82–7% and 60% to zero by conventional PEC. The enhanced treatment efficiency achieved by thin-film PEC process was attributed to the significantly reduced path length of irradiation light source. The wastewater was kept circulating during the experiments to timely refresh the aqueous film on the TiO₂/Ti anode and promote the mass transfer of the target pollutants and the degradation products in the bulk solution. The thin-film PEC reactor can degrade both simulated and real dye wastewater efficiently under UV light irradiation. Results suggested that thin-film PEC was particularly superior for treating a high concentration solution. The thin-film PEC reactor was also applied to treat RhB solution efficiently under solar light irradiation. The recycle experiments demonstrated excellent stability and reliability of the slant-placed TiO₂/Ti anode. This study proposed a simple and effective method to design PEC reactor applicable for industrial dye wastewater treatment.     

The combination of photocatalysis process (UV/TiO2(P25) and UV/ZnO) with activated sludge culture for the degradation of sulfamethazine

The major factors affecting the removal efficiency of sulfamethazine (SMT) by photocatalysis process in the presence of TiO₂ P25 or ZnO, namely the pH, the amount of catalyst and the initial SMT concentration were examined. The obtained results showed the absence of adsorption of SMT on the catalysts and the absence of degradation of SMT by direct photolysis under UV light in the absence of catalyst. The variation of the pH solution in the range 4–9 did not cause any significant degradation of SMT. The optimal amounts of each catalyst were, respectively, 0.5 and 0.25 g/L for TiO₂ P25 and ZnO. Increasing the initial SMT concentration impacted negatively the removal efficiency, which decreased from 31% to 13% and from 100% to 27% in the presence of TiO₂ P25 and ZnO in the presence of 10 mg/L and 50 of SMT after 30-min reaction time, respectively. The obtained results showed better efficiency of ZnO than TiO₂ P25 regarding both removal efficiency and chemical oxygen demand (COD) abatement. However, removal efficiency and COD abatement were not complete, even after 7 h of photocatalysis, about 92% and 41%, respectively. The biodegradability was examined after photocatalysis performed in the following conditions: [SMT]₀ = 50 mg/L, pH = 6, T = 25°C, ω = 360 rpm and 0.5 g/L of TiO₂ P25 or 0.25 g/L of ZnO. In these conditions, the removal efficiencies were, respectively, 26% and 41% in the presence of TiO₂ P25 and 55 and 92% in the presence of ZnO after 4 and 7 h of pretreatment times, respectively. The BOD₅/COD ratio increased substantially and, respectively, from 0 to 0.25 and from 0 to 0.16 in the presence of TiO₂ P25 and ZnO after 7 h of irradiation. Even if the limit of biodegradability (0.4) was not achieved, a subsequent biological treatment was considered in the presence of TiO₂ P25, leading to 58% COD abatement after a 28-day culture.     

ML-WO3/TiO2异质结的制备及其对罗丹明B的光催化降解

采用空间限域法制备了单层三氧化钨纳米片(ML-WO₃),然后将其与TiO₂复合得到ML-WO₃/TiO₂纳米材料,被用来在模拟太阳光下对罗丹明B进行光催化降解。ML-WO₃/TiO₂的组成和光学特性通过扫描电镜、透射电镜、高分辨透射电镜、X射线衍射、紫外-可见吸收光谱和光致发光光谱手段进行表征。结果证实,纳米ML-WO₃/TiO₂克服了纯TiO₂带隙较大的缺陷,在全波段太阳光表现出比ML-WO₃和TiO₂更强的吸收性能,ML-WO₃与TiO₂之间具有明显的协同效应。活性物种捕获实验表明.OH和.O_2^-自由基是RhB降解的主要活性物种。ML-WO₃和TiO₂之间构建的Z型异质结电荷转移路径能够保证光生载流子的高效分离和重组。在5次循环实验后ML-WO₃/TiO₂的光催化活性仍能接近80%,具有良好的光化学稳定性。通过高效液相色谱-质谱检测RhB的中间产物,推测了RhB可能的降解路径。     

Preparation and Characterization of Titanium Dioxide (TiO2) from Sludge produced by TiCl4 Flocculation with FeCl3, Al2(SO4)3 and Ca(OH)2 Coagulant Aids in Wastewater

Abstract

In this study, TiCl₄ coagulant together with coagulant aids such as FeCl₃, Al₂(SO₄)₃, and Ca(OH)₂ were investigated to improve the photoactivity of titanium dioxide (TiO₂) produced from sludge and to increase the resulting low pH value. After TiCl₄ flocculation with three coagulant aids, the settled floc (sludge) was incinerated at 600°C to produce TiO₂ doped with Fe, Al, and Ca elements. Fe-, Al-, and Ca-doped TiO₂ was characterized in terms of structural, chemical, and photo-electronic properties. All the coagulant aids used together with Ti-salt flocculation effectively increased the pH values. The surface area of TiO₂-WO (without any coagulant aids), Fe/TiO₂, Al/TiO₂, and Ca/TiO₂ was 122 m²/g, 77 m²/g, 136 m²/g and 116 m²/g, respectively. The TiO₂-WO, Fe/TiO₂, Al/TiO₂, and Ca/TiO₂ was found to be of anatase phase. The XRD pattern on the Fe/TiO₂ included an additional peak of hematite (α-Fe₂O₃). The majority of gaseous acetaldehyde with TiO₂-WO and Ca/TiO₂ for photocatalytic activity was completely removed within 40 minutes under UV irradiation.     

Effects of Temperature and Photocatalysts on Removal of Polycyclic Aromatic Hydrocarbons (PAHs) from Automotive Industry Sludge

This study was carried out to investigate the removability of polycyclic aromatic hydrocarbon (PAH) compounds existed in automotive industry treatment sludge. The impacts of temperature, UV, titanium dioxide (TiO₂), and diethyl amine (DEA) were studied in a controlled device which was specifically designed for this study. Sludge samples were collected from the treatment plant of an automotive manufacturing facility in Bursa, Turkey. The ∑₁₀ PAH concentration value in the sludge was 4480 ± 1450 ng/g dry matter (DM). ∑₁₀ PAH removal ratio was 30% at 37°C without UV irradiation. Moreover, the PAH content in the sludge was reduced up to 65% through applying UV irradiation. This figure reached 100% by using photo-catalysts (TiO₂ or DEA) at the rate of 20% of the DM of the sludge.     

Selective synthesis of mixed alcohols from syngas over catalyst Fe2O3/Al2O3 in slurry reactor

The Fe₂O₃/Al₂O₃ catalyst was studied to selectively synthesize mixed alcohols from syngas in a continuously stirred slurry reactor with the oxygenated solvent Polyethylene Glycol-400 (PEG-400). The selectivity of mixed alcohols in the products reached as high as 95 wt.% and the C₂₊ alcohols (mainly ethanol) was more than 40 wt.% in the total alcohol products at the reaction conditions of 250 °C, 3.0 MPa, H₂/CO = 2 and space velocity = 360 ml/g_cat h. The hydrogen temperature programmed reduction (H₂-TPR) and X-ray photoelectron spectroscopy (XPS) measurements of the catalyst confirmed that the FeO phase was responsible for the high selectivity to mixed alcohols in the process. And the oxygenated solvent PEG-400 was also necessary for the selective synthesis of mixed alcohols in the reaction system.     

UV/H2O2 treatment of Rhodamine B in aqueous solution: Influence of operational parameters and kinetic modeling

The decolorization and degradation of Rhodamine B (RB) were investigated using UV radiation in the presence of H₂O₂ in a batch photoreactor at different light intensities. H₂O₂ and UV light have a negligible effect when they were used on their own. Removal efficiency of RB was sensitive to the operational parameters such as initial concentrations of H₂O₂ and RB, initial pH and light intensity. The results indicated that efficiency of process decreased with addition of inorganic ions and alcohols to the dye solution as hydroxyl radical scavengers. The semilogarithmic graphs of the concentrations of RB versus time were linear, suggesting pseudo-first order reaction for decolorization and degradation processes. A simple kinetic model is proposed which confirms pseudo-first-order reaction. The electrical energy per order (EE/O) values for decolorization and degradation of RB solution were calculated. Results shows that applying an optimum hydrogen peroxide concentration can reduce the EE/O.     

Effects of H2S and process conditions in the synthesis of mixed alcohols from syngas over alkali promoted cobalt-molybdenum sulfide

The present work is an investigation of how the process conditions influence the synthesis of mixed alcohols from syngas over a K₂CO₃/Co/MoS₂/C catalyst. The emphasis in the investigations is upon the effects of H₂S in the syngas feed. However the effects of the temperature and of the partial pressures of H₂ and CO are also investigated. With or without H₂S in the feed the pre-sulfided catalyst requires an initiation period to reach a stabilized behavior, but the duration of this period depends upon the H₂S level. Operation with a feed containing more than 103 ppmv H₂S leads to a fairly rapid stabilization of the product distribution and ensures that higher alcohols are the dominant reaction products. With less than 57 ppmv H₂S in the feed the stabilization of the product distribution is much slower, and methanol is the dominant product. An investigation of the reaction kinetics indicates a high CO coverage and low hydrogen coverage. Hydrogen sulfide in the syngas feed generally promotes chain growth for both alcohols and hydrocarbons, but lowers the alcohol selectivity by enhancing the hydrocarbon formation. The highest alcohol productivity reached in these investigations was 0.276 g/g cat./h, and this was achieved at 350 °C, 100 bar, GHSV = 5244 h⁻¹, Feed: 49.9 vol% H₂, 50.1 vol% CO. Finally it is found that sulfur fed to the reactor as H₂S is incorporated into the condensed alcohol product, and the incorporation of sulfur species into the product continues for some time after H₂S has been removed from the feed. When the catalyst is operated with an S-free syngas feed, the amount of sulfur in the condensed liquid product decreases over time, but after 35 h of operation with an S-free syngas the alcohol product still contains 340 ppmw of sulfur. Thiols appear to be the dominant sulfur compounds in the product.     

TiO2/H2O2 mediated photocatalytic transformation of UV filter 4-methylbenzylidene camphor (4-MBC) in aqueous phase: Statistical optimization and photoproduct analysis

Central composite design (CCD) based on response surface methodology (RSM) was employed in the present study in combination with “profiling and desirability function” to evaluate the effects of main variables (TiO₂, H₂O₂, and light intensity) affecting 4-methylbenzylidene camphor (4-MBC) photocatalytic degradation and for optimization of the process.Besides statistical optimization of the UV filter decomposition, the investigation involved a study of the identification of intermediate compounds, mineralization, as well as toxicity evaluation. The transformation of 4-MBC proceeds through: (i) demethylation of the bridged structure; (ii) hydroxylation of the methylbenzylidene moiety; (iii) bihydroxylation/demethylation reaction. Even if all the identified compounds are degraded themselves within 30 min, the complete carbon mineralization is only achieved after 24 h of irradiation. Toxicity assays using Vibrio fischeri, have shown that 4-MBC intermediates exhibit acute toxicity.     

Effect of precursor characteristics on zirconia and ceria particle morphology in spray pyrolysis

Ultrasonic spray pyrolysis of acetate-based precursors with precisely measured precursor drop size was employed to produce ZrO₂ and CeO₂ particles. A bimodal size distribution of the product particles indicates a significant influence of the gas-to-particle conversion mechanism in addition to the conventionally accepted one-particle-per-drop mechanism. Due to the differences in solubility of the precursors, ZrO₂ particles are spherical in shape and smooth on their surfaces while the CeO₂ particles are bowl-like in shape with uneven surfaces. Spherical and monodispersed particles with a peak diameter <100 nm can be obtained by reducing the precursor concentrations to 0.01 wt.% in both the different precursor system.     

Preparation of highly dispersed SiO2 and Pt particles in Nafion112 for self-humidifying electrolyte membranes in fuel cells

We have developed preparation protocol of practically large size self-humidifying polymer electrolyte membranes (PEMs) with highly dispersed nanometer-sized Pt and/or SiO₂ for fuel cells. The Pt particles were expected to catalyze the recombination of H₂ and O₂, leading to a suppression of the chemical short-circuit reaction at the electrodes, while the SiO₂ particles were expected to adsorb the water produced at the Pt particles together with that produced at the cathode reaction. Stable SiO₂ particles were formed in a commercial PEM (Nafion^®112) via in situ sol-gel reactions at 70 °C. It was found by SAXS that the hydrophilic cluster size increased by water adsorbed SiO₂, which may contribute to the increase in the proton conductivity once SiO₂ adsorbed water. Pt particles were uniformly dispersed in a Na⁺-form normal-PEM or SiO₂-PEM by an ion-exchange reaction with [Pt(NH₃)₄]Cl₂, followed by a reduction with 1-pentanol at 125 °C. The newly prepared Pt-SiO₂-PEM was found to perform a self-humidifying operation in a standard-size PEFC (25 cm² electrode area) with H₂ and O₂ humidified at 30 °C. The performance of the Pt-SiO₂-PEM cell operated with the low humidity reactant gases was as high as the normal-PEM cell fully humidified, because the ohmic resistance of the former cell was as low as the latter cell.     

Kinetics and specificity of Lipozyme-catalysed oil hydrolysis in supercritical CO2

Blackcurrant seed oil is rich in linoleic and linolenic acids. Selective enzyme-catalysed oil hydrolysis was studied with aim to obtain different levels of α- and/or γ-linolenic acid in the mixture of liberated fatty acids and in the fraction of di- and monoacylglycerols, making them suitable for special dietary needs. The oil was dissolved in supercritical carbon dioxide flowing through a packed bed reactor (temperature 40 °C, pressure 15–28 MPa, and superficial velocity 0.1–0.7 mm s⁻¹) with Lipozyme^®, a 1,3-specific lipase from Mucor miehei immobilised on a macroporous ion-exchange resin. The enzyme activity was stable as long as water precipitation in the reactor was prevented. The reaction was found to be controlled by both Michaelis–Menten kinetics and mass transfer. The maximum rate of fatty acids liberation per unit amount of enzyme, 2.6 × 10⁻³ mol s⁻¹ kg⁻¹, was achieved at the maximum flow velocity and pressure. Compared to oil, the liberated fatty acids contained more α-linolenic, palmitic and stearic acids, while di- and monoacylglycerols contained increased levels of γ-linolenic and stearidonic acids.     

Continuous enzymatic production of biodiesel from virgin and waste sunflower oil in supercritical carbon dioxide

A continuous process for biodiesel production in supercritical carbon dioxide was implemented. In the transesterification of virgin sunflower oil with methanol, Lipozyme TL IM led to fatty acid methyl esters yields (FAME) that exceeded 98% at 20 MPa and 40 °C, for a residence time of 20 s and an oil to methanol molar ratio of 1:24. Even for moderate reaction conversions, a fractionation stage based on two separators afforded FAME with >96% purity. Lipozyme TL IM was less efficient with waste cooking sunflower oil. In this case, a combination of Lipozyme TL IM and Novozym 435 afforded FAME yields nearing 99%.     

Similarity and differences in the oxidative dehydrogenation of C2–C4 alkanes over nano-sized VOx species using N2O and O2

The effect of O₂ and N₂O on alkane reactivity and olefin selectivity in the oxidative dehydrogenation of ethane, propane, n-butane, and iso-butane over highly dispersed VO_x species (0.79 V/nm²) supported on MCM-41 has been systematically investigated. For all the reactions studied, olefin selectivity was significantly improved upon replacing O₂ with N₂O. This is due to suppressing CO_x formation in the presence of N₂O. The most significant improving effect of N₂O was observed for iso-butane dehydrogenation: S(iso-butene) was ca. 67% at X(iso-butane) of 25%.Possible origins of the superior performance of N₂O were derived from transient experiments using ¹⁸O₂ traces. ¹⁸O¹⁶O species were detected in ¹⁸O₂ and ¹⁸O₂–C₃H₈ transient experiments indicating reversible oxygen chemisorption. In the presence of alkanes, the isotopic heteroexchange of O₂ strongly increased. Based on the distribution of labeled oxygen in CO_x and in O₂ as well as on the increased CO_x formation in sequential O₂–C₃H₈ experiments, it is suggested that non-lattice oxygen species (possibly of a bi-atomic nature) originating from O₂ are non-selective ones and responsible for CO_x formation. These species are not formed from N₂O.     

Adsorptive crystallization of benzoic acid in aerogels from supercritical solutions

In this work, adsorption and crystallization of benzoic acid in different porous carriers (silica aerogel, MCM41, Trisopor glass, zeolite) from supercritical CO₂ solutions is studied. The main purpose is to reveal the influence of the adsorptive properties of the carrier on the crystallization behavior of the solute. Therefore, both adsorption and crystallization processes are studied as a function of carrier's surface properties. Adsorption of the solute and CO₂ is measured in situ using a magnetic suspension balance, whereas crystallization is realized in a high pressure view cell. The carriers could be loaded with up to ∼35 wt.% of benzoic acid, depending on the nature and the amount of the functional groups of the carrier. The size of the benzoic acid particles obtained inside the aerogel matrix depends on the crystallization conditions and is in the range of ∼20 nm-50 μm. The crystallinity of the particles was studied and it is shown that the physical state of the loaded benzoic acid inside the pores of aerogels is influenced by benzoic acid-aerogel surface interactions: strong interactions favor the amorphous form, weak interactions favor crystalline particles. The amorphous form of benzoic acid is shown to be stable over a long time period. Thus, silica aerogels can be used for stabilizing amorphous forms of organic compounds, which can be used for instance in pharmaceutical applications for the improvement of drug bioavailability.