Evaporation and air-stripping to assess and reduce ethanolamines toxicity in oily wastewater

Toxicity from industrial oily wastewater remains a problem even after conventional activated sludge treatment process, because of the persistence of some toxicant compounds. This work verified the removal efficiency of organic and inorganic pollutants and the effects of evaporation and air-stripping techniques on oily wastewater toxicity reduction. In a lab-scale plant, a vacuum evaporation procedure at three different temperatures and an air-stripping stage were tested on oily wastewater. Toxicity reduction/removal was observed at each treatment step via Microtox bioassay. A case study monitoring real scale evaporation was also done in a full-size wastewater treatment plant (WWTP). To implement part of a general project of toxicity reduction evaluation, additional investigations took into account the monoethanolamine (MEA), diethanolamine (DEA) and triethanolamine (TEA) role in toxicity definition after the evaporation phase, both as pure substances and mixtures. Only MEA and TEA appeared to contribute towards effluent toxicity.     

Treatment of 1,10-phenanthroline laboratory wastewater using the solar photo-Fenton process

The red Fe(2+)-phenanthroline complex is the basis of a classical spectrophotometric method for determination of iron. Due to the toxicity of this complexing agent, direct disposal of the wastewaters generated in analytical laboratories is not environmentally safe. This work evaluates the use of the solar photo-Fenton process for the treatment of laboratory wastewaters containing phenanthroline. Firstly, the degradation of phenanthroline in water was evaluated at two concentration levels (0.1 and 0.01%, w/v) and the efficiencies of degradation using ferrioxalate (FeOx) and ferric nitrate were compared. The 0.01% w/v solution presented much higher mineralization, achieving 82% after 30min of solar irradiation with both iron sources. The solar photo-Fenton treatment of laboratory wastewater containing, in addition to phenanthroline, other organic compounds such as herbicides and 4-chlorophenol, equivalent to 4,500mgL(-1) total organic carbon (TOC) resulted in total degradation of phenanthroline and 25% TOC removal after 150min, in the presence of either FeOx or ferric nitrate. A ratio of 1:10 dilution of the residue increased mineralization in the presence of ferrioxalate, achieving 38% TOC removal after 120min, while use of ferric nitrate resulted in only 6% mineralization over the same period.     

Electrochemical destruction of dinitrotoluene isomers and 2,4,6-trinitrotoluene in spent acid from toluene nitration process

Mineralization of dinitrotoluene (DNT) isomers and 2,4,6-trinitrotoluene (TNT) in spent acid was conducted by in situ electrogenerated hydrogen peroxide. The electrolytic experiments were carried out to elucidate the influence of various operating parameters on the performance of mineralization of total organic compounds (TOC) in spent acid, including electrode potential, reaction temperature, oxygen dosage and concentration of sulfuric acid. It is worth noting that organic compounds could be completely mineralized by hydrogen peroxide obtained from cathodic reduction of oxygen, which was mainly supplied by anodic oxidation of water. Based on the spectra identified by gas chromatograph/mass spectrometer (GC/MS), it is proposed that oxidative degradation of 2,4-DNT and/or 2,6-DNT, 2,4,6-TNT results in o-mononitrotoluene (MNT) and 1,3,5-trinitrobenzene, respectively. Due to the removal of TOC and some amount of water, the electrolytic method established is promising for industrial application to regeneration of spent acid from toluene nitration process.     

Bio-treatment of oily sludge: the contribution of amendment material to the content of target contaminants, and the biodegradation dynamics

The objective was to investigate the aerobic biodegradation of oily sludge generated by a flotation-flocculation unit (FFU) of an oil refinery wastewater treatment plant. Four 1m(3) pilot bioreactors with controlled air-flow were filled with FFU sludge mixed with one of the following amendments: sand (M1); matured oil compost (M2); kitchen waste compost (M3) and shredded waste wood (M4). The variables monitored were: pH, total petroleum hydrocarbons (TPHs), polycyclic aromatic hydrocarbons (PAHs), total carbon (C(tot)), total nitrogen (N(tot)) and total phosphorus (P(tot)). The reduction of TPH based on mass balance in M1, M2, M3 and M4 after 373 days of treatment was 62, 51, 74 and 49%; the reduction of PAHs was 97%, +13% (increase), 92 and 88%, respectively. The following mechanisms alone or in combination might explain the results: (i) most organics added with amendments biodegrade faster than most petroleum hydrocarbons, resulting in a relative increase in concentration of these recalcitrant contaminants; (ii) some amendments result in increased amounts of TPH and PAHs to be degraded in the mixture; (iii) sorption-desorption mechanisms involving hydrophobic compounds in the organic matrix reduce bioavailability, biodegradability and eventually extractability; (iv) mixture heterogeneity affecting sampling. Total contaminant mass reduction seems to be a better parameter than concentration to assess degradation efficiency in mixtures with high content of biodegradable amendments.     

Effects of reaction conditions on nuclear laundry water treatment in Fenton process

This study presents the efficiency of Fenton process in the degradation of organic compounds of nuclear laundry water. The influence of Fe(2+) and hydrogen peroxide ratio, hydrogen peroxide dose, pH and treatment time were investigated. The degradation of non-ionic surfactant and other organic compounds was analysed as COD, TOC and molecular weight distribution (MWD). The most cost-effective degradation conditions were at H(2)O(2)/Fe(2+) stoichiometric molar ratio of 2 with 5 min mixing and H(2)O(2) dose of 1000 mg l(-1). With the initial pH of 6, the reductions of COD and TOC were 85% and 69%, respectively. However, the removal of the organic compounds was mainly carried out by Fenton-based Fe(3+) coagulation rather than Fenton oxidation. Fenton process proved to be much more efficient than previously performed ozone-based oxidation processes.     

Electrodialytic removal of cadmium from wastewater sludge

This paper presents for the first time laboratory results demonstrating electrodialytic removal of Cd from wastewater sludge, which is a method originally developed for soil remediation. During the remediation a stirred suspension of wastewater sludge was exposed to an electric dc field. The liquid/solid (ml/g fresh sludge) ratio was between 1.4 and 2. Three experiments were performed where the sludge was suspended in distilled water, citric acid or HNO3. The experimental conditions were otherwise identical. The Cd removal in the three experiments was 69, 70 and 67%, respectively, thus the removal was approximately the same. Chemical extraction experiments with acidic solutions showed that 5-10 times more Cd could be extracted from decomposed sludge than from fresh sludge. It is likely that the mobilization of Cd during decomposition of the sludge contributes to the efficient removal of Cd by the electrodialytic method. Extraction experiments and electrodialytic remediation using distilled water as enhancement agent showed that 0.3% Cd could be extracted from decomposed sludge during 1 week in closed flasks, whereas 69% was removed during 2 weeks of electrodialytic remediation in a stirred solution in contact with atmospheric air. A combination of aerobic decomposition and electrodialytic treatment could be a promising method for Cd removal from wastewater sludge, and thus Cd could be removed without the addition of chemicals to the sludge.     

Photo-assisted oxidation of an oily wastewater using hydrogen peroxide

The primary objective was to study the purification of an oily wastewater from a lubricant production unit using ultraviolet irradiation and hydrogen peroxide. The influence of hydrogen peroxide concentration, initial pH of the solution and of the addition of ferric ions on the chemical oxygen demand (COD) was examined. In each case, the concentration of the compounds contained in the oily wastewater was determined. It was shown that a 20-45% COD removal was achieved with 830-1660 mg l(-1) H(2)O(2). Gas chromatography-mass spectrometry analysis showed that the organic compounds of the wastewater decomposed to organic acids that were very resistant to photo-oxidation. Among these compounds, ethylene glycol remained almost unchanged by the attack from hydroxyl radicals. Acidic pH and Fe(III) addition enhanced significantly the photo-oxidation of the wastewater.     

基于SnO2/Fe3O4粒子电极的三维电极体系的电催化性能

通过水热法合成复合金属氧化物SnO_2/Fe_3O_4粒子电极,然后采用X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)、磁滞回线等技术分别对粒子电极的晶体组分、形貌、元素组成和分子结构以及粒子电极的磁性特征进行表征。采用循环伏安法分析了三维电极系统的电化学性能,并进行了电催化氧化降解罗丹明B(RhB)的实验。结果表明,SnO_2/Fe_3O_4粒子电极负载稳定、导电性强、便于回收再利用,有利于电催化氧化降解反应。三维电极降解罗丹明B的析氧电流高于其他电极体系,电催化活性效果明显,90min内罗丹明B的降解率为100%、TOC去除率为83%,反应中产生的·OH是降解有机物的主要活性基。粒子电极在重复利用5次的情况下,对罗丹明B的降解率仍保持93%以上、TOC去除率保持在77%以上,具有稳定的电催化性能。     

Effects of nickel(II) addition on the activity of activated sludge microorganisms and activated sludge process

The effects of Ni(II) in a synthetic wastewater on the activity of activated sludge microorganisms and sequencing batch reactor (SBR) treatment process were investigated. Two parallel lab-scale SBR systems were operated. One was used as a control unit, while the other received Ni(II) concentrations equal to 5 and 10 mg/l. The SBR systems were operated with FILL, REACT, SETTLE, DRAW and IDLE modes in the time ratio of 0.5:3.5:1.0:0.75:0.25 for a cycle time of 6 h. The addition of Ni(II) into SBR system caused drastically dropped in TOC removal rate (k) and specific oxygen uptake rate (SOUR) by activated sludge microorganisms due to the inhibitory effects of Ni(II) on the bioactivity of microorganisms. The addition of 5 mg/l Ni(II) caused a slight reduction in TOC removal efficiency, whereas 10 mg/l Ni(II) addition significantly affected the SBR performance in terms of suspended solids and TOC removal efficiency. Termination of Ni(II) addition led to almost full recovery of the bioactivity in microorganisms as shown in the increase of specific oxygen uptake rate (SOUR) and SBR treatment performance.     

Prepared bed bioremediation of oily sludge in an oilfield in northern China

Field-scale bioremediation of oily sludge in prepared beds was studied at Shengli oilfield in northern China. The influence of manure, coarse sand, sawdust, a specialized microbial preparation and greenhouse conditions on the efficiency of removal of oil and grease was evaluated. After bioremediation for 230 d, oil and grease content fell by 32–42 g kg⁻¹ dry sludge in treated plots, indicating removal of 27–46% compared with only 15% in the control plot. Addition of manure, coarse sand, sawdust and greenhouse conditions significantly (p < 0.05) increased the amount removed. Moreover, the physico-chemical properties of the sludge in all treated plots improved significantly after bioremediation. Microbial biomass in sludge and community-level physiological profiling examined using BIOLOG microplates was also studied. Total petroleum hydrocarbon degraders and polycyclic aromatic hydrocarbon degraders increased in all treated oily sludge. The activity of sludge microbial communities increased markedly in the treated plots compared with the control. Canonical correspondence analysis showed that differences in substrate utilization patterns were highly correlated (p < 0.05) with sludge hydrolyzable N and oil and grease content. The biological toxicity of the oily sludge was lower following bioremediation in most of the treated plots as evaluated using Photobacterium phosphoreum T3.     

Evaluation of biodegradability and oxidation degree of hospital wastewater using photo-Fenton process as the pretreatment method

In this work, the photo-Fenton process was used for the pretreatment of hospital wastewater with the objective of improving its overall biodegradability and determining the degree of increased oxidation. The chemical oxygen demand (COD), 5-day biochemical oxygen demand (BOD5), total organic carbon (TOC) and toxicity towards the gram negative marine bioluminescent bacteria of the species V. fischeri were selected as the environmental sum parameters to follow the performance of this process. The enhancement of biodegradability, evaluated in terms of the BOD5/COD ratio, increased from 0.3 to 0.52 and the oxidation degree, calculated in terms of AOS, leveled up from -1.14 to +1.58 at the optimum conditions; a dosage ratio of COD:H2O2:Fe(II) at 1:4:0.1, and a reaction pH of 3. The reduction in the inhibition percentage from the toxicity test indicated the safe levels for micro-organisms in degrading the residual organic substance in this method. Almost total removal percentages of COD, BOD5, and TOC were found by a sequential activated sludge process for the pre-treated wastewater. Results obtained from this work indicated that the photo-Fenton process could be a suitable pretreatment method in reducing toxicity of pollutants and enhancing biodegradability of hospital wastewaters treated in a coupled photochemical-biological system.     

含油污泥颗粒的流态化行为研究

在一内径为0.056m、高为1.6m的冷模玻璃流化床中研究含油污泥与石英砂混合颗粒的冷模流化行为,含油污泥干基含油率为17.63%(质量分数),筛分成0.20~0.30、0.30~0.45、0.45~0.90mm3种粒径范围,与石英砂混合后进行流化实验。结果表明:各种颗粒混合物中油泥质量分数在0~30%范围内均可以实现正常流化,超出此范围,流化中出现明显的粘壁、沟流等不正常的流化现象;混合颗粒中含油率越高,初始流化速度越大;含油泥混合颗粒与典型的B类颗粒纯石英砂的塌落行为有显著差别,塌落时间较长,而床层膨胀率却较低。     

Hydrothermal oxidation: application to the treatment of different cutting fluid wastes

The aim of this work is to present the application of the hydrothermal oxidation in supercritical conditions, also named supercritical water oxidation (SCWO) to the treatment of two commercial cutting fluids: Biocut and Servol. Experiments were carried out in a continuous flow system at a constant pressure of 25 MPa, using pure oxygen as oxidant in excess, and different temperatures ranging from 673 to 773 K. Both semi-synthetic cutting fluids are a mixture of several compounds so the efficiency of the oxidation process was followed in terms of the reduction in chemical oxygen demand (COD) and total organic carbon (TOC). A comparison of the results obtained in the study showed that it is possible to apply successfully SCWO for both cutting fluids, obtaining more than 95% for both COD and TOC removal at 773 K. However, the results also show that different residence times are needed to obtain the same percentage of COD or TOC removal depending on the cutting fluid treated, being in all cases Servol easier to oxidize than Biocut. A kinetic model to predict COD and TOC conversion has been proposed for both cutting fluids. A two-parameter mathematical model involving two steps (a fast reaction followed by a slow reaction) was used to describe the Biocut SCWO kinetics and to calculate the kinetic constants.     

Ecotoxicological evaluation of the wastewater treatment process of the sewage treatment plant of Thessaloniki, Greece

The LUMISTox toxicity test was employed to assess the removal of municipal wastewater toxicity during the biological treatment with activated sludge in the wastewater treatment plant of Thessaloniki, Greece. Possible associations of toxicity data with chemical parameters of organic pollution of wastewaters, namely BOD(5), COD, DOC, SS and persistent organic pollutants (POPs) were also investigated. Toxicity and chemical parameters were concurrently measured at three sampling points of the treatment plant, the entrance of the unit (raw wastewater, RW), the effluent of the secondary sedimentation tank (SSE), and the final sewage sludge (FS). Substantial reduction of toxicity was observed from RW to SSE (mean+/-S.D. of bioluminescence inhibition 36+/-9.4% and 13+/-4.0%, respectively) indicating removal of toxicants during primary and secondary clarification, also suggesting that a large part of the toxicity measured is attributed to the biodegradable fraction of the organic content of wastewater. Significant positive correlations were observed between % inhibition values and wastewater parameters (BOD, COD, SS). In sludge, correlations were in general poor. Negative strong correlation was observed between EC(20/15) and TOC suggesting that the organic content of sludge contributes to the toxicity measured. Toxicity was positively correlated with the concentrations of certain POPs in RW, while weaker negative correlations were observed in SSE. Correlations in sewage sludge were less significant. It was concluded that toxicity testing is a useful tool supplementing chemical analyses in the evaluation of the potential hazard from effluent discharges and disposal of waste sludge.     

陶瓷膜处理炼油厂"三泥"水相的研究

采用陶瓷微滤膜对“三泥”水相进行处理．通过渗透液油含量的测定,证明此方法能明显地降低传统方法仰处理的水相的油,尤其是乳化油的含量．同时,确定了合适的膜孔径,研究了操作压力、膜面流速和操作温度对渗透通量的影响．为炼油厂“三泥”的处理提供了一种新的方法．     

Complete degradation of Orange G by electrolysis in sub-critical water

Complete degradation of azo dye Orange G was studied using a 500 mL continuous flow reactor made of SUS 316 stainless steel. In this system, a titanium reactor wall acted as a cathode and a titanium plate-type electrode was used as an anode in a subcritical reaction medium. This hydrothermal electrolysis process provides an environmentally friendly route that does not use any organic solvents or catalysts to remove organic pollutants from wastewater. Reactions were carried out from 30 to 90 min residence times at a pressure of 7 MPa, and at different temperatures of 180-250°C by applying various direct currents ranging from 0.5 to 1A. Removal of dye from the product solution and conversion of TOC increased with increasing current value. Moreover, the effect of salt addition on degradation of Orange G and TOC conversion was investigated, because in real textile wastewater, many salts are also included together with dye. Addition of Na(2)CO(3) resulted in a massive degradation of the dye itself and complete mineralization of TOC, while NaCl and Na(2)SO(4) obstructed the removal of Orange G. Greater than 99% of Orange G was successfully removed from the product solution with a 98% TOC conversion.     

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.     

Non-thermal plasma-induced photocatalytic degradation of 4-chlorophenol in water

TiO(2) photocatalyst (P-25) (50mgL(-1)) was tentatively introduced into pulsed high-voltage discharge process for non-thermal plasma-induced photocatalytic degradation of the representative mode organic pollutant parachlorophenol (4-CP), including other compounds phenol and methyl red in water. The experimental results showed that rate constant of 4-CP degradation, energy efficiency for 4-CP removal and TOC removal with TiO(2) were obviously increased. Pulsed high-voltage discharge process with TiO(2) had a promoted effect for the degradation of these pollutants under a broad range of liquid conductivity. Furthermore, the apparent formation rates of chemically active species (e.g., ozone and hydrogen peroxide) were increased, the hydrogen peroxide formation rate from 1.10x10(-6) to 1.50x10(-6)Ms(-1), the ozone formation rate from 1.99x10(-8) to 2.35x10(-8)Ms(-1), respectively. In addition, this process had no influence on the photocatalytic properties of TiO(2). The introduction of TiO(2) photocatalyst into pulsed discharge plasma process in the utilizing of ultraviolet radiation and electric field in pulsed discharge plasma process enhanced the yields of chemically active species, which were available for highly efficient removal and mineralization of organic pollutants.     

Electro-kinetic dewatering of oily sludges

An oily sludge from a rendering facility was treated using electro-kinetic (EK) techniques employing two different experimental designs. The bench scale used vertical electrodes under different operational conditions, i.e. varied electrode spacing at 4, 6 and 8 cm with electric potential of 10, 20 and 30 V, respectively. The highest water removal efficiency (56.3%) at bench scale was achieved at a 4 cm spacing and 30 V. Comparison of the water removal efficiency (51.9%) achieved at the 20 V at 4 cm spacing showed that power consumption at 30 V was 1.5 times larger than that at 20 V, suggesting a further increase of electric potential is unnecessary. The solids content increased from an initial 5 to 11.5 and 14.1% for 20 and 30 V, respectively. The removal of oil and grease (O&G) was not significant at this experimental design. Another larger scale experiment using a pair of horizontal electrodes in a cylinder with 15 cm i.d. was conducted at 60 V at an initial spacing of 22 cm. More than 40.0% of water was removed and a very efficient oil separation from the sludge was achieved indicating the viability of electro-kinetic recovery of oil from industrial sludge.     

The degradation of landfill leachate in the presence of different catalysts by sonolytic and sonocatalytic processes

In the study, the degradation of landfill leachate by single ultrasound (sonolytic) and sonolytic combined with Fe²⁺ and TiO₂ catalysts was carried out in laboratory conditions. The effect of pH and ultrasonic wave amplitude was also investigated in terms of color removal, total organic carbon (TOC) and chemical oxygen demand (COD) from leachate by the sonolytic degradation process. In this process, the color removal efficiency was recorded as 81.81% at 620?nm, pH?=?2.0 and 70% wave amplitude. The sonocatalytic degradation of landfill leachate accompanied by different catalysts was studied by using the 70% wave amplitude at pH?=?2.0 and room temperature for 20?min. The sonocatalytic degradation of leachate by using Fe²⁺ and TiO₂ was found to be significantly higher than sonolytic degradation (p?2+ concentration increased from 1.0 to 3.0?mg/L, the COD and color removal of leachate significantly decreased (p?相似文献