Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: kinetics and biodegradability enhancement

Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were investigated as suitable precursors for the biological treatment of industrial wastewater containing sodium dodecylbenzene sulfonate (DBS). Two hours WAO semi-batch experiments were conducted at 15 bar of oxygen partial pressure (P(O2)) and at 180, 200 and 220 degrees C. It was found that the highest temperature provides appreciable total organic carbon (TOC) and chemical oxygen demand (COD) abatement of about 42 and 47%, correspondingly. Based on the main identified intermediates (acetic acid and sulfobenzoic acid) a reaction pathway for DBS and a kinetic model in WAO were proposed. In the case of CWAO experiments, seventy-two hours tests were done in a fixed bed reactor in continuous trickle flow regime, using a commercial activated carbon (AC) as catalyst. The temperature and P(O2) were 140-160 degrees C and 2-9 bar, respectively. The influence of the operating conditions on the DBS oxidation, the occurrence of oxidative coupling reactions over the AC, and the catalytic activity (in terms of substrate removal) were established. The results show that the AC without any supported active metal behaves bi-functional as adsorbent and catalyst, giving TOC conversions up to 52% at 160 degrees C and 2 bar of P(O2), which were comparable to those obtained in WAO experiments. Respirometric tests were completed before and after CWAO and to the main intermediates identified through the WAO and CWAO oxidation route. Then, the readily biodegradable COD (COD(RB)) of the CWAO and WAO effluents were found. Taking into account these results it was possible to compare whether or not the CWAO or WAO effluents were suitable for a conventional activated sludge plant inoculated with non adapted culture.     

Wet electrolytic oxidation of organic sludge

Electrolysis of an aqueous solution at subcritical water conditions, referred here as wet electrolytic oxidation (WEO), results in a completely different reaction product compared to that from usual water electrolysis. Oxygen, hydrogen and chlorine evolution is almost completely suppressed when carrying out the electrolysis of aqueous NaCl solution at temperatures higher than 250 degrees C. Chemical oxygen demand (COD) compounds can be completely mineralized by this electrolytic reaction, but this work focused in partial oxidation of organic sludge and combining with biological process. The treatment of organic sludge by WEO increased the biodegradability of organic sludge due to the formation of organic acids. The electrochemical reaction of WEO suppressed the evolution of color that often appears in subcritical water treatment of organic waste.     

Characteristics of titania supported copper oxide catalysts for wet air oxidation of phenol

Various techniques have been used to characterize the CuO(x)/TiO(2) catalysts with different copper loading. Surface area, pore volume and pore size distribution of the prepared catalysts were estimated from nitrogen adsorption isotherm. Temperature programmed reduction (TPR), X-ray diffraction (XRD), electron spin resonance (ESR), X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge structure (XANES) experiments were performed to investigate the chemical state of the copper species. The chemical state of copper in the CuO(x)/TiO(2) catalysts varied with copper loading (1-25wt.%): highly dispersed Cu(2+) cluster for 1 and 5wt.%, and bulk CuO for 7-25wt.%. The activity and mineralization selectivity of the CuO(x)/TiO(2) catalysts increased with copper loading up to 20wt.%, and remained almost constant for higher copper loading. The optimum copper loading was 20wt.% for the wet air oxidation of phenol over the CuO(x)/TiO(2) catalysts in this work. The stability of the CuO(x)/TiO(2) catalysts with different copper loading was also studied with respect to carbonaceous deposits and copper leaching.     

Heterogeneous catalytic wet air oxidation of refractory organic pollutants in industrial wastewaters: a review

Catalytic wet air oxidation (CWAO) is one of the most economical and environmental-friendly advanced oxidation process. It makes a promising technology for the treatment of refractory organic pollutants in industrial wastewaters. Various heterogeneous catalysts including noble metals and metal oxides have been extensively studied to enhance the efficiency of CWAO. The present review is concerned about the literatures published in this regard. Phenolics, carboxylic acids, and nitrogen-containing compounds were taken as model pollutants in most cases, and noble metals such as Ru, Rh, Pd, Ir, and Pt as well as oxides of Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, and Ce were applied as heterogeneous catalysts. Reports on their characterization and catalytic performances for the CWAO of aqueous pollutants are reviewed. Discussions are also made on the reaction mechanisms and kinetics proposed for heterogeneous CWAO and also on the typical catalyst deactivations in heterogeneous CWAO, i.e. carbonaceous deposits and metal leaching.     

Catalytic wet air oxidation of chlorophenols over supported ruthenium catalysts

A series of noble metal (Pt, Pd, Ru) loaded zirconia catalysts were evaluated in the catalytic wet air oxidation (CWAO) of mono-chlorophenols (2-CP, 3-CP, 4-CP) under relatively mild reaction conditions. Among the investigated noble metals, Ru appeared to be the best to promote the CWAO of CPs as far as incipient-wetness impregnation was used to prepare all the catalysts. The position of the chlorine substitution on the aromatic ring was also shown to have a significant effect on the CP reactivity in the CWAO over 3wt.% Ru/ZrO(2). 2-CP was relatively easier to degradate compared to 3-CP and 4-CP. One reason could be the higher adsorption of 2-CP on the catalyst surface. Further investigations suggested that 3wt.% Ru/ZrO(2) is a very efficient catalyst in the CWAO of 2-CP as far as high 2-CP conversion and TOC abatement could still be reached at even lower temperature (393K) and lower total pressure (3MPa). Additionally, the conversion of 2-CP was demonstrated to increase with the initial pH of the 2-CP solution. The dechlorination reaction is promoted at higher pH. In all cases, the adsorption of the reactants and the reaction intermediates was shown to play a major role. All parameters that would control the molecule speciation in solution or the catalyst surface properties would have a key effect.     

Wet peroxide oxidation and catalytic wet oxidation of stripped sour water produced during oil shale refining

Catalytic wet oxidation (CWO) and wet peroxide oxidation (WPO) of stripped sour water (SSW) from an oil shale refinery was investigated. Greater than 70% total organic carbon (TOC) removal from SSW was achieved using Cu(NO(3))(2) catalysed WO under the following conditions using a glass lined reaction vessel: 200 degrees C, pO(2)=0.5MPa, 3h, [Cu(NO(3))(2)]=67mmol/L. Significant TOC removal ( approximately 31%) also occurred in the system without added oxygen. It is proposed that this is predominantly due to copper catalysed oxidative decarboxylation of organics in SSW based on observed changes in copper oxidation state. Greater than 80% TOC removal was achieved using WPO under the following conditions: 150 degrees C, t=1.5h, [H(2)O(2)]=64g/L. Significantly more TOC could be removed from SSW by adding H(2)O(2) in small doses as opposed to adding the same total amount in one single dose. It was concluded that WPO was a far more effective process for removing odorous compounds from SSW.     

Study of thermal degradation of organic light emitting device structures by X-ray scattering

We report the process of thermal degradation of organic light emitting devices (OLEDs) having multilayered structure of [LiF/tris-(8-hydroxyquinoline) aluminum(Alq₃)/N,N′-Bis(naphthalen-1-yl)-N,N′-bis(phenyl)benzidine (NPB)/copper phthalocyanine (CuPc)/indium tin oxide (ITO)/SiO₂ on a glass] by synchrotron X-ray scattering. The results show that the thermally induced degradation process of OLED multilayers has undergone several evolutions due to thermal expansion of NPB, intermixing between NPB, Alq₃, and LiF layers, dewetting of NPB on CuPc, and crystallization of NPB and Alq₃ depending on the annealing temperature. The crystallization of NPB appears at 180 °C, much higher temperature than the glass transition temperature (T_g = 96 °C) of NPB. The results are also compared with the findings from the atomic force microscope (AFM) images.     

茶叶中有机酸的测试方法概述

针对茶叶中有机酸测定前处理分析测试条件等不统一,导致测试结果无可比性的问题,该文在参阅1907年以来国内外关于茶叶中有机酸分析的30余篇文献的基础上,对茶叶中有机酸的分析方法做了较系统的归纳阐述,并对目前常用的分析方法包括高效液相色谱法、离子色谱法以及毛细管电泳色谱法等进行了评述,提出了茶叶中有机酸测定应进行标准化,以确保测试结果的可比性。     

Removal of salicylic acid on perovskite-type oxide LaFeO3 catalyst in catalytic wet air oxidation process

It has been found that salicylic acid can be removal effectively at the lower temperature of 140 degrees C on perovskite-type oxide LaFeO3 catalyst in the catalytic wet air oxidation (CWAO) process. Under the same condition, the activities for the CWAO of phenol, benzoic acid and sulfonic salicylic acid have been also investigated. The results indicated that, with compared to the very poor activities for phenol and benzoic acid, the activities for salicylic acid and sulfonic salicylic acid were very high, which are attributed to their same intramolecular H-bonding structures. With the role of hard acidity of intramolecular H-bonding, salicylic acid and sulfonic salicylic acid can be adsorbed effectively on the basic center of LaFeO3 catalyst and are easy to take place the total oxidation reaction. However, at temperatures higher than 140 degrees C, the intramolecular H-bonding structure of salicylic acid was destroyed and the activities at 160 and 180 degrees C decreased greatly, which confirms further the key role of intramolecular H-bonding in the CWAO. Moreover, the LaFeO3 catalyst also indicated a superior stability of activity and structure in CWAO of salicylic acid.     

Attack of cement pastes exposed to organic acids in manure

Manure such as silage effluents and liquid manure contains organic acids which constitute a severe chemical threat toward the concrete of agricultural structures. The purposes of this study were to identify the chemical composition parameters that influence durability by analysing the behaviour of the chemical elements of the cement paste (Ca, Si, Al, Fe and Mg) in organic acid solutions and to compare the intensity of the chemical attack by the different acids found in liquid manure. This study was carried out on cement pastes made from four binders (ordinary Portland cement, slag cement, OPC blended with silica fume and OPC blended with fly ash). The hardened cement pastes were first crushed, then immersed in solutions made of five organic acids with an initial pH of 4 and constantly stirred. The pH and the concentrations of major elements were monitored over time.

The results show that Si, Al, and Fe appear to be favourable elements for the chemical resistance of binders whereas the amount of Ca should be limited. Moreover, it is shown that the four acids found in liquid manure (acetic, propionic, butyric, iso-butyric) are equally aggressive. Lactic acid, present with acetic acid in silage effluent, is more aggressive according to the value of its pK_a.     

Hot water extraction with in situ wet oxidation: kinetics of PAHs removal from soil

Finding environmentally friendly and cost-effective methods to remediate soils contaminated with polycyclic aromatic hydrocarbons (PAHs) is currently a major concern of researchers. In this study, a series of small-scale semi-continuous extractions--with and without in situ wet oxidation--were performed on soils polluted with PAHs, using subcritical water (i.e. liquid water at high temperatures and pressures, but below the critical point) as the removal agent. Experiments were performed in a 300 mL reactor using an aged soil sample. To find the desorption isotherms and oxidation reaction rates, semi-continuous experiments with residence times of 1 and 2 h were performed using aged soil at 250 degrees C and hydrogen peroxide as oxidizing agent. In all combined extraction and oxidation flow experiments, PAHs in the remaining soil after the experiments were almost undetectable. In combined extraction and oxidation no PAHs could be detected in the liquid phase after the first 30 min of the experiments. Based on these results, extraction with hot water, if combined with oxidation, should reduce the cost of remediation and can be used as a feasible alternative technique for remediating contaminated soils and sediments.     

大气中烧结多孔氮化硅的相变和氧化机理研究

以α—Si3N4为原料，分别以Y2O3-Al2O3和MgO-Al2O3-SiO2两个体系作为烧结助剂，在大气中对氮化硅坯体在1400～1550℃进行烧结。研究了烧结温度、烧结助剂体系对氮化硅的氧化程度、氧化产物的影响。结果表明，以MgO-Al2O3-SiO2作烧结助剂有利于α-Si3N4转变为β-Si3N4，且该烧结助剂体系的的抗氧化能力也明显优于Y2O3-Al2O3体系。氮化硅在不同温度烧结时形成的氧化产物不同。     

改性PbO2 电极电催化降解水中硝基苯酚

为研究PbO2电极的性能,在酸性溶液中,以电沉积法制备了改性钛基PbO2电极,优化并确定了电极的制备工艺,并利用SEM对电极的表面形貌进行了检测.以硝基苯酚为目标有机物,考察了电极的电催化氧化性能.采用铋掺杂PbO2电极处理水中邻硝基苯酚、间硝基苯酚和对硝基苯酚,并对不同硝基苯酚的矿化过程以及降解动力学进行了比较.研究表明:改性PbO2电极的电催化性能优于传统的PbO2电极;邻硝基苯酚在本研究条件下更易被降解.     

Effects of dissolved low molecular weight organic acids on oxidation of ferrous iron by Acidithiobacillus ferrooxidans

A few researchers have reported on work concerning bioleaching of heavy-metal-contaminated soil using Acidithiobacillus ferrooxidans, since this acidophile is sensitive to dissolved low molecular weight (LMW) organic acids. Iron oxidation by A. ferrooxidans R2 as well as growth on ferrous iron was inhibited by a variety of dissolved LMW organic acids. Growth experiments with ferrous iron as an oxidant showed that the inhibition capability sequence was formic acid>acetic acid>propionic acid>oxalic acid>malic acid>citric acid. The concentrations that R2 might tolerate were formic acid 0.1mmolL(-1) (2mmolkg(-1)soil), acetic and propionic acids 0.4mmolL(-1) (8mmolkg(-1)soil), oxalic acid 2.0mmolL(-1) (40mmolkg(-1)soil), malic acid 20mmolL(-1) (400mmolkg(-1)soil), citric acid 40mmolL(-1) (800mmolkg(-1)soil), respectively. Although R2 was sensitive to organic acids, the concentrations of LMW organic acids in the contaminated soils were rather lower than the tolerable levels. Hence, it is feasible that R2 might be used for bioleaching of soils contaminated with metals or metals coupled with organic compounds because of the higher concentrations of LMW organic acids to which R2 is tolerant.     

Effect of potential electron acceptors on anoxic ammonia oxidation in the presence of organic carbon

A novel route of anoxic ammonia removal in the presence of organic carbon was identified recently from ecosystems contaminated with ammonia. Sequencing batch reactor (SBR) studies were carried out in anoxic condition at oxidation–reduction potential varied from −185 to −275 mV for anoxic ammonia oxidation with adapted biomass (mixed culture). SBR studies were carried out in absence and in the presence of externally added organic carbon and/or in the presence of inorganic electron acceptors like NO₂⁻, NO₃⁻ and SO₄²⁻. The results showed anoxic ammonia oxidation to nitrate (in contrast to reported anammox process) in the presence of organic carbon available through endogenous respiration whereas anoxic ammonia oxidation was effective in the presence of externally added organic compound for nitrogen removal. The presence of externally added inorganic electron acceptors like NO₂⁻, NO₃⁻ and SO₄²⁻ was effective in anoxic ammonia oxidation, but failed to follow the reported anammox reaction's stoichiometry in nitrogen removal in the presence of organic carbon. However, the presence of NO₂⁻ affected best in total nitrogen removal compared to other electron acceptors and maximum ammonia removal rate was 100 mg NH₄⁺/g MLVSS/d. Based on the results, it is possible to suggest that rate of anoxic ammonia oxidation depends up on the respiration activities of mixed culture involving organic carbon, NO₂⁻, NO₃⁻ and SO₄²⁻. The process shows possibilities of new pathways of ammonia oxidation in organic contaminated sediments and/or wastewater in anoxic conditions.     

循环流化床锅炉风帽合金的组织及抗高温氧化性能研究

针对循环流化床锅炉风帽的严重高温氧化腐蚀问题,研制出适用于风帽的高温合金AN1(Cr23Ni32MoNb),结合金相(OM)、X射线衍射(XRD)、场发射扫描电镜(FE-SEM)、能谱(EDS)等分析方法对风帽试样的微观组织和高温氧化性能进行了研究,并与25-20钢和316钢进行对比分析。结果表明,AN1铸态组织为典型的树枝状晶结构,由奥氏体基体和Cr23C6、NbC等晶间碳化物组成,固溶处理后,枝晶结构基本消失;1000℃氧化100h,AN1的高温氧化抗力分别为25-20钢和316钢的2.2和3.8倍;AN1氧化实验后的表层相结构主要由γ奥氏体、Cr2O3和Cr与Mn的复合氧化膜组成。     

The influence of the moisture content of the atmosphere on alumina scale formation and growth during high temperature oxidation of PM2000

Abstract

Preliminary studies have been undertaken on cyclic and isothermal oxidation at 1,300°C of thin (125 μm) samples of commercial ODS alloy PM2000 for up to 350h in two different oxidising environments; dry and moist air. Scanning electron microscopy (SEM) and electron microprobe analysis (EPMA) have been used to study the influence of such environments on alumina scale formation and growth. Initial mass gain observations showed that the alumina scale, which formed on the samples oxidised in air+2.5vol% H₂O grew faster in the early stages of oxidation than in the case of dry air. However the SEM analysis revealed that the scale morphologies in both dry air and air+2.5vol% H₂O were similar. In both cases the scales consisted of equiaxed grains at the scale–gas interface with Ti-rich particles in the outermost part of the scale. The major factor for the total scale failure, the formation of non-protective iron oxide, is the depletion of Al levels to a critical value, below which no protective alumina scale can form; and this occurred slightly faster in moist air than in dry air     

A non-vacuum method for synthesis of ZnO films by thermal oxidation of ZnS films in air

A non-vacuum method for preparation of ZnO films via thermal oxidation of ZnS films deposited by thin layer thermolysis is described. Transmission electron microscopic studies reveals that the films are polycrystalline with preferentially oriented along (100) direction and grain size of 5-10 nm. The films have about 95% transmission in the visible-near infrared (VIS-NIR) region and an energy band gap of 3.22 eV.     

Effects of activated sludge on the degradation of chlorate in soils under varying environmental conditions

Incubation experiments were conducted to examine the effects of activated sludge on degradation of chlorate in soils. The results show that application of activated sludge could significantly promote the decomposition of soil chlorate though the degradation rate of chlorate did not necessarily increase with increasing application rate of the sludge. The effectiveness of activated sludge on soil chlorate degradation was significantly affected by temperature, moisture content and pH. There is a tendency that the rate of chlorate decomposition increased with increasing temperature and moisture content until optimal values of temperature and moisture content were reached. This can be attributed to the enhanced activity of chlorate-reducing microorganisms in hot and more reducing soil conditions. Soil pH also had important controls on the decomposition of chlorate. The experimental results demonstrate that neutral pH more favoured the degradation of soil chlorate, compared to either acidic or alkaline pH. While soil organic matter content could affect chlorate decomposition, its impact on the effectiveness of activated sludge on chlorate degradation was minor. This study has implications for developing cost-effective techniques for remediating chlorate-contaminated soils, particularly in the longan-producing countries.