Iron(II) Sulfate(VI) from Titania Production as a Raw Material for Preparation of Hydrogen Sulfide Sorbents

A hybrid sorbent material for removal of hydrogen sulfide from air was developed. The material is based on activated carbon and iron compounds obtained from waste iron(II) sulfate(VI) heptahydrate. The iron salt is deposited on the carbonaceous support and subjected to oxidation (Fe²⁺ to Fe³⁺) using atmospheric oxygen under alkaline conditions. An effect of H₂O₂ addition to the process on the composition of the resultant material was also examined. X-ray diffraction (XRD) analyses confirmed easy conversion of waste FeSO₄·7H₂O to iron oxides Fe₃O₄ and FeOOH. The activated carbon supporting iron oxides revealed a higher efficiency in H₂S elimination from air compared to the commercial activated carbon, without any modification.     

Oxidation of Herbicides in Groundwater by the Fenton Process: A Realistic Alternative for O3/H2O2 Treatment?

Oxidation with O₃/H₂O₂ and Fe²⁺/H₂O₂ are optional for the degradation of herbicides and pesticides in water. The choice of which process will be applied depends upon the degree of degradation of organic micropollutants and the process conditions related to the formation of oxidation by-products, and also on the total costs and the safety and reliability of the process. Under real conditions, atrazine and some phenylureaherbicides were oxidized with O₃/H₂O₂. Comparable experiments under conditions of different pH, iron and DOC content were performed with Fe²⁺/H₂O₂, in order to gain information on the influence of these parameters. The oxidation results of both processes as well as the formation of bromate as one of the oxidation by-products are described. It was found that 80% of atrazine and >99% of some phenylureaherbicides could be degraded with O₃/H₂O₂ at pH 7.8 (H₂O₂/O₃ ratio 3.7 g/g). Under these conditions, bromate was formed up to 5 μg/1. Comparable results were obtained with Fe²⁺/H₂O₂ at a pH value of 5.5, whereas the formation of bromate was kept below 0.2 μg/L.     

Kinetics of Multi‐Step Redox Processes by Time‐Resolved In Situ X‐ray Diffraction

The kinetics of redox reactions of iron oxide in oxygen carrier 50Fe₂O₃/MgAl₂O₄ are examined using different time‐resolved techniques. Reduction kinetics are studied by H₂ temperature‐programmed reduction (H₂‐TPR) monitored by time‐resolved in situ XRD. In contrast to conventional TPR, in situ XRD distinguishes the three‐stage reduction of Fe₂O₃ → Fe₃O₄ → FeO → Fe. It also shows that the oxidation of Fe → Fe₃O₄ by CO₂ has no intermediate crystalline phases, explaining why its kinetics can easily be investigated by conventional CO₂ temperature‐programmed oxidation (CO₂‐TPO). A shrinking core model which takes into account solid state diffusion allows describing the experimental data.     

Synthesis of monodispersed micaceous iron oxide by the oxidation of iron with oxygen under hydrothermal conditions

The oxidation behavior of iron powder with oxygen was investigated in 5–25 m NaOH solutions at 5 MPa of oxygen partial pressure and 130–290°C, where m = mol(kg H₂O)^?1. Monodispersed micaceous iron oxide, α-Fe₂O₃, was synthesized by the oxidation of iron powder with 5 MPa of oxygen in 10–16 m NaOH solutions at 250–270°C. The diameter of micaceous iron oxide greatly changed depending on the reaction conditions such as the temperature, reaction time and concentrations of NaOH and coexisting ions.     

Modeling dye degradation kinetic using dark- and photo-Fenton type processes

Dark- and photo-Fenton type processes, Fe²⁺/H₂O₂, Fe³⁺/H₂O₂, Fe⁰/H₂O₂, UV/Fe²⁺/H₂O₂, UV/Fe³⁺/H₂O₂ and UV/Fe⁰/H₂O₂, were applied for the treatment of model colored wastewater containing two reactive dyes, C.I. Reactive Blue 49 and C.I. Reactive Blue 137, and degradation kinetics were compared. Dye degradation was monitored by the means of UV/VIS, adsorbable organic halides (AOX) and total organic carbon (TOC) analysis, thus determining decolorization and dechlorination of triazine structure, as well as mineralization of model colored wastewater. Both dark- and photo-Fenton type processes were proven to be very efficient for color removal; ≥98% was achieved in all cases. Significant improvements in the mineralization of studied dyes were achieved by the assistance of UV light, as it was expected. It was demonstrated that the degradation kinetic of applied dyes depended on the presence of UV light, as well as type of iron catalyst and dye structure. On bases of the obtained experimental results, the mathematical models were developed describing dye degradation kinetics in all studied systems. Since UV light was used in order to enhance the efficiency of dark-Fenton type processes, mathematical model describing dye degradation by UV photolysis providing the values of quantum yields for each of the dye was developed and incorporated in model for photo-Fenton type processes. A sensitivity analysis for the evaluation of importance of each reaction used in mathematical models was also performed.     

Study on an iron–manganese Fischer–Tropsch synthesis catalyst prepared from ferrous sulfate

A systematic study was undertaken to investigate the effects of the initial oxidation degree of iron on the bulk phase composition and reduction/carburization behaviors of a Fe–Mn–K/SiO₂ catalyst prepared from ferrous sulfate. The catalyst samples were characterized by powder X-ray diffraction (XRD), Mössbauer spectroscopy, X-ray photoelectron spectroscopy (XPS) and H₂ (or CO) temperature-programmed reduction (TPR). The Fischer–Tropsch synthesis (FTS) performance of the catalysts was studied in a slurry-phase continuously stirred tank reactor (CSTR). The characterization results indicated that the fresh catalysts are mainly composed of α-Fe₂O₃ and Fe₃O₄, and the crystallite size of iron oxides is decreased with the increase of the initial oxidation degree of iron. The catalyst with high content of α-Fe₂O₃ in its as-prepared state has high content of iron carbides after being reduced in syngas. However, the catalyst with high content of Fe₃O₄ in its as-prepared state cannot be easily carburized in CO and syngas. FTS reaction study indicates that Fe-05 (Fe³⁺/Fe_total = 1.0) has the highest CO conversion, whereas Fe-03 (Fe³⁺/Fe_total = 0.55) has the lowest activity. The catalyst with high CO conversion has a high selectivity to gaseous hydrocarbons (C₁–C₄) and low selectivity to heavy hydrocarbons (C₅₊).     

Effect of organic acid to enhance the oxidative power of the fenton-like system: Computational and empirical evidences

A Fenton-like system based on the combination of organic acid and hydrogen peroxide over an iron oxide surface was investigated. DFT calculations showed that HCOOH and H₂O₂ interact to produce the pair H₂O₂//HCOOH which leads to the formation of ¹OH more strongly than H₂O₂ alone, upon acceptance of a single electron. Empirical tests using H₂O₂ and HCOOH over iron oxides showed that Fe²⁺ contents and HCOOH enhance degradation of the reactive textile drimaren red dye in agreement with calculations.     

Sewage sludge treatment using microwave‐enhanced advanced oxidation processes with and without ferrous sulfate addition

BACKGROUND: Microwave‐enhanced advanced oxidation processes with and without the addition of ferrous sulfate (MW/H₂O₂/Fe²⁺‐AOP and MW/H₂O₂‐AOP respectively) were studied for reduction of solids and solubilisation of nutrients from secondary sewage sludge. RESULTS: For the MW/H₂O₂/Fe²⁺‐AOP the yields of solubilisation of orthophosphate and ammonia decreased with increasing temperature. The best results (88.1 mg L^?1 for orthophosphate and 22.7 mg L^?1 for ammonia) were obtained at a treatment temperature of 40 °C. In contrast, the MW/H₂O₂‐AOP had an advantage when it was operated at higher temperatures of 60 and 80 °C. The highest yields of solubilisation were obtained at 60 °C for orthophosphate (81.1 mg L^?1) and at 80 °C for both ammonia (35.0 mg L^?1) and soluble chemical oxygen demand (1954 mg L^?1). Over the temperature range used in this study, the MW/H₂O₂‐AOP gave a better performance than the MW/H₂O₂/Fe²⁺‐AOP. CONCLUSION: For sewage sludge treatment the MW/H₂O₂‐AOP is more effective than the MW/H₂O₂/Fe²⁺‐AOP in terms of solid reduction and nutrient solubilisation. It will also be more cost‐effective, as it does not require iron addition in the process. Copyright © 2008 Society of Chemical Industry     

Mössbauer effect study of the Fe-substituted NASICON

Fe-substituted NASICON was prepared by co-precipitation method and the content of iron at different oxidation states was estimated by Mössbauer spectroscopy (MS). Compounds with different phase composition were obtained depending on the preparation procedure. In the case of samples sintered in reducing atmosphere, NASICON containing di- and trivalent iron was detected. The lattice constants were calculated by Rietveld method. Higher values of the unit cell parameters for Na₃Zr_1−yFe_1−y²⁺Fe_2y³⁺P₃O₁₂ compared to the structural analogue γ-Na₃Fe₂P₃O₁₂ indicated the partial replacement of smaller Fe³⁺ ions by bigger Fe²⁺ and Zr⁴⁺ in the NASICON lattice. The validation of Mössbauer spectroscopy as the useful tool in the calculation of iron content was also performed. The sintering in air led to the multiphase product, which was identified by XRD and MS.     

CuI and H2O2 Inactivate and FeII Inhibits [Fe]‐Hydrogenase at Very Low Concentrations

[Fe]‐Hydrogenase (Hmd) catalyzes reversible hydride transfer from H₂. It harbors an iron‐guanylylpyridinol as a cofactor with an Fe^II that is ligated to one thiolate, two COs, one acyl‐C, one pyridinol‐N, and solvent. Here, we report that Cu^I and H₂O₂ inactivate Hmd (half‐maximal rates at 1 μM Cu^I and 20 μM H₂O₂) and that Fe^II inhibits the enzyme with very high affinity (K_i=40 nM ). Infrared and EPR studies together with competitive inhibition studies with isocyanide indicated that Cu^I exerts its inhibitory effect most probably by binding to the active site iron‐thiolate ligand. Using the same methods, it was found that H₂O₂ binds to the active‐site iron at the solvent‐binding site and oxidizes Fe^II to Fe^III. Also it was shown that Fe^II reversibly binds away from the active site iron, with binding being competitive to the organic hydride acceptor; this inhibition is specific for Fe^II and is reminiscent of that for the [FeFe]‐hydrogenase second iron, which specifically interacts with H₂.     

Development of iron oxide sorbents for Hg removal from coal derived fuel gas: Sulfidation characteristics of iron oxide sorbents and activity for COS formation during Hg removal

The aim of this study is to develop a process for the removal of Hg⁰ using H₂S over iron oxides sorbents, which will be located just before the wet desulfurization unit and catalytic COS converter of a coal gasification system. It is necessary to understand the reactions between the iron oxide sorbent and other components of the fuel gas such as H₂S, CO, H₂, H₂O, etc. In this study, the sulfidation behavior and activity for COS formation during Hg⁰ removal from coal derived fuel gas over iron oxides prepared by precipitation and supported iron oxide (1 wt% Fe₂O₃/TiO₂) prepared by conventional impregnation were investigated. The iron oxide samples were dried at 110 °C (designated as Fe₂O₃-110) and calcined at 300 and 550 °C (Fe₂O₃-300 and Fe₂O₃-550). The sulfidation behavior of iron oxide sorbents in coal derived fuel gas was investigated by thermo-gravimetric analysis (TGA). COS formation during Hg⁰ removal over iron oxide sorbents was also investigated using a laboratory-scale fixed-bed reactor. It was seen that the Hg⁰ removal activity of the sorbents increased with the decrease of calcinations temperature of iron oxide and extent of sulfidation of the sorbents also increased with the decrease of calcination temperature. The presence of CO suppressed the weight gain of iron oxide due to sulfidation. COS was formed during the Hg⁰ removal experiments over Fe₂O₃-110. However, in the cases of calcined iron oxides (Fe₂O₃-300, Fe₂O₃-550) and 1 wt% Fe₂O₃/TiO₂, formation of COS was not observed but the Hg⁰ removal activity of 1 wt% Fe₂O₃/TiO₂ was high. Both FeS and FeS₂ were active for Hg⁰ removal in coal derived fuel gas without forming any COS.     

The Nature and Properties of Iron-Containing Nanoparticles Dispersed in an Aluminosilicate Matrix of Cenospheres

The forms of iron in the composition of cenospheres prepared from energy ashes are investigated using the electron paramagnetic resonance (EPR) method, Mössbauer spectroscopy, and thermodynamic analysis. Cenospheres of controlled composition are produced by sieve, gravimetric, and magnetic separation. It is established that iron in two states (Fe³⁺, Fe²⁺) enters into the cenosphere composition. At an Fe₂O₃ content of 3–4 wt %, iron(III) predominantly occurs in two forms: single ions in the glass and particles of the superparamagnetic phase with a spinel structure. These particles are 30–50 Å in size and are dispersed in aluminosilicate glass. The sublattices of the superparamagnetic spinel are diamagnetically diluted with Mg²⁺ and Al³⁺ ions. At an Fe₂O₃ content of higher than 7 wt %, cenospheres also contain a magnetic phase based on defect magnetite.     

Photo-fenton and UV photo degradation of naphthalene with zero- and two-valent iron in the presence of persulfate

An initial set of 12 kinetic experiments was carried out to remove naphthalene from an aqueous effluent by photo-Fenton involving Fe⁰ and Fe²⁺ at two different concentrations of H₂O₂ (150 and 300?mg?L^?1) and three different pHs (3, 5, and 7) (2²×3¹ experiments). The rate constants (k) for the reaction of naphthalene degradation by involving Fe²⁺ as reactant were in general higher than those with Fe⁰, but the use of Fe²⁺ increased the concentration of naphthalene at equilibrium (C_e) when compared with the same response obtained with Fe⁰ at analogous conditions. A second set of twelve kinetic experiments of photo-Fenton degradation was also performed with persulfate as additive at the conditions already reported, but at a constant concentration of H₂O₂ of 150?mg?L^?1 (2¹×3¹ experiments with NaCl +2¹×3¹ experiments without NaCl). In almost all the runs in which only the source of iron was varied, k from the kinetic data involving Fe²⁺ was higher than that involving Fe⁰, but no difference was observed in terms of C_e that was always zero. The addition of persulfate to treat the effluent either containing or not containing salt enhanced the chemical kinetics, and shifted the equilibrium toward the full removal of naphthalene. A final set of nine experiments of UV photo degradation of naphthalene by involving persulfate without iron, with Fe⁰ and Fe²⁺ in the pH range from 3 to 7 (3² experiments) mainly showed that the use of H₂O₂ may be avoided to remove rapidly and completely naphthalene from wastewater.     

An efficient electron transfer at the Fe/iron oxide interface for the photoassisted degradation of pollutants with H2O2

Fe-200 was synthesized through the calcination of iron powder at 200 °C for 30 min in air. On the basis of characterization by X-ray diffraction and X-ray photoelectron spectroscopy, Fe-200 had a core–shell structure, in which the surface layer was mainly composed of Fe₂O₃ with some FeOOH and FeO, and the core retained metallic iron. The kinetics and mechanism of the interfacial electron transfer on Fe-200 were investigated in detail for the photoassisted degradation of organic pollutants with H₂O₂. Under deoxygenated conditions in the dark, the generation of hydroxyl radicals in aqueous Fe-200 dispersion verified that galvanic cells existed at the interface of Fe⁰/iron oxide, indicating the electron transfer from Fe⁰ to Fe³⁺. Furthermore, the effects of hydrogen peroxide and different organic pollutants on the interfacial electron transfer were examined by the change rate of the Fe³⁺ concentration in the solution. The results indicated that hydrogen peroxide provided a driving force in the electron transfer from Fe²⁺ to Fe³⁺, while the degradation of organic pollutants increased the electron transfer at the interface of Fe⁰/iron oxide due to their reaction with OH.     

Gaseous Elemental Mercury Removal Using Combined Metal Ions and Heat Activated Peroxymonosulfate/H2O2 Solutions

Several novel oxidation removal processes of elemental mercury (Hg⁰) from flue gas using combined Fe²⁺/Mn²⁺ and heat activated peroxymonosulfate (PMS)/H₂O₂ solutions in a bubbling reactor were proposed. The operating parameters (e.g., PMS/H₂O₂ concentration, Fe²⁺/Mn²⁺ concentration, solution pH, activation temperature, and Hg⁰/NO/SO₂/O₂/CO₂ concentration), mechanism and mass transfer-reaction kinetics of Hg⁰ removal were investigated. The results show that heat and Fe²⁺/Mn²⁺ have significant synergistic effect for activating PMS and PMS/H₂O₂ to produce free radicals to oxidize Hg⁰. Hg⁰ removal is strongly affected by PMS/H₂O₂ concentration, Fe²⁺/Mn²⁺ concentration, activation temperature, and solution pH. · and ·OH produced from combined heat and Fe²⁺/Mn²⁺ activated PMS/H₂O₂ play a leading role in Hg⁰ removal. Under optimized experimental conditions, Hg⁰ removal efficiencies reach 100, 94.9, 66.9, and 58.9% in heat/Fe²⁺/PMS/H₂O₂, heat/Mn²⁺/PMS/H₂O₂, heat/Fe²⁺/PMS, and heat/Mn²⁺/PMS systems, respectively. Hg⁰ removal processes in four systems belong to fast reaction and were controlled by mass transfer under optimized experimental conditions. © 2018 American Institute of Chemical Engineers AIChE J, 65: 161–174, 2019     

Iron exchanged ZSM-5 and Y zeolites calcined at different temperatures: activity in N2O decomposition

ZSM-5 and Y zeolites were modified with iron by an ion-exchange method and then calcined at 773, 873, 973 and 1,073 K. The obtained materials were characterized with respect to textural parameters (low-temperature N₂ sorption), structure (X-ray diffraction, UV–vis–DRS), redox properties (H₂-temperature programmed desorption, TPD) and surface acidity (NH₃-TPD). The obtained results have shown that the structure of zeolites influenced form, aggregation and content of the introduced iron species. In case of the FAU type structure characterized by wide pores (max. ring size, T-atoms—12) mainly iron in form of mononuclear Fe³⁺ cations and Fe _x ³⁺ O_y oligonuclear clustered species was found. On the other hand for the MFI type structure characterized by smaller pores (max. ring size, T-atoms—10) significant contribution of iron in the form of bulky Fe₂O₃ clusters located possibly on the outer surface of ZSM-5 was detected. Such significant differences in distribution of iron species is probably related to various mobility of iron species in the pore systems of both zeolites. The obtained materials were tested as catalysts in the process of N₂O decomposition. Calcination of zeolites at different temperatures influenced neither the properties nor the activity of the obtained catalysts.     

Effect of iron oxide content on the crystallisation of a diopside glass–ceramic glaze

The effect of iron oxide content on the crystallisation of a diopside glass–ceramic glaze was investigated using a glass–ceramic frit in the K₂O–ZnO–MgO–CaO–Al₂O₃–SiO₂ system and a granite waste glass. Measurements by X-ray diffraction (XRD) combined with scanning electron microscopy (SEM) and EDX microanalysis showed that the distribution of Fe³⁺ ions among different crystalline phases such as franklinite (ZnFe₂O₄) and hematite Fe₂O₃ depends on the iron content in the original diopside mixture. Thus, the original glaze crystallises to franklinite or hematatite when iron content is greater than 2 and 15%, respectively.     

Effect of UV Radiation on the Removal of Carboxylic Acids from Water by H2O2 and O3 in the Presence of Metallic Ions

The effect of UV radiation on the removal of formic, oxalic and maleic acids from water by metallic ion (Fe²⁺ or Cu²⁺)/H₂O₂ and metallic ion/O₃ was studied and compared. The results showed that metallic ion/O₃/UV has higher efficiency than metallic ion/H₂O₂/UV for oxalic acid removal. UV radiation significantly increases the efficiency of metallic ion/H₂O₂ for formic and maleic acids removal while its effect on the efficiency of metallic ion/O₃ for formic acid removal is minor_. However, at pH 2, O₃ alone showed higher efficiency than metallic ion/H₂O₂/UV for formic acid removal. Contrary to the relative efficiency of metallic ions in the previous systems, Cu²⁺ exhibited higher rate than Fe²⁺ for the removal of the degradation products of maleic acid by O₃. UV radiation exhibited a minor effect on the efficiency of Cu²⁺/O₃, while it exhibited a large effect on the efficiency of Fe²⁺/O₃ for the removal of the degradation products of maleic acid.     

Reaction of Ozone with Ag(I)—Mechanistic Considerations

Ozone reacts slowly with Ag⁺ (circumneutral pH, k = (11 ± 3) × 10^?2 M^?1 s^?1). After some time, ozone decay kinetics may suddenly become faster with the concomitant formation of silver sol. As primary process, an O-transfer from O₃ to Ag(I) is suggested, whereby Ag(III) is formed [Ag⁺ + O₃ + 2 H₂O → Ag(OH)₃ + O₂ + H⁺]. This conproportionates with Ag(I), which is in large excess, leading to Ag(II) [Ag⁺ + Ag(OH)₃ ? 2 Ag(OH)⁺ + HO^?]. Further, Ag(II) reacts with ozone in a high exergonic reaction [Ag(OH)⁺ + O₃ → Ag + 2 O₂ + H⁺], where ozone acts as a reducing agent. Thereby, a single silver atom, Ag, is formed that can be oxidized by O₂ and O₃ or can aggregate to a silver sol. Aggregation slows down the rate of oxidation. When Ag⁺ is complexed by acetate ions, ozone decay and silver sol formation are speeded up by enhancing Ag(II) formation [Ag(I)acetate + O₃ → Ag(III)acetate → Ag(II) + CO₂ + ?CH₃]. In the presence of oxalate, the formed complex reacts faster with ozone than Ag⁺, and Ag(III)oxalate decarboxylates rapidly [Ag(I)oxalate + O₃ → Ag(III)oxalate → Ag⁺ + 2 CO₂]. This enhances ozone decay but prevents silver sol formation. Quantum chemical calculations have been carried out for substantiating mechanistic suggestions.     

Hydroxylation of phenol with H2O2 over transition metal containing nano-sized hollow core mesoporous shell carbon catalyst

The catalytic performance of transition metal (Fe²⁺ or Cu²⁺) containing nano-sized hol low core mesoporous shell carbon (HCMSC) heterogeneous catalysts for the hydroxylation of phenol with hydrogen peroxide (H₂O₂) in water was investigated in a batch reactor. The metal-containing HCMSC catalyst showed higher activity than the same metal ion-exchanged zeolites. The nature of the metal and its content in the HCMSC had remarkable influence on the reaction results under the typical reaction conditions (PhOH/H₂O₂=3, reaction temperature=60 ‡C). Fe²⁺ containing HCMSC catalyst showed high catalytic activity with phenol conversion of 29%, selectivity to catechol (CAT) and hydroquinone (HQ) about 85%, H₂O₂ effective conversion about 70% and selectivity to benzoquinone (BQ) below 1% in the batch system.