Removal of Dyes from Water Using a TiO2 Photocatalyst Supported on Black Sand

A TiO₂ photocatalyst was prepared by depositing silica and titanium dioxide on the surface of black sand that made the photocatalyst recoverable using a magnetic field. The magnetic photocatalyst was used to remove six aqueous dyes from water and the removal was attributed to both adsorption and photocatalytic oxidation. Removal by adsorption was more noticeable with the cationic dyes than with the anionic dyes. The difference was related to the electrostatic interaction between the charged dye molecular and the silica-occupied surface of the photocatalyst. Removal by photocatalytic oxidation occurred with anionic dyes, while it was not appreciable with cationic dyes. It was postulated that photocatalytic oxidation might have happened with cationic dyes as well, but the strong adsorption made the photocatalytic oxidation undetectable.     

TiO2 Immobilized Biodegradable Polymer for Photocatalytic Removal of Chlorophenol

This study concentrated on the direct immobilization of anatase nano titanium dioxide particles (TiO₂, 44?nm particle size) into or onto a biodegradable polymer, polycaprolactone, by solvent-cast processes. The photocatalytic properties of the produced materials were tested by photocatalytic removal of organic contaminant 4-chlorophenol. Produced TiO₂ immobilized polymer successfully removed 4-chlorophenol (4-CP, 20?ppm which is equal to 1.56?×?10^?4?M) from aqueous solution without additional pH arrangement employing a UV-A light (365?nm) source. Immobilization of n-TiO₂ onto polycaprolactone (PCL) produced improved 4-CP removal percentages, reaching to nearly 85?%. Increased PCL mass significantly increases the removal percentage of 4-CP. When a UVC lamp emitting 254?nm light is used, the removal percentage reaches to 89?%. UV irradiation did not cause any change in the microstructure of the polymeric material (confirmed with ATR-FTIR analysis). This is an important evidence that the material could be reused for further photocatalytic treatments. Produced material seems to be highly promising for successful removal of organic pollutants beside its biodegradable nature.     

Reduced Graphene Oxide/Attapulgite-Supported Nanoscale Zero-Valent Iron Removal of Acid Red 18 from Aqueous Solution

In this paper, reduced graphenoxide/attapulgite (rGO/APT)-supported nanoscale zero-valent iron (nZVI) composites (rGO/APT-nZVI) were synthesized to remove acid red 18 (AR18) and other organic dyes from aqueous solutions. The structure of synthetic rGO/APT-nZVI composite was characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), transmission electron microscope (TEM), and X-ray diffraction (XRD), and the removal properties of rGO/APT-nZVI on AR18 were investigated. The factors of various experimental parameters (ratio, pH, initial concentration, temperature, and time) impacting on removal of AR18 were studied as well. Comparison experiment of different materials showed that 93.5% of AR18 was removed using rGO/APT-nZVI, while only 7.9% and 64.8% of AR18 were removed using rGO/APT-nZVI after reacting for 30 min with an initial AR18 concentration of 100 mg L^?1, respectively. Moreover, kinetic and thermodynamic analyses were used to study the reduction process, and possible mechanism of AR18 removal was discussed. The results show that the rGO/APT-nZVI composites can effectively degrade AR18 over a wide range of pH and keep degradation activity in a long storage. In addition, the superior behaviors for other organic dyes removal highlight the great potential as an efficient adsorbent for water pollution.     

Advanced Oxidation Processes in Triton X-100 and Wash-up Liquid Removal from Wastewater Using Modified TiO2/Al2O3 Photocatalysts

Photocatalytic methods were applied to remove the recalcitrant or toxic pollutants from the water. The two models of wastewater containing either non-ionic surfactant Triton X-100 or commercially available wash-up liquid were tested in a self-constructed band reactor during the laboratory studies. The photocatalyst, being typed TiO₂, was supported by porous Al₂O₃ and modified by the addition of Cu, Fe, Zn, Ni, Mo or Co. The photocatalysts were characterised by N₂ adsorption?Cdesorption, XRF, XRD, SEM-EDX, Raman and UV?CVis spectroscopy. All catalysts were efficient in the photocatalytic oxidation of surfactants, and they enabled at least 85?% COD reduction. TiO₂/Al₂O₃ photocatalysts modified by the transition metals were efficient only for more complicated compositions of surfactants. The effect of H₂O₂ (0.01?vol.%) addition was also examined and compared with a type of compound and catalyst used??in this case a positive effect for Triton X-100 was only observed over the photocatalyst modified by Ni. When it comes to the wash-up liquid photoremoval, all studied photocatalysts seem to be slightly influenced by H₂O₂ addition. It was also observed that it is not economically justified to conduct such treatment for more than 2?h.     

Analysis of Acid Alizarin Violet N Dye Removal Using Sugarcane Bagasse as Adsorbent

With the development of the textile industry, there has been a demand for dye removal from contaminated effluents. In recent years, attention has been directed toward various natural solid materials that are capable of removing pollutants from contaminated water at low cost. One such material is sugarcane bagasse. The aim of the present study was to evaluate adsorption of the dye Acid Violet Alizarin N with different concentrations of sugarcane bagasse and granulometry in agitated systems at different pH. The most promising data (achieved with pH 2.5) was analyzed with both Freundlich and Langmuir isotherms equations. The model that better fits dye adsorption interaction into sugarcane bagasse is Freundlich equation, and thus the multilayer model. Moreover, a smaller bagasse granulometry led to greater dye adsorption. The best treatment was achieved with a granulometry value lower than 0.21 mm at pH 2.50, in which the total removal was estimated at a concentration of 16.25 mg mL⁻¹. Hence, sugarcane bagasse proves to be very attractive for dye removal from textile effluents.     

Removal of Cu2+ and Cd2+ from Aqueous Solution by Bentonite Clay Modified with Binary Mixture of Goethite and Humic Acid

Pre-modification of bentonite clay with goethite, humic acid, and a binary mixture of goethite and humic acid reagents increased its cation exchange capacity from 95 to 105.32, 120.4, and 125.8 meq/100 g of bentonite clay, respectively. The effective pre-modification of bentonite clay with goethite, humic acid, and goethite–humic acid reagents was confirmed from their Fourier transform infrared spectra which suggested that modification was effective on the AlAlOH and Si–O sites for goethite and humic acid modification and AlAlOH for goethite–humic acid modification. The presence of 0.001 M NaNO₃ electrolyte increased the adsorption capacity of bentonite clay. Temperature was observed to favor the adsorption of Cu²⁺ and Cd²⁺ onto both the raw and modified bentonite clay samples. The goethite–humic acid-modified bentonite gave the best adsorption capacity of ≈10 and 16 mg/g at 30 and 50°C, respectively, for both metal ions. The inner sphere complexation mechanism was suggested for the adsorption of both metal ions onto the modified adsorbents. Modifying bentonite clay with a binary mixture of goethite and humic acid reduced the selectivity of bentonite clay for either Cu²⁺ or Cd²⁺. Preadsorbed goethite and humic acid on bentonite clay will further reduce the mobility of heavy metal ions in soils and in aquatic environments.     

Adsorption of Cesium from Aqueous Solution of Highly Concentrated Nitric Acid Using Supermolecule/Ordered Mesoporous Carbon Composite

Calix[4]arene-crown-6 compounds are promising ligands in the removal of cesium. With this aim, a macrocyclic compound, calix[4]arene-crown-6, was chemically immobilized onto inorganic ordered mesoporous carbon material. Several adsorption parameters such as nitric acid concentration, contact time, initial cesium content, operation temperature, and competing ions were studied. The results demonstrated the prepared material conserved high cesium selectivity of calix[4]arene-crown-6 and physicochemistry stability of the ordered mesoporous carbon matrix and showed the superior cesium adsorption performance. The optimum adsorption acidity determined as 3.0 M nitric acid was consistent with the actual acidity value in the back-end of the nuclear fuel cycle. The Langmuir model indicated the monolayer coverage adsorption and the highest mass adsorption capacity was calculated as 128.06 mg cesium/g. The pseudo-second-order model and D-R model proved the adsorption was a chemical process. Thermodynamics parameters showed the adsorption was spontaneous and exothermal in nature. Competing ions hardly affected cesium adsorption. Furthermore, the adsorbent showed almost intact adsorption capacity after five adsorption-elution cycles. The comprehensive performance highlights the composite material as a promising adsorbent for cesium adsorption from wastewaters.

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Graphical Abstract

     

Highly Efficient Removal of Cu(II) from Aqueous Solution by Using Graphene Oxide

Chemical reagents used by the textile industry are very diverse in their composition, ranging from inorganic compounds to polymeric compounds. Strong color is the most notable characteristic of textile effluents, and a large number of processes have been employed for color removal. In recent years, attention has been directed toward various natural solid materials that are able to remove pollutants from contaminated water at low cost, such as sugarcane bagasse. Cell immobilization has emerged as an alternative that offers many advantages in the biodegradation process, including the reuse of immobilized cells and high mechanical strength, which enables metabolic processes to occur under adverse conditions of pH, sterility, and agitation. Support treatment also increases the number of charges on the surface, thereby facilitating cell immobilization processes through adsorption and ionic bonds. Polyethyleneimine (PEI) is a polycationic compound known to have a positive effect on enzyme activity and stability. The aim of the present study was to investigate a low-cost alternative for the biodegradation and bioremediation of textile dyes, analyzing Saccharomyces cerevisiae immobilization in activated bagasse for the promotion of Acid Black 48 dye biodegradation in an aqueous solution. A 1 % concentration of a S. cerevisiae suspension was evaluated to determine cell immobilization rates. Once immobilization was established, biodegradation assays with free and immobilized yeast in PEI-treated sugarcane bagasse were evaluated for 240 h using UV–vis spectrophotometry. The analysis revealed significant relative absorbance values, indicating the occurrence of biodegradation in both treatments. Therefore, S. cerevisiae immobilized in sugarcane bagasse is very attractive for use in biodegradation processes for the treatment of textile effluents.     

Decomposition of Gaseous Acetone in an Annular Photoreactor Coated with TiO2 Thin Film

Photocatalytic decomposition of gaseous acetone was studied with a fixed-bed annular reactor using TiO₂ as the photocatalyst. The relation of UV light intensity to the reaction rate was found to be roughly first-ordered. The decomposition of acetone was obviously enhanced with increasing retention time. Removal of acetone was slightly increased with the relative humidity for experiments conducted with relative humidity below 20%. However, the removal of acetone was decreased drastically with relative humidity for experiments conducted with relative humidity greater than 20%. Decomposition of acetone was promoted considerably with increasing oxygen concentration for experiments conducted with oxygen less than 200,000 ppmv, yet the decomposition of acetone was kept relatively constant for experiments conducted with oxygen above 200,000 ppmv. Based on the mass balance for carbon species, the amount of organic intermediates formed for experiments conducted under various conditions were found to be minimal. Experimental results for the decomposition of gaseous acetone by UV/TiO₂ process can be adequately described by the developed two-site Langmuir–Hinshelwood (L–H) kinetic model.     

乙醇胺改性硅胶吸附剂对模拟沼气中CH_4/CO_2的分离性能

沼气的主要成分是CH4和CO2,有效地去除沼气中的CO2是确保沼气成为优质燃气的必要条件。吸附法是去除沼气中CO2的有效方法,研制性能优良的吸附剂是吸附法研究的核心问题。该文以FNG-II型硅胶为载体,乙醇胺(ethanolamine,MEA)为改性剂,制备了MEA改性硅胶吸附剂,表示为FS-MEA(FNG-II Silica-ethanolamine)。用X射线衍射、N2物理吸附脱附法、热重-差热、红外光谱等手段对吸附材料的结构、比表面积、孔结构、改性后结构变化等进行了分析。通过动态吸附分离试验,考察了FS-MEA对CH4/CO2的分离性能。结果表明:改性方法可将MEA附着在载体内孔表面,制得的FS-MEA可有效地分离CH4/CO2,但经过2次使用再生后,FS-MEA对CH4/CO2的分离性能有所下降,因此必须提高乙醇胺改性硅胶吸附剂的再生性能,才有可能使其应用于沼气提纯。     

Combined Removal of SO2, H2S AND NOx from Gas Streams by Chemical Absorption with Aqueous Solution of 12-Molybdophosphoric Acid and its Reduced Species

Selective removal of SO₂, H₂S and NO_x from gas streams (air or towngas) was investigated using aqueous solutions of 12-molybdophosphoric acid and its reduced molybdenum blue species. The experimental results showed that H₂S and SO₂ in the gas streams can be removed quantitatively by yellow solution of 12-molybdophosphoric acid. The H₂S was oxidized into recoverable elemental sulfur and SO₂ into H₂SO₄, while the yellow solution was reduced into blue species (reduced molybdenum blue). The obtained reduced molybdenum blue solution was then used for the quantitative removal of NO_x, which was reduced into N₂ and the blue solution was then oxidized back into yellow species. It is possible that the regenration of scrubbing solution is not required and no chemical is consumed during absorption, when NO_x, SO₂ and/or H₂S coexisted in wastegases and the molar ratios of NO₂/(SO₂ + H₂S) is just equal to 1/2, although, in most cases, the ratio in real practical wastegases is not always equal to the value. The absorption mechanism was studied in detail. It was found that only one molybdenum atom in 12-molybdophosphoric acid was reduced from Mo(VI) to Mo(V) by H₂S or H₂SO₃ and the Mo(V) was oxidized back into Mo(VI) in the case of No_x absorption. 12-molybdophsophoric acid used in this work is inexpensive, commercially available, easily regeneratable, relatively nontoxic, and gives no secondary pollutant in the process.     

Synergistic Degradation of Eosin Y by Photocatalysis and Electrocatalysis in UV Irradiated Solution Containing Hybrid BiOCl/TiO2 Particles

The present work focused on treatment of eosin (EO) by photocatalysis (PC) combined with electrocatalysis (EC) process. Bismuth oxychloride/titanium dioxide (BiOCl/TiO₂) hybrid particles, which were used as new heterogeneous photocatalysts, were exploited in a reverse microemulsion approach and were characterized by XRD, UV?CVis diffuse spectra, BET, and SEM technologies. All degradation experiments were performed using a self-assemble experimental setup, in which PC and EC could be carried out simultaneously or individually. The results indicated that BiOCl/TiO₂ showed enhanced photocatalytic performance under UV irradiation, and 50% BiOCl/TiO₂ exhibited the best photoactivity due to its high degree of crystallization, the mesoporous structure and corresponding large special surface area, improved absorption ability in UV region, and the heterojunction formed between two coupling particles. The combined degradation process displayed synergistic effect on the degradation of EO owing to the generation of H₂O₂ at graphite cathode. The parameters such as, pH, reaction current, and initial concentration of EO were monitored in order to optimize the operating conditions. Pseudo-first-order kinetics was proposed and roughly fitted the combined degradation of EO. The combined system in this work suggested a new research idea for the degradation of dye wastewater.     

Performances of Methyl Blue and Arsenic(V) Adsorption from Aqueous Solution onto Magnetic 0.8Ni0.5Zn0.5Fe2O4/0.2SiO2 Nanocomposites

Washing-down parlours and standing areas, following milking on dairy farms, produce dairy soiled water (DSW) that contains variable concentrations of nutrients. Aerobic woodchip filters can remove organic matter, nutrients and suspended solids (SS) in DSW, but the effluent exiting the filters may have to be further treated before it is suitable for re-use for washing yard areas. The performance of a single-layer sand filter (SF) and a stratified SF, loaded at 20 L m^?2 day^?1, to polish effluent from a woodchip filter was investigated over 82 days. Average influent unfiltered chemical oxygen demand (COD_T), total nitrogen (TN), ammonium–N (NH₄–N), ortho-phosphorus (PO₄–P) and SS concentrations of 1,991?±?296, 163?±?40, 42.3?±?16.9, 27.2?±?6.9 and 84?±?30 mg L^?1 were recorded. The single-layer SF decreased the influent concentration of COD_T, TN, NH₄–N, PO₄–P and SS by 39, 36, 34, 58 and 52 %, respectively. Influent concentrations of COD_T, TN_T, NH₄–N, PO₄–P and SS were decreased by 56, 57, 41, 74 and 62 % in the stratified SF. The single-layer SF and the stratified SF were capable of reducing the influent concentration of total coliforms by 96 and 95 %, respectively. Although a limited amount of biomass accumulated in the uppermost layers of both SFs, organic and particulate matter deposition within both filters affected rates of nitrification. Both types of SFs produced final water quality in excess of the standards for re-use in the washing of milking parlours.     

镁铝双氢氧化物和镁铁铝改性蒙脱土去除水体中磷的吸附效果研究

通过间歇式批实验和动力学实验研究了不同pH条件下磷酸盐在镁铝双氢氧化物（Mg-Al-LDH）、钠基膨润土（Na-Mt）及镁铁铝改性膨润土（Mg-Al-Mt、Fe-Mt和Fe-Al-Mt）的吸附特征。结果表明,在pH4.5～9.0范围内,随着pH的升高,Na-Mt,Fe-Mt和Fe-Al-Mt3种矿物对磷的吸附率相应减少,镁铝双氢氧化物对磷的吸附率有所增加;Mg-Al-LDH、Fe-Mt和Fe-Al-Mt的对磷吸附率约为95%,比Mg-Al-Mt高40%,比Na-Mt高80%。用Langmuir方程描述磷的等温吸附过程,最大吸附容量（Qm）大小顺序为Fe-Al-Mt〉Fe-Mt〉Mg-Al-LDH〉Mg-Al-Mt〉Na-Mt,b值大小依次为Mg-Al-LDH〉Fe-Mt〉Fe-Al-Mt〉Mg-Al-Mt〉Na-Mt,最大缓冲容量（Qmb）以Mg-Al-LDH的为最大,Na-Mt的为最小;Freundlich等温吸附方程参数KF代表相对吸附容量,以Mg-Al-LDH的KF值最高,依次是Fe-Mt、Fe-Al-Mt和Mg-Al-Mt,Na-Mt的KF值最小,这与Qmb的结果一致;决定系数（R2）表明,Langmuir等温吸附方程能更好地拟合铁改性蒙脱土和铁铝改性蒙脱土,而Freundlich方程对钠蒙脱土,双氢氧化物和镁铝改性蒙脱土的拟合效果要好。磷酸盐吸附过程分为快反应和慢反应,用动力学实验数据进行拟合,准二级动力学方程能够更好的拟合改性蒙脱土和Mg-Al-LDH对磷的动力学吸附数据,其决定系数为0.999;Elovich方程拟合改性蒙脱土磷酸盐的吸附数据也有很好的相关性（R2为0.89～0.94）。Na-Mt矿物磷酸盐的吸附用抛物线扩散方程描述最为合适,原因可能是磷酸盐镶嵌在矿物层间是一个扩散过程,不涉及化学吸附过程。     

Development of an Environmentally Friendly Adsorbent for the Removal of Toxic Heavy Metals from Aqueous Solution

An effective adsorbent for the removal of heavy metals was manufactured by immobilization of jujube powder. The adsorptions of Cd, Zn and Cu from aqueous solutions by jujube complex beads (Type 1 and Type 2) were studied in a batch adsorption system. The adsorption data were fitted well with the Langmuir isotherm models. The adsorption capacities (β) for Cd, Zn and Cu were 4.23, 2.93 and 3.64 mg/g in Type 1 and 1.24, 0.70 and 1.35 mg/g in Type 2 beads. The removal efficiencies of the Type 2 beads, with a larger unit surface area, were lower than those of the Type 1 due to part of the casein or cyclic AMP being destroyed during the drying process of the Type 1. These values for Type 1 beads were higher than those of all other adsorbents for each heavy metal. A comparison of the kinetic models on the overall adsorption rate showed that the adsorption system was best described by pseudo-first-order kinetics. The removal efficiencies of Cd, Zn and Cu exhibited similar tendencies to those observed in the equilibrium tests. This indicates that the jujube complex beads developed in this study can be used as promising adsorbents for the removal of heavy metals from wastewater.     

Invasive Freshwater Macrophyte Alligator Weed: Novel Adsorbent for Removal of Malachite Green from Aqueous Solution

The batch sorption experiments were carried out using a novel adsorbent, freshwater macrophyte alligator weed, for the removal of basic dye malachite green from aqueous solution. Effects of process parameters such as initial solution pH, contact time, adsorbent concentration, particle size, and ion strength were investigated. The adsorbent was characterized by FT-IR. The adsorption of malachite green by alligator weed was solution pH dependent. The adsorption reached equilibrium at 240 min for two particle size fractions. The pseudo-first-order equation, Ritchie second-order equation, and intraparticle diffusion models were tested. The results showed that adsorption of malachite green onto alligator weed followed the Ritchie second-order equation very well and the intraparticle diffusion played important roles in the adsorption process. The Langmuir and Freundlich equations were applied to the data related to the adsorption isotherms and the observed maximum adsorption capacity (q _max) was 185.54 mg g^?1 at 20°C according to the Langmuir model. The effects of particle size, adsorbent concentration, and ionic strength on the malachite green adsorption were very marked. The alligator weed could serve as low-cost adsorbents for removing malachite green from aqueous solution.