Comparison of Catalytic Degradation of Aniline by Immobilized Iron Oxide Catalysts

Abstract In this study, iron oxides immobilized onto silica and alumina granular carriers in a fluidized-bed reactor were applied as silica granule (SG) and alumina granule (AG) catalysts, respectively; the SG and AG catalysts were used to explore the catalytic decomposition of H2O2. Effects of H2O2 concentration and temperature on the oxidation of aniline were determined to compare the reactive efficiencies of the SG and AG catalysts. Results showed that H2O2 decomposition could be efficiently catalyzed by the SG and AG catalysts. Degradation rates of aniline increased with increasing H2O2 concentration and temperature in both catalyst systems. The AG catalyst (smaller particle size) had more surface sites for precipitation of iron oxide than the SG catalyst (larger particle size). Consequently, in the initial stages of the reaction, hydroxyl radicals (?OH) were generated more rapidly with the AG catalyst than with the SG catalyst and the degradation of aniline by the AG catalyst was faster than that by ...     

Carbon‐neutral jet‐fuel re‐synthesised from sequestrated CO2

A chemical pathway combining reverse water gas shift, Fischer‐Tropsch synthesis and hydro‐cracking was considered to re‐synthesise jet fuel from CO₂ captured at high purity by oxy‐fuelling of a typical coal‐fired power station (Drax, UK). The oxygen for oxy‐fuelling and hydrogen for the fuel re‐synthesis process are sourced by electrolysis of water. According to material and energy balances , 3.1 MT/year of jet fuel and 1.6 MT/year each of gas oil and naphtha can be produced from the Drax annual emissions of 20 MT of CO₂, sufficient to supply 23% of the UK jet fuel requirements. The overall re‐synthesis requires 16.9 GW, to be sourced renewably from (offshore) wind power, and releases 4.4 GW of exothermic energy giving scope for improvements via process integration. The energy re‐synthesis penalty was 82% ideally and 95% on a practical basis. With the cost of offshore wind power predicted to reduce to 2.0 p/kWh by 2020, this ‘re‐syn’ jet fuel would be competitive with conventional jet fuel, especially if carbon taxes apply. The re‐use of CO₂ sequestrated from coal power stations to form jet‐fuel would halve the combined CO₂ emissions from the coal power and aviation sectors.     

Removing lignin model pollutants with BiFeO3–g-C3N4 compound as an efficient visible-light-heterogeneous Fenton-like catalyst

BiFeO_3–g-C_3N_4 nanoscaled composite was prepared with a hydrothermal method and evaluated as a highly efficient photo-Fenton like catalyst under visible light irradiation. The BiFeO_3–g-C_3N_4 composite exhibited much stronger adsorption ability to lignin model pollutant(guaiacol) than that of BiFeO_3, which may be due to the higher specific surface area(BiFeO_3–g-C_3N_4: 35.59 m~2/g BiFeO_3: 7.42 m~2/g) and the adsorption form of π–π stack between g-C_3N_4 and guaiacol. The composite exhibited excellent visible light-Fenton like catalysis activity, being influenced by the solution pH value and the proportions of BiFeO_3 and g-C_3N_4 nanosheets. Under optimal conditions with visible light irradiation, the BiFeO_3–g-C_3N_4 composite yielded fast degradation of guaiacol with an apparent rate constant of 0.0452 min~(-1), which were 5.21 and 6.80 folds of that achieved by using BiFeO_3 and the mixture of BiFeO_3 and g-C_3N_4 nanosheets, respectively. The significantly enhanced visible light-Fenton like catalytic properties of the BiFeO_3–g-C_3N_4 composite in comparison with that of BiFeO_3 was attributed to a large surface area, much increased adsorption capacity and the semiconductor coupling effect between BiFeO_3 and g-C_3N_4 in the composite.     

Fe3O4/FeS2活化H2O2降解典型苯胂酸类污染物

利用水热法成功制备了Fe₃O₄/FeS₂催化剂,并将其用于构建非均相芬顿体系降解典型的苯胂酸类污染物（洛克沙胂,ROX）.XRD、SEM、XPS和磁学测量系统（VSM）等表征结果表明,Fe₃O₄/FeS₂呈明显的颗粒状且具有良好的磁性.降解实验结果显示,在最优条件下（初始pH值为4.5、ROX起始浓度为20mg/L、Fe₃O₄/FeS₂投加量为0.15g/L和H₂O₂浓度为0.034g/L,Fe₃O₄/FeS₂介导的非均相芬顿体系可以超快速降解ROX,1min后的降解效率达到96.74%,明显优于单独的Fe₃O₄或FeS₂体系.此外,Fe₃O₄/FeS₂可以通过磁铁进行快速回收利用,同时也具有良好的重复利用性能,使用3次后,ROX的降解效率仍超过80%.机理分析表明,Fe₃O₄/FeS₂能够快速地催化H₂O₂产生具有强氧化性的羟基自由基（·OH）.在·OH的作-用下,ROX分子结构中C-As、C-N和C-C等化学键发生断裂,发生脱砷、脱硝和开环等反应,进而生成一系列的有机产物（如酚类、醌类、小分子有机酸等）和无机产物（As （V）和NO₃^-）.之后,无机砷能够被吸附在催化剂表面,而有机产物则进一步被矿化.     

Enhanced activation of peroxydisulfate by strontium modified BiFeO3perovskite for ciprofloxacin degradation

A series of Sr-doped BiFeO₃ perovskites (Bi_1-xSr_xFeO₃, BSFO) fabricated via sol-gel method was applied as peroxydisulfate (PDS) activator for ciprofloxacin (CIP) degradation. Various technologies were used to characterize the morphology and physicochemical features of prepared BSFO samples and the results indicated that Sr was successfully inserted into the perovskites lattice. The catalytic performance of BiFeO₃ was significantly boosted by strontium doping. Specifically, Bi_0.9Sr_0.1FeO₃ (0.1BSFO) exhibited the highest catalytic performance for PDS activation to remove CIP, where 95% of CIP (10 mg/L) could be degraded with the addition of 1 g/L 0.1BSFO and 1 mmol/L PDS within 60 min. Moreover, 0.1BSFO displayed high reusability and stability with lower metal leaching. Weak acidic condition was preferred to neutral and alkaline conditions in 0.1BSFO/PDS system. The boosted catalytic performance can be interpreted as the lower oxidation state of Fe and the existence of affluent oxygen vacancies generated by Sr doping, that induced the formation of singlet oxygen (¹O₂) which was confirmed as the dominant reactive species by radical scavenging studies and electron spin resonance (ESR) tests. The catalytic oxidation mechanism related to major ¹O₂ and minor free radicals was proposed. Current study opens a new avenue to develop effective A-site modified perovskite and expands their application for PDS activation in wastewater remediation.     

氧化法处理水中酚的研究方法综述

目前氧化法处理含酚废水的方法有化学氧化法即臭氧氧化法、Fenton试剂氧化法等，酶催化氧化法以及光化学氧化法即光敏化氧化、光催化氧化法等；分析了它们的优势及存在的问题；并提出了今后的研究方向，即臭氧-生物活性炭、臭氧辐射、臭氧-H2O2技术，水溶性酶制剂连接到固体载体上制成固化酶，H2O2－BAC、O3－H2O2－BAC联用技术等。     

Use of catalytic wet air oxidation (CWAO) for pretreatment of high-salinity high-organic wastewater

Catalytic wet air oxidation (CWAO) coupled desalination technology provides a possibility for the effective and economic degradation of high salinity and high organic wastewater. Chloride widely occurs in natural and wastewaters, and its high content jeopardizes the efficacy of Advanced oxidation process (AOPs). Thus, a novel chlorine ion resistant catalyst B-site Ru doped LaFe_1-xRu_xO_3-δ in CWAO treatment of chlorine ion wastewater was examined. Especially, LaFe_0.85Ru_0.15O_3-δ was 45.5% better than that of the 6%RuO₂@TiO₂ (commercial carrier) on total organic carbon (TOC) removal. Also, doped catalysts LaFe_1-xRu_xO_3-δ showed better activity than supported catalysts RuO₂@LaFeO₃ and RuO₂@TiO₂ with the same Ru content. Moreover, LaFe_0.85Ru_0.15O_3-δ has novel chlorine ion resistance no matter the concentration of Cl⁻ and no Ru dissolves after the reaction. X-ray diffraction (XRD) refinement, X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM), and X-ray absorption fine structure (XAFS) measurements verified the structure of LaFe_0.85Ru_0.15O_3-δ. Kinetic data and density functional theory (DFT) proved that Fe is the site of acetic acid oxidation and adsorption of chloride ions. The existence of Fe in LaFe_0.85Ru_0.15O_3-δ could adsorb chlorine ion (catalytic activity inhibitor), which can protect the Ru site and other active oxygen species to exert catalytic activity. This work is essential for the development of chloride-resistant catalyst in CWAO.

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