有机磷农药废水湿式空气氧化预处理的研究

以ｏ，ｏ－二甲氧基硫代磷酰氯生产废水为代表，在２Ｌ不锈钢高压釜中研究了有机磷农药废水湿式空气氧化预处理工艺，得到了实现有机磷、有机硫去除８０－９０％，ＣＯＤ去除６０％的工艺条件及其优化组合，工艺条件相当缓和，废水处理后，其可生化降解性显著提高，ＢＯＤ５／ＣＯＤ由０．２增至０．４－０．５。工艺条件用于处理其它几中有机磷废水取得同样好的效果。     

AOX Formation and Elimination in the Oxidative Treatment of Synthetic Wastewaters in a UV-Free Surface Reactor (6 pp)

Intention, Goal, Scope, Background The effect of chloride concentration and pH on the UV oxidation systems was examined. Phenol and methanol were used as organic substances. The treatment of these chemicals by UV oxidation using a newly developed lab scale pretest UV-Free Surface Reactor (UV-FSR) with and without Cl– addition at different pH values, is evaluated. Results of this study indicated that the Cl– concentration of the water and the chemical structure of the substances is more important than the pH of the water. There was no AOX at the beginning of the experiments, but a de-novo synthesis of AOX was observed during the batch experiments. This is caused by the high chloride content of the wastewaters. It can be supposed that OHradicals oxidize some chloride-ions to form chlorine, which further reacts with organic compounds. During the treatment, these AOX compounds which are produced from the beginning of the reaction are destroyed again. Evaluations of these experiments were done according to TOC and AOX results. Approximately 80% and 99% TOC removal efficiencies were obtained for the treatment of Phenol and Methanol-containing wastewaters, respectively. Objective In the literature, there are no relevant publications concerning the AOX formation of wastewater by wet oxidation- iron catalysed or by application of UV. For that reason, the main objectives of this study were: 1. to see the influence of chloride concentration and pH on the AOXde-novo formation with newly developed UV-Free Surface Reactor (UV-FSR), 2. to make a comparison of different AOPs, 3. to observe the effect of the chloride concentration on the TOC degradation efficiency, 4. to optimise reaction conditions. Methods In synthetic wastewaters, Methanol (CH3OH) and Phenol (C6H5 OH) are used as pollutants. The concentration of each substance was 1000 mg/l and COD values were calculated theoretically. The H2O2 addition was calculated according to the COD with a convenient stoichiometric factor (e.g. 1). During experiments, the pH was always kept constant with the addition of either 25% H2SO4 or 33% NaOH depending on the experimental conditions. Each substance was treated with the addition of 1000 mg/l Cl–, 10000 mg/l Cl– and without Cl– addition at pH 3, pH 7 and pH 10, respectively. NaCl was used as a Cl– source. Adsorbable Organic Halogenides (AOX) were determined using a TOX analyser (European Standard EN 1485 H 14, 1996). TOC measurements were carried out using an Elementar High TOC Analyzer equipped with an auto sampler. The H2O2 concentration was measured according to German Standard Methods (DIN 38409, Part 15, 1987). Results and Discussion The first step was to determine the effect of pH on the AOX formation in the process. Therefore, experiments were carried out at three different pHs: acidic (pH 3), neutral (pH 7) and basic (pH 10) conditions at a constant initial Methanol concentration of 1000 mg/l and a hydrogen peroxide concentration of 3185 mg/l (1 x stoichiometric). All results were evaluated according to applied pH. At these conditions, the amount of H2O2 (53 ml / 10 l) concentration was nearly zero after 1 hour batch treatment of Methanol. There was no AOX at the beginning of the experiments, but the AOX value increased after 6–18 min. At the end of 1 hour batch treatment this produced AOX was treated again. The maximum AOX production was obtained with the addition of 10000 mg/l Cl–, whereas there is no AOX production during the experiment when Cl– was not used. In all studies, however, TOC values decreased to almost zero after 1 hour batch treatment. After the experiments with Methanol, Phenol treatment was carried out at different pHs as a second experiment. pH was kept constant with the addition of either H2SO4 or NaOH depending on the experimental conditions. During experiments with Phenol, the colour of the water changed from colourless to a yellowish- red. After 1 hour treatment, the colour of the water was red. Therefore, these experiments were continued until the water became colourless again, and this took about 5 hours. Although there was no AOX at the beginning of the experiments, it increased after 30 min to 1 hour oxidation with the addition of 1000 mg/l Cl– and 10000 mg/l Cl–. There was no AOX production during the experiments when Cl– was not added. At the end of 5 hours of treatment, formed AOX was degraded and the TOC concentration decreased from 766 mg/l to approximately 200 mg/l. Conclusion. These experiments of this study showed that the effects of Cl– concentration of the water and the chemical structure of the substances is more than that of the pH on the AOX formation. During the batch experiments, a de-novo synthesis of AOX was observed very impressively due to the high chloride content of the wastewaters. It can be implied that OH-radicals oxidize some chloride-ions to form chlorine, which further reacts with organic compounds so that AOXde-novo is formed. At the end of the reaction times these AOX compounds are also destroyed. Recommendation and Outlook It is more cost effective to use these processes for only purposes such as toxicity reduction, enhancement of biodegradability, decolourisation and removal of micropollutants. However, the most important point is the optimization of the reaction conditions for the process of concern. The AOP applied can be used, for instance, for AOX reduction and TOC removal of industrial wastewaters.     

Production of Ethanol by an Integrated Valorization of Olive Oil Byproducts. The Role of Phenolic Inhibition (2 pp)

Background, Aim and Scope Agricultural industrial wastes can frequently be used as raw materials in the production of bio-fuels. Olive-oil milling wastewater is considered as one of the most polluting agro-industrial residues, but fortunately due to its high content of organic matter, it has the potential to be a valuable starting material to obtain bio-ethanol via fermentation with Saccharomyces cerevisiae. The fermentation of olive-oil milling wastewater has been demonstrated with good yield of ethanol (8-12%v/v) once the level of reducing sugars is appropriate and the phenolic fraction, which inhibits the yeast, is removed. Materials and Methods: - Results: - Discussion: - Conclusions: - Recommendations and Perspectives: -     

OFFSITE MEASUREMENT OF THE VISUAL CLARITY OF WATERS1

ABSTRACT: The black disk method for measuring visual water clarity in situ is becoming established as a simple but robust method for optically characterizing natural waters. However, in spite of its virtues, the method is limited by a practical visibility minimum of around 0.1 m and the requirement for direct access to the water body at a point where there is adequate lighting for the visual observations. A method has been devised for measuring black disk clarity off-site on samples of waters, diluted if necessary, and contained in a trough constructed of galvanized steel. In 23 streams, rivers, and lakes of diverse optical and physical character, measurements of visual clarity of water samples contained in troughs agreed closely with in situ measurements and correlated well (inversely) with the beam attenuation coefficient measured by transmissometer. Therefore, at sites where in situ measurement is difficult, visual clarity of waters can be measured offsite on a water sample. Furthermore, the visibility of samples diluted with tap water of known clarity was predictable from a simple balance on light attenuation. This means that useful visual clarity measurements on very turbid waters and effluents can be made in a trough containing volumetrically diluted samples, so extending application of the black disk method to very low visual ranges.     

Agronomic application of olive mill wastewaters with phosphate rock in a semi-arid Mediterranean soil modifies the soil properties and decreases the extractable soil phosphorus

Olive mill wastewater (OMW), a by-product of the olive-mill industry, is produced in large amounts in Mediterranean countries. The presence of indigenous phosphate deposits in some countries like Tunisia provides an incentive for direct application or local chemical treatment at low cost to improve the solubility of low reactive phosphate rocks (PRs). The use of naturally occurring low-molecular weight organic acids (LMWOAs) that are present in OMW represents a new perspective in PR research and a possible solution for the recycling of the OMW. The present work was aimed at evaluating, under natural situations (field of olive trees), the effects of agronomic application of OMW (amounts applied: 30, 60 m(3) ha(-1)) with PR (amounts applied: 150 kg ha(-1)) on olive trees soil properties. We measured organic C, nitrogen (N), extractable phosphorus (P), exchangeable calcium (Ca), and exchangeable potassium (K), as well as other properties (pH and electrical conductivity). Our data provide evidence that agronomic application of OMW with PR has important effects on soil properties. Increases in organic C, total N, extractable P and exchangeable potassium (K) were found after the first agronomic application of OMW and PR. These increases were only temporary, following the second agronomic application of OMW and PR, significant reductions were detected in the extractable soil P (19.67 mg kg(-1) in the control soil vs. 8.99 mg kg(-1) in the amended soil). Changes in the extractable soil P could alter plant productivity and plant community structure because shifts in nutriment availability can affect the balance between limiting and non-limiting nutrients.