Investigation on solar photocatalytic degradation of various dyes in the presence of Er3+:YAlO3/ZnO–TiO2 composite

In this work, Er³⁺:YAlO₃/ZnO–TiO₂ and ZnO–TiO₂ composites were prepared by the ultrasonic dispersion and liquid boiling method. In succession, they were then characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Acid red B as a model dye compound was degraded under solar light irradiation to evaluate the photocatalytic activities of the Er³⁺:YAlO₃/ZnO–TiO₂ and ZnO–TiO₂ composites. We found that the photocatalytic activity of ZnO–TiO₂ composite can be enhanced by adding an appropriate amount of Er³⁺:YAlO₃. We reviewed influencing factors, such as Er³⁺:YAlO₃ content, heat-treated temperature and heat-treated time on the photocatalytic activity of the Er³⁺:YAlO₃/ZnO–TiO₂ composites. In addition, the effects of solar light irradiation time, dye initial concentration, Er³⁺:YAlO₃/ZnO–TiO₂ amount and solution acidity on the photocatalytic degradation of acid red B dye in aqueous solution were investigated in detail. Simultaneously, the degradation and comparison of other dyes such as methyl orange (MO), rhodamine B (RM-B), azo fuchsine (AF), congo red (CG-R) and methyl blue (MB) were also reviewed. In addition, we attempted to explore both the principle of possible excitation of Er³⁺:YAlO₃/ZnO–TiO₂ under solar light irradiation and the mechanism of photocatalytic degradation.     

Unexpected difference in phenol sorption on PTMA- and BTMA-bentonite

The comparison of phenol sorption on phenyltrimethylammonium (PTMA)- and benzyltrimethylammonium (BTMA)-bentonite shows a clear difference as far as phenol sorption isotherms are concerned. For PTMA-bentonite the sorption isotherm is of a straight-line character which results from simple partitioning of phenol between the aqueous and organic phases sorbed on the bentonite surface. For BTMA-bentonite the isotherm has a convex shape, characteristic of physicochemical sorption.For the first time a three-parametric model, including the dissociation constant of phenol pK_a, distribution constant of phenol Kd_phen and phenolate anion Kd_phen⁻ between the aqueous phase and the bentonite phases is used for the evaluation of phenol sorption on organoclays with pH change. The model shows that the values of Kd_phen are higher than those of Kd_phen⁻ for all investigated initial phenol concentrations.The inspection of the FTIR spectrum of BTMA-bentonite loaded with phenol in the regions 1300–1600 and 1620–1680 cm⁻¹ shows the features of π–π electron interaction between the benzene rings of phenol and the BTMA cation together with the phenol–water hydrogen bond strengthened by this interaction.     

Phenol degradation using combined effects of hydrodynamic cavitation and oxidant: Doehlert matrix

Hydrodynamic cavitation (HC)-based treatments have been proposed for the degradation of phenol as a toxic pollutant. The present work aimed to optimize the degradation of phenol using HC by means of Doehlert experimental design, which has not been previously addressed. Initially, operational parameters of hydraulic characteristics of the pump, inlet pressure, solution pH, and initial concentration were optimized; later, the effects of pH solution and H₂O₂ loading or initial pollutant concentration on phenol degradation were explored using the Doehlert experimental design. It was observed that phenol degradation is strongly dependent on the pH of the solution. Also, the acidic condition favors the formation of hydroxyl radicals and thus, the degradation of phenol. Based on the Doehlert matrix, the 94.1% phenol degradation and 68.60% total organic carbon (TOC) were obtained in 180 min at 304.5 mg/L of hydrogen peroxide at an initial concentration of 20 mg/L, 2.0 pH, and 90 psi inlet pressure, providing a cavitational yield of 6.33 × 10⁻⁶ mg/J and minimum treatment cost of US$/L 0.13. Overall, it has been observed that HC can be a promising route for the removal of pollutants (phenol) effectively using hydrogen peroxide as an additive.     

Studies on solvent extraction of iron(III) as a step for conversion of a waste effluent to a value added product

Solvent extraction of iron(III) from actual sulphate waste pickle liquor was investigated using trialkylphosphine oxide diluted with kerosene. The waste pickle liquor was procured from a local company which deals with the manufacturing of pipes and tubes made of iron and steel. Various parameters were studied to optimise a suitable condition for the maximum extraction of iron. The composition of the aqueous feed used in the experiment was 60.88 g/L Fe(III), 53 g/L acid with traces of Cu, Ni and Co. An ambient extraction at 30 °C yielded acceptable kinetics and loading efficiency for 40% trialkylphosphine oxide with a saturated loading capacity of 51.85 g/L in four contacts at O/A ratio of 1/1 in a multiple contact mode. Iron from the loaded organic was stripped using various strippants such as distilled water, H₂SO₄ and oxalic acid. Since only 32% of loaded Fe could be stripped with 2 M H₂SO₄ in five contacts, further stripping was done with 5% oxalic acid which showed a very promising result. It was found that almost 100% of Fe(III) could be stripped out with 5% oxalic acid at O/A of 1/1 in five contacts.     

Effects of NO,NO<Subscript>2</Subscript>, CO and SO<Subscript>2</Subscript> on NO oxidation over Pt/TiO<Subscript>2</Subscript> for hybrid fast SCR process

The selective catalytic reduction (SCR) rate of NO with N-containing reducing agents can be enhanced considerably by converting part of NO into NO₂. The enhanced reaction rate is more pronounced even at lower temperatures by using an equimolar mixture of NO and NO₂ (fast SCR reaction). The oxidation characteristics of NO over catalyst Pt/TiO₂ have been determined in a fixed bed reactor (8 mm-ID) with different concentrations of oxygen, nitric oxide and nitrogen dioxide in the presence of 8% water. The conversion of NO to NO₂ increases with increasing oxygen (O₂) concentration from 3 to 12%, but it levels off at higher O₂ concentrations. The NO conversion to NO₂ decreases with increasing NO concentration and it also decreases by an addition of NO₂ in the feed stream. Therefore, the oxidation of NO over Pt/TiO₂ catalyst could be auto-inhibited by the reaction product of NO₂. The effects of CO and SO₂ on NO oxidation characteristics have also been determined. In fact, the presence of SO₂ significantly suppresses oxidation of NO but due to the less stability of sulfate on anatase structure in TiO₂, it becomes less significant. On the other hand, the presence of CO increases NO oxidation significantly due to the auto-inhibition effect by CO. Moreover, the effect of SO₂/CO on NO oxidation has also been determined and it was observed that NO oxidation decreases with the increase in SO₂/CO ratio.     

The Immobilization of Titanium Dioxide on Organic Polymers,for a Cost Effective and Energy Efficient Means of Improving Indoorair Quality

The formation and spray coating, with Degussa P25 titanium dioxide (TiO₂), of a room temperature curable resin to form a photocatalytically active material is described in this paper. The TiO₂ surface layers produced have been characteristed with the aid of scanning electron microscope analysis. The photocatalytic activity of the samples tested using a gas phase continuous flow type photoreactor, the test pollutant being propene. Analysis of the test results indicates the potential of TiO₂ coated polymers to form effective photocatalytic materials, with the potential to improve indoor air quality and reduce the energy consumption of ventilation systems.     

Utilization of UV‐A and UV‐C radiation in advanced oxidation processes with the intention of removing color and organic matter from the gross leachate of a stabilized sanitary landfill

The present work investigated color and biochemical oxygen demand (COD) removal from treated landfill leachate via advanced oxidative processes (AOPs) artificially emitted. The AOP H₂O₂/UV, TiO₂/UV, and photolysis were tested in two bench‐scale photoreactors: The first one with UV‐C lamp and the other with UV‐A lamp associated or not with coagulation / flocculation pretreatment. Crude leachate samples with pH ranging from 8 to 3 were used, and time varied in 30, 45, and 60 minutes. Experiments were performed in two stages: step 1 with a 20 mL volume from each sample and step 2 with repetition of the best results from the previous step, adopting the 150 mL volume. In step 1, the AOP applied in the crude leachate sample showed the best results, standing out H₂O₂/UV‐C with 30 minutes and TiO₂/UV‐A with 60 minutes. In step 2, H₂O₂/UV‐C had a 60% color removal and 25% COD reduction, while TiO₂/UV‐A had a 10% color removal and 20% COD reduction. Therefore, the H₂O₂/UV‐C process was the most efficient, because the complex characteristics of the effluent interfered in the TiO₂/UV‐A efficiency, but it is necessary to eliminate the process interferences. The use of artificial radiation is a viable alternative; however, it can be costly, being relevant in the associations between processes with artificial UV and solar UV, as the natural radiation becomes more attractive and allows the process operating costs reduction.     

Super effective Zn-Fe-doped TiO2 nanofibers as photocatalyst for ammonia borane hydrolysis

In this study, the photocatalytic activity of TiO₂ nanofibers toward ammonia borane hydrolysis has been strongly modified by doping the nanostructure by ZnO and Fe₂O₃ oxides. Due to the differences in the work function and band gap energy among the three semiconductors (TiO₂, ZnO and Fe₂O₃), illumination of TiO₂ leads to accumulate the electrons and holes on the conduction and valance bands of Fe₂O₃ and ZnO, respectively. Accordingly, the experimental results indicated that the surface of the obtained nanofibers is very active which results in an instant hydrolysis of ammonia borane molecules reaching the active zone surrounding the nanofibers. Moreover, negative activation energy was determined as increasing the temperature led to decrease the photocatalytic performance. Furthermore, kinetic studies indicated that the heterogeneous catalytic reaction describing the ammonia borane hydrolysis process is zero order which additionally supports the super activity of the introduced nanofibers. It was also observed that Fe₂O₃ content in the introduced nanofibers has distinct influence as the best performance was obtained at 1 wt%. The modified TiO₂ nanofibers were prepared by calcination of electrospun nanofibers composed of titanium isopropoxide, zinc acetate and iron acetate in air at 700 °C for 1 h. Overall, the present study opens a new avenue to overcome the fast electrons/holes recombination dilemma facing TiO₂-based nanostructures.     

Possible Utilization of Silica Gel Sludge for the Removal of Phenol from Aqueous Solutions: Laboratory Studies

This paper discusses the adsorption capacity of silica gel sludge for phenol removal from aqueous solution. Kinetic experiments showed that phenol adsorption was completed after 2 h. Adsorption isotherms were measured for phenol from aqueous solution onto silica gel sludge under various pHs and temperatures. Results showed that the adsorption capacities for phenol was increased as pH decreased from 6.5 to 2. Temperature also was found to affect the adsorption isotherm. As temperature increases from 30 to 50°C, the adsorption capacity increases. The adsorption equilibrium of phenol on silica gel sludge was described by the linear Freundlich and Langmuir models. Furthermore, results showed that the isotherm parameters fit both linearized Langmuir and Freundlich adsorption isotherms. The Freundlich and Langmuir parameters at optimum pH was found as K _f=2.89, 1/n=0.23 and K _d=22.0, q _m=7.98, respectively. Whereas, for those at optimum temperature it was observed as K _f=2.87, 1/n=0.16 and K _d=20.93, q _m=7.91, respectively.     

Adsorptive removal of Cd(II) and Pb(II) ions from aqueous solutions by using Turkish illitic clay

The ability of Turkish illitic clay (TIC) in removal of Cd(II) and Pb(II) ions from aqueous solutions has been examined in a batch adsorption process with respect to several experimental conditions including initial solution pH, contact time, initial metal ions concentration, temperature, ionic strength, and TIC concentration, etc. The characterization of TIC was performed by using FTIR, XRD and XRF techniques. The maximum uptake of Cd(II) (11.25 mg g⁻¹) and Pb(II) (238.98 mg g⁻¹) was observed when used 1.0 g L⁻¹ of TIC suspension, 50 mg L⁻¹ of initial Cd(II) and 250 mg L⁻¹ of initial Pb(II) concentration at initial pH 4.0 and contact time of 240 min at room temperature. The experimental data were analyzed by the Langmuir, Freundlich, Temkin and Dubinin Radushkevich (D-R) isotherm models. The monolayer adsorption capacity of TIC was found to be 13.09 mg g⁻¹ and 53.76 mg g⁻¹ for Cd(II) and Pb(II) ions, respectively. The kinetics of the adsorption was tested using pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion models. The results showed that the adsorption of Cd(II) and Pb(II) ions onto TIC proceeds according to the pseudo-second-order model. Thermodynamic parameters including the Gibbs free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) changes indicated that the present adsorption process was feasible, spontaneous and endothermic in the temperature range of 5–40 °C.     

Heterostructure CdS/ZnS nanoparticles as a visible light-driven photocatalyst for hydrogen generation from water

(CdS)_x/(ZnS)_1–x nanoparticles were synthesized as a visible light-driven photocatalyst using the stepped microemulsion technique with a series of the ratio factors (x). The photocatalytic test results showed that (CdS)_x/(ZnS)_1-x with x = 0.8 had the highest photo-reactivity for H₂ production from water under visible light. The composite (CdS)_0.8/(ZnS)_0.2 catalyst had a heterogeneous structure that exhibited a much greater photocatalytic hydrogen production activity than either pure CdS or the homogeneous Cd_0.8Zn_0.2S solid solution. ZnS deposition also was shown to largely improve the stability of CdS in the heterostructured CdS/ZnS catalyst. Thermal treatment of the catalyst, i.e., annealing (CdS)_0.8/(ZnS)_0.2 at 723 K, improved the crystallinity of the catalyst and increased its photocatalytic H₂ production rate by more than 36 times. Deposition of Ru on the surface of the catalyst particles by in situ photo-deposition further increased the photo-H₂ generation rate by 3 times. The photocatalyst of 0.5%Ru/CdS/ZnS achieved the highest H₂ production activity, at a rate of 12650 μmol/g-h and with a light to hydrogen energy conversion efficiency of 6.5%.     

Tandem bed configuration for sorption-enhanced steam reforming of methane

The required properties of a CO₂ sorbent for sorption-enhanced steam–methane reforming (SESMR) are derived following a top-down approach. First the required CO₂ equilibrium pressure of the sorbent is derived from system restraints, then a suitable sorbent is searched for matching the required CO₂ pressure. The selected material, barium orthotitanate Ba₂TiO₄, has been characterized and tested on lab-scale. From this follows that the capacity and kinetics are poor compared with CaO, which has been investigated for SESMR. The best use of Ba₂TiO₄ is in combination with CaO, making use of the good properties of both: the high capacity and good kinetics of CaO, and the low CO₂ equilibrium pressure of Ba₂TiO₄ allowing high CH₄ conversion at relatively low steam-to-methane ratios (3–4).     

Nanocatalyzed biodiesel synthesis from the oily contents of Marine brown alga Dictyota dichotoma

This research article demonstrates biodiesel synthesis through the methanolysis of the oily contents (4.02 ± 0.27% w/w on dried basis) of Dictyota dichotoma collected from the coast of Hawksbay, Pakistan. The metal oxides (CaO, MgO, ZnO, and TiO₂) used as nanocatalysts were refluxed (5% K₂SO₄), calcinated (850 °C) and characterized by Atomic Force Microscopy (AFM) which produced 93.2% w/w FAME (biodiesel) at relatively mild condition (5% catalyst, 65 °C, 3 h, 18:1 molar ratio) using CaO. Whereas, MgO, ZnO, and TiO₂ produced 92.4%, 72.5%, and 31.8% w/w FAME, respectively at elevated condition (225 °C). Thus, CaO was considered to be the best catalyst among the others. This tri-phase reaction require continuous fast mixing and the yield depends on the reaction parameters like catalyst amount, temperature, reaction time and molar ratio (methanol: oil). The reusability of these heterogeneous catalysts simplified the purification step, reduced the waste generation and make the final product technically and economically viable.     

Chilled ammonia process for CO2 capture

The chilled ammonia process absorbs the CO₂ at low temperature (2–10 °C). The heat of absorption of carbon dioxide by ammonia is significantly lower than for amines. In addition, degradation problems can be avoided and a high carbon dioxide capacity is achieved. Hence, this process shows good perspectives for decreasing the heat requirement. However, a scientific understanding of the processes is required. The thermodynamic properties of the NH₃–CO₂–H₂O system were described using the extended UNIQUAC electrolyte model developed by Thomsen and Rasmussen in a temperature range from 0 to 110 °C and pressure up to 100 bars. The results show that solid phases consisting of ammonium carbonate and bicarbonate are formed in the absorber. The heat requirements in the absorber and in the desorber have been studied. The enthalpy calculations show that a heat requirement for the desorber lower than 2 GJ/ton CO₂ can be reached.     

Utilization of calcite and waste glass for preparing construction materials with a low environmental load

In this study, porous calcite materials are hydrothermally treated at 200 °C using powder compacts consisting of calcite and glasses composed of silica-rich soda-lime. After treatment, the glasses are converted into calcium aluminosilicate hydrates, such as zeolite phases, which increase their strength. The porosity and morphology of new deposits of hydrothermally solidified materials depend up on the chemical composition of glass. The use of calcite and glass in the hydrothermal treatment plays an important role in the solidification of calcite without thermal decomposition.     

Trapping and decomposing of color compounds from recycled water by TiO2 coated activated carbon

Five types of commercially available activated carbons (ACs) were coated with TiO₂ nanoparticles prepared using a sol–gel method. Color and trace organics remaining in the actual treated effluent were adsorbed by TiO₂ coated ACs. The absorbed organic compounds were then decomposed using a photocatalytic process, and the ACs were regenerated for reuse. The efficiency of the process was assessed by the characterization of true color and A₂₅₄ (the organics absorption at the wavelength of 254 nm) at the beginning and the end of the experiment. The effects of UV light source, UV irradiation time, hydrogen peroxide and ultrasound on the efficiency of photocatalytic regeneration were also investigated. Significant differences in the efficiency were observed between uncoated ACs and TiO₂ coated samples. Among the 5 types of ACs tested, AC-3, AC-4 and their coated ones achieved better efficiency in color and A₂₅₄ removal, with around 90% or more color and A₂₅₄ being removed within 1 h of treatment. The data obtained in this study also demonstrated that the photocatalytic process was effective for decomposing the adsorbed compounds and regenerating the spent TiO₂/AC-3. Finally, it was found that this regeneration process could be greatly enhanced with the assistance of H₂O₂ and ultrasound by reducing the required regeneration time.     

Characterization of MSWI fly ash through mineralogy and water extraction

This paper investigates the mineralogical characteristics of fresh, aged and hot water extracted MSWI fly ash for providing the baseline information of minerals stability which controls the released heavy metals into the environment. Quantitative determination of bulk phase abundance in the fresh fly ash by the XRD Rietveld refinement method provided composition levels for amorphous and crystalline phases such as potassium tetrachlorozincate (K₂ZnCl₄), gehlenite, halite, quartz, anhydrite, and feldspar. The minerals association in the fly ash is clearly unstable and subject to mineralogical reactions. The phases of K₂ZnCl₄, halite and anhydrite in the fresh fly ash were involved in hydration and dissolution/precipitation processes to form new minerals such as the Zn-bearing mineral gordaite, syngenite, gypsum and hydrocalumite. The solubility-controlling phases and extractability of heavy metals were examined in a Soxhlet hot water-extractor. Here the soluble salts were simply removed from fly ash while Ca-, Al-, Si- and SO₄²⁻-bearing hydrate minerals were precipitated from the extraction solution. Furthermore, a low release of heavy metals Zn, Pb and Cd in hot water was noticed, indicating a strong retention of the trace metals in the mineral phases remaining in the insoluble fly ash residues.     

Limitations for brine acidification due to SO2 co-injection in geologic carbon sequestration

Co-injection of sulfur dioxide during geologic carbon sequestration can cause enhanced brine acidification. The magnitude and timescale of this acidification will depend, in part, on the reactions that control acid production and on the extent and rate of SO₂ dissolution from the injected CO₂ phase. Here, brine pH changes were predicted for three possible SO₂ reactions: hydrolysis, oxidation, or disproportionation. Also, three different model scenarios were considered, including models that account for diffusion-limited release of SO₂ from the CO₂ phase. In order to predict the most extreme acidification potential, mineral buffering reactions were not modeled. Predictions were compared to the case of CO₂ alone which would cause a brine pH of 4.6 under typical pressure, temperature, and alkalinity conditions in an injection formation. In the unrealistic model scenario of SO₂ phase equilibrium between the CO₂ and brine phases, co-injection of 1% SO₂ is predicted to lead to a pH close to 1 with SO₂ oxidation or disproportionation, and close to 2 with SO₂ hydrolysis. For a scenario in which SO₂ dissolution is diffusion-limited and SO₂ is uniformly distributed in a slowly advecting brine phase, SO₂ oxidation would lead to pH values near 2.5 but not until almost 400 years after injection. In this scenario, SO₂ hydrolysis would lead to pH values only slightly less than those due to CO₂ alone. When SO₂ transport is limited by diffusion in both phases, enhanced brine acidification occurs in a zone extending only 5 m proximal to the CO₂ plume, and the effect is even less if the only possible reaction is SO₂ hydrolysis. In conclusion, the extent to which co-injected SO₂ can impact brine acidity is limited by diffusion-limited dissolution from the CO₂ phase, and may also be limited by the availability of oxidants to produce sulfuric acid.     

Carbon dioxide capture and recovery by means of TSA and/or VSA

Experimental work is performed with a 5A zeolite on a small laboratory column with heating from the wall. Carbon dioxide adsorption occurs at atmospheric pressure and different CO₂ concentrations in nitrogen. Comparisons of different methods of desorption by heating, purge and/or vacuum are studied. Desorption by heating only leads to almost pure CO₂ (around 99% purity) and a recovery nearly linear to the heating temperature, ranging from 45% at 130 °C to 79% at 210 °C. Recovery can be subsequently increased with a nitrogen purge to more than 98% but the recovered carbon dioxide is diluted due to the dispersive character of the desorption wave and the operation time is long. Increasing the flow rate decreases the desorption time but has no effect on the purity because the total purge volume remains about the same. Substitution of the purge step with a vacuum step leads to pure CO₂ and almost total recovery. Desorption under vacuum only without heating leads to pure CO₂ (around 99% purity) but limited recovery (85% in the present work).Desorption under vacuum seems to be more simple for large-scale applications. When using a water liquid ring pump, the temperature of the ring must be kept as low as possible to provide a high operating capacity.     

Structure and thermal stability of toxic chromium(VI) species doped onto TiO2 powders through heat treatment

Chromium(VI)-containing sorbents in the form of sludge or solid residue from treatment processes are often landfilled or used as fill materials, therefore the long-term stability of metal binding is important. The reduction of Cr(VI)–Cr(III) through heat treatment may be a useful detoxification method. After heating at 500, 900, 1000, and 1100 °C for 4 h, the transformation of chemical states of chromium on 105 °C-dried, 7.9% Cr(VI)-doped TiO₂ powders was studied on the basis of surface area measurements, scanning electron microscopy (SEM) images, X-ray diffraction (XRD), and extended X-ray absorption fine structure (EXAFS) spectra. It was shown that Cr(VI) was reduced to Cr(III) in the Cr(VI)-doped samples after heating within 500–900 °C. The present results also suggested that the chromium octahedral was bridged to the titanium tetrahedral and was incorporated in TiO₂ minerals formed after 1000 °C treatment.