超临界水氧化处理废水研究进展

超临界水氧化是一种很有前途的废水处理方法。全面综述了超临界水的特性 ,超临界水氧化的基本原理、工艺流程及应用现状。对超临界水氧化现存的问题 ,如反应器的腐蚀和无机盐的沉积进行了描述 ,并就可能的解决方法进行了讨论。对超临界水氧化领域中未来的研究和技术方法提出了建议     

含酚废水的超临界水氧化研究进展

本文对近年来超临界水氧化法 (SCWO)在含酚废水处理方面的发展进行了综述。主要介绍了含酚废水催化超临界水氧化技术的进展 ,讨论了催化剂、影响因素、转化率、机理及动力学等方面的内容     

Phosphorus release from ash, dried sludge and sludge residue from supercritical water oxidation by acid or base

Leaching of ash and dried sewage sludge were investigated and compared with the leaching results of sludge residue from supercritical water oxidation (SCWO). This article focuses on how the composition of ash and sludge residues influences the extraction of phosphate and heavy metals and if different treatment temperatures of the sludge effect the leachability. Results showed that acid leaching gave a higher release of phosphate than alkaline leaching for all ash and sludge residue samples. Also, alkaline leaching dissolved phosphate with a lower metal contamination than acid leaching. Furthermore, it was found that iron had a low release at both alkaline and acid leaching from ash and from SCWO residue. The difference in composition of ash and sludge residue samples had no significant influence on release of phosphate at high concentrations of acid. Phosphate release from ash, dried sludge at 300 degrees C and SCWO residue showed similar results at 1M acid leaching. However, it seems to be easier to release phosphate from the SCWO residue than from the ash at low acid concentrations. SCWO residue showed higher release than the other ashes at 0.5M HCl. Results for alkaline leaching showed higher release from ash at 1M NaOH than from SCWO residue or from dried sludge at 300 degrees C. The leaching of phosphate from dried sludge seems to be temperature dependent, as the dried sludge treated at higher temperature showed less release of phosphate. It was found that the pre-treatment of the ash may be important for better release of phosphate.     

响应面法优化超临界水氧化处理农药废水

在间歇式超临界水氧化系统中对草甘膦农药废水进行降解实验。选取温度、反应时间、过氧量3个量为因素量,总有机碳(TOC)去除率为响应量进行中心组合设计（CCD）。在实验的基础上,利用响应面分析法（RSM）对实验结果进行分析及参数优化：建立了TOC去除率与各个因素关系的二次多项式数学模型;分析了各个因素单独的及相互作用对TOC去除率的影响;优化结果表明,在温度483℃、反应时间29.2 min、过氧量148.4%的条件下,达到了最佳效果,此时TOC的去除率为100%。     

Effects of potassium alkalis and sodium alkalis on the dechlorination of o-chlorophenol in supercritical water

Effects of potassium alkalis and sodium alkalis on the dechlorination of o-chlorophenol (o-CP) in supercritical water (SCW) were studied in this paper under the conditions of 450 degrees C and 25 MPa. Experimental results indicated that the dechlorination of o-CP can be accelerated significantly by all alkalis investigated. The dechlorination of o-CP proceeded mainly via two pathways: hydrodechlorination and hydrolysis. Both of the two pathways can be promoted by alkalis, and the dechlorination of o-CP can be accelerated by both the cations and hydroxide ion dissociated from alkalis. The overall dechlorination of o-CP can be accelerated by cations via promoting the hydrodechlorination pathway, while, hydroxide ion via promoting the hydrolysis pathway. In addition, the hydrodechlorination can be accelerated faster by sodium alkalis than that by potassium ones, while, the hydrolysis can be promoted faster by potassium alkalis. This difference may be caused by the different charge density between potassium ion and sodium ion, and the different solubility and dissociation constant between potassium alkalis and sodium alkalis in SCW. Dechlorination of o-CP with addition of alkalis prior to supercritical water oxidation (SCWO) process not only can avoid the reactor corrosion caused by the generated hydrochloric acid in direct SCWO of o-CP, but also can reduce the formation of toxic chlorinated byproducts compared with direct SCWO process or SCWO of o-CP with addition of alkali.     

基于腐蚀与盐堵塞问题的超临界水氧化研究进展

超临界水氧化(简称SCWO)以其特有的优点成为了引人注目的有机废水处理方法.在操作过程中,有机物与氧化剂呈现为快速的均相反应,在数分钟内便可完全氧化生成CO2和H20.尽管已建造了工业规模的SCWO装置并用于处理化学废水,但该技术所存在的设备腐蚀以及设备因盐沉积而堵塞的问题制约着该技术的推广应用.为解决上述问题,科技工作者对SCWO工艺进行了改进,并提出了多种新颖的SCWO反应器设计思想.综述了基于解决设备腐蚀与盐堵塞问题的SCWO研究进展,并对相关问题进行了讨论.     

超临界水氧化法改善有机污染物可生化性的研究

难生化有机污染物二甲基甲酰胺、乙睛、氨基萘磺酸或羟基萘磺酸的高浓度水溶液 (4777— 2 82 4 4mg/L) ,经超临界水氧化处理后 ,其可生化性都有了大幅度的提高。二甲基甲酰胺、乙睛、氨基萘磺酸和羟基萘磺酸处理前的BOD5/CODCr,分别为 8.4 %、1.5 6 %、1.5 6 %和 2 .73%。经过超临界水氧化处理 ,它们的BOD5/CODCr可分别达到 2 3.2 %、5 5 .1%、5 0 .2 %和 38.8%。且随着处理温度的升高和COD去除率的上升 ,可生化性越来越好。这表明 ,超临界水氧化法不仅可以用来彻底降解有机污染物 ,也可以用于难生化有机污染物的预处理 ,为难生化有机污染物的生物处理创造条件     

高级氧化技术在含酚废水处理中的应用

合理高效地处理含酚废水是工业废水处理的主要任务之一。重点介绍了高级氧化技术 ,如超声波氧化、超临界水氧化、湿式氧化和光催化氧化等在含酚废水处理中的研究近况和应用前景 ,探讨了各种技术的应用和发展趋势     

一种固态磷酸根离子选择电极

针对检测水中磷酸根离子浓度的问题,研究了一种以玻碳为基底的固态磷酸根离子选择电极。在一定条件下采用循环伏安法聚合硫酸钴和硫酸钠的混合溶液,并根据正交实验得出电极最佳制备条件。采用直接电位法测定电极性能指标,得到斜率为-41.7 mV,检测下限为6.3×10-5 mol·L-1,电极的线性响应范围在10-1~10-4 mol·L-1的固态磷酸根离子选择电极;电极具有较短的响应时间,很好的稳定性,对磷酸根的检测研究具有一定的意义。     

无机盐离子对负载型催化剂Co3O4/GO降解PVA废水的影响

以氧化石墨烯(GO)作为Co3O4的载体,制备出应用于基于硫酸根自由基的高级氧化技术的负载型催化剂复合物——Co3O4/GO,采用XRD、FT-IR、Raman、EDS和SEM表征测试,并考察了无机盐离子(Cl-、HCO3-、H2PO4-和NO3-)对催化降解PVA的影响。结果表明,Co3O4已成功负载到GO上;负载型催化剂Co3O4/GO具有很高的催化活性;不同无机盐离子对催化降解反应的影响不同。本研究内容将对实际PVA废水处理过程起到借鉴和指导作用。     

蒸发壁式超临界水氧化反应器处理分散红和活性红染料废水的比较

采用蒸发壁式超临界水氧化反应器对染料分散红C.I.60和活性艳红M-2B配制的模拟废水进行降解实验.实验结果表明,2种染料的COD和TN去除率随着反应温度、氧化剂过量比(r)的升高而上升.COD去除率活性红要高于分散红,而TN去除率则相反.根据GC-MS分析和陶瓷膜SEM图像,分析测得2种染料主要反应中间产物均含有苯酚和苯甲酸,2种染料的反应对陶瓷膜均有轻微的腐蚀.     

Removing and recovering gas-phase elemental mercury by Cu(x)Co(3-x)O(4) (0.75< or = x < or =2.25) in the presence of sulphur compounds

The Hg(0) oxidation ability and reusability of Cu(x)Co(3-x)O(4) were investigated in an attempt to improve SO(2) anti-poisoning ability of metal oxide and produce more economic and effective sorbents for the control of Hg(0) emission from combustion processes. The influence of copper content on Cu(x)Co(3-x)O(4)'s (0.75< or = x < or =2.25) oxidation ability of Hg(0) in the presence of SO(2) was investigated. According to the X-ray diffraction, Brunauer-Emmett-Teller (BET) and mass balance analysis on mercury, we found that Cu(1.5)Co(1.5)O(4) showed the highest S(BET) and best Hg(0) oxidation ability. With continuous increase of x from 0.75 to 2.25, Cu(x)Co(3-x)O(4)'s SO(2) anti-poisoning ability increased. The analysis results of the X-ray photoelectron spectroscopy manifested that the adsorptive mercury species on spent Cu(1.5)Co(1.5)O(4) was HgO. The spent Cu(1.5)Co(1.5)O(4) could be regenerated by thermal decomposition at 673K and regenerated Cu(1.5)Co(1.5)O(4) showed higher Hg(0) oxidation ability due to Hg-doping. Regenerated enrichment Hg(0) was collected using activated carbon at an ambient temperature to eliminate the secondary pollution.     

负载型Co3O4活化过二硫酸盐非自由基降解有机污染物

通过在三维矿物载体表面包覆金属-多酚配合物并煅烧实现了Co₃O₄纳米颗粒的原位负载,制得了易分离回收的负载型Co₃O₄催化剂,利用SEM、XRD以及XPS表征分析其形貌和微观结构,采用活化过二硫酸盐(PDS)降解药、护品类有机污染物以评价其催化性能。以双酚A为目标污染物,考察了初始pH、PDS浓度、催化剂投加量、共存阴离子(CO₃²⁻、SO₄²⁻、NO₃⁻、Cl⁻)以及腐殖酸(HA)对BPA降解效率的影响。结果表明,负载型Co₃O₄能有效活化PDS降解有机物,在Co₃O₄投加量0.075 g·L⁻¹,BPA初始浓度0.04 mmol·L⁻¹,PDS初始浓度0.4 mmol·L⁻¹以及初始pH=7的最优条件下,120 min内BPA可被完全去除。淬灭实验与EPR实验结果表明,负载型Co₃O₄活化PDS通过单线态氧(¹O₂)主导的非自由基途径氧化分解有机物。     

pH-Dependent fate and transport of NTA-complexed cobalt through undisturbed cores of fractured shale saprolite

The codisposal of toxic metals and radionuclides with organic chelating agents has been implicated in the facilitated transport of the inorganic contaminants away from primary waste disposal areas. We investigated the transport of Co(II)NTA through undisturbed cores of fractured shale saprolite. Experiments were conducted across the pH range 4 to 8 by collecting cores from different locations within the weathering profile. Aqueous complexation, adsorption, dissociation and oxidation reactions influenced Co(II)NTA transport. The suite of reaction products identified in column effluent varied with experimental pH. At low pH and in the presence of abundant exchangeable aluminum, Co transport occurred predominantly as the Co2+ ion. At higher pH, Co was transported primarily as Co(II)NTA and the Co(III) species Co(III)(HNTA)2 and Co(III)(IDA)2. The formation of the geochemical oxidation products (Co(III) species) has far reaching implications as these compounds are kinetically and thermodynamically stable, are transported more rapidly than Co(II)NTA, and are resistant to biodegradation. These results demonstrate that natural minerals, in the physical structure encountered naturally, can be more important in the formation of mobile, stable contaminant forms than they can be for the retardation and dissociation of the contaminants.     

Degradation of atrazine using solar driven fenton-like advanced oxidation processes

Atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) was degraded using cobalt-peroximonosulfate (Co/PMS) advanced oxidation process (AOP). Three Co concentrations (0.00, 0.25 and 0.50 mM) and five peroximonosulfate (PMS) concentrations (0, 5, 8, 16 and 32 mM) were tested. Maximum degradation reached was 88% using dark Co/PMS in 126 minutes when 0.25 mM of cobalt and 32 mM of PMS were used. Complete atrazine degradation was achieved when the samples were irradiated by the sun under the same experimental conditions described. Tests for identification of intermediate products allowed identification and quantification of deethylatrazine in both dark and radiated conditions. Kinetic data for both processes was calculated fitting a pseudo-first order reaction rate approach to the experimental data. Having kinetic parameters enabled comparison between both conditions. It was found that the kinetic approach describes data behavior appropriately (R2 > or = 0.95). Pseudo-kinetic constants determined for both Co/PMS processes, show k value of 10(-4) for Co/PMS and a k value of 10(-3) for Co/PMS/ultraviolet (UV). This means, that, with the same Co/PMS concentrations, UV light increases the reaction rate by around one order of magnitude than performing the reaction under dark conditions.     

Kinetics of oxidative decolorization and mineralization of Acid Orange 7 by dark and photoassisted Co2+-catalyzed peroxymonosulfate system

A kinetic model was proposed and used to interpret the experimental data for degradation of Acid Orange 7 (AO7) in aqueous solution induced by Co(2+)/peroxymonosulfate (Co/PMS) reagent in terms of both decolorization and mineralization. The pseudo first-order decolorization rate constants are related to [Co(2+)], [PMS], reciprocal of [H(+)] and [AO7](0). Activation energy of the AO7 decolorization process was determined to be 75.7 kJ mol(-1). UV and visible light can accelerate the decolorization and mineralization process due to different mechanisms. In the combined UV/Co/PMS system, UV light can decompose PMS to generate hydroxyl ((*)OH) and sulfate radicals (SO(4)(*-)), while in the Vis/Co/PMS system, excited AO7 molecules can transfer electrons to PMS or Co(3+) and thus accelerate the decomposition of PMS and catalytic cycle of Co(3+)/Co(2+).     

Degradation of atrazine using solar driven fenton-like advanced oxidation processes

Atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) was degraded using cobalt-peroximonosulfate (Co/PMS) advanced oxidation process (AOP). Three Co concentrations (0.00, 0.25 and 0.50 mM) and five peroximonosulfate (PMS) concentrations (0, 5, 8, 16 and 32 mM) were tested. Maximum degradation reached was 88% using dark Co/PMS in 126 minutes when 0.25 mM of cobalt and 32 mM of PMS were used. Complete atrazine degradation was achieved when the samples were irradiated by the sun under the same experimental conditions described. Tests for identification of intermediate products allowed identification and quantification of deethylatrazine in both dark and radiated conditions. Kinetic data for both processes was calculated fitting a pseudo-first order reaction rate approach to the experimental data. Having kinetic parameters enabled comparison between both conditions. It was found that the kinetic approach describes data behavior appropriately (R² ≥ 0.95). Pseudo-kinetic constants determined for both Co/PMS processes, show k value of 10^?4 for Co/PMS and a k value of 10^?3 for Co/PMS/ultraviolet (UV). This means, that, with the same Co/PMS concentrations, UV light increases the reaction rate by around one order of magnitude than performing the reaction under dark conditions.     

基于碳烟颗粒催化氧化的三维有序大孔催化剂制备及性能

三维有序大孔钴锰尖晶石催化剂（3DOM CoMn2O4）以及三维有序大孔镧、铈掺杂的钴锰尖晶石催化剂（3DOM RxCo1-xMn2O4（R=Ce, La））由胶晶模板法成功合成。通过对所得的催化剂在NOx协助下的碳烟催化氧化活性评价,优化了Ce/Co和La/Co的配比。此外,还对目标催化剂进行了XRD、N2吸脱附、Raman、H2-TPR、SEM、XPS等表征。结果表明：3DOM结构增强了催化剂与碳烟颗粒之间的接触,对碳烟氧化等“固-固-气”非均相催化反应具有明显的提升作用。此外,铈和镧的掺杂增大了活性氧物种的浓度,从而增强了钴锰尖晶石催化剂的催化氧化能力。在松散接触工况下,3DOM Ce0.9Co0.1Mn2O4的Tig（起燃温度）和Tm（CO2出口浓度最大时的温度）分别为285 oC和377 oC,3DOM La0.3Co0.7Mn2O4的Tig和Tm分别为287 oC和376 oC。     

Development and validation of a terrestrial biotic ligand model predicting the effect of cobalt on root growth of barley (Hordeum vulgare)

A Biotic Ligand Model was developed predicting the effect of cobalt on root growth of barley (Hordeum vulgare) in nutrient solutions. The extent to which Ca(2+), Mg(2+), Na(+), K(+) ions and pH independently affect cobalt toxicity to barley was studied. With increasing activities of Mg(2+), and to a lesser extent also K(+), the 4-d EC50(Co2+) increased linearly, while Ca(2+), Na(+) and H(+) activities did not affect Co(2+) toxicity. Stability constants for the binding of Co(2+), Mg(2+) and K(+) to the biotic ligand were obtained: logK(CoBL)=5.14, logK(MgBL)=3.86 and logK(KBL)=2.50. Limited validation of the model with one standard artificial soil and one standard field soil showed that the 4-d EC50(Co2+) could only be predicted within a factor of four from the observed values, indicating further refinement of the BLM is needed.     

Evaluation of plant availability of soil trace metals by chemical fractionation and multiple regression analysis

Soil samples with a range of chemical and physical properties were collected from 10 different rural regions of China. Trace metals (Ni, Co, Cu, and Pb) in the soils were partitioned by a sequential extraction procedure into Mg(NO(3))(2) extractable (F1), CH(3)COONa extractable (F2), NH(2)OH.HCl extractable (F3), HNO(3)?H(2)O(2) extractable (F4), and residual (F5) fractions. Chemical fractionation showed that F1 fraction of the metals was less than 1% and residue was the dominant form for Cu and Ni in all samples, and for Co in most of the samples. Significant interrelationships of the fractions varied considerably with the different metals. Winter wheat (Triticum aestivum L.) and alfalfa (Medicago sativa L.) had been grown on the soils in a pot-culture experiment under greenhouse conditions for 40 days. Metal availability to the plants was evaluated by simple and multiple regression analysis. The Mg(NO(3))(2) extractable Co (F1) was significantly correlated with Co concentrations in different parts of wheat and in the whole of alfalfa. For the other metals, the independent variables of the multiple regression models, chosen by stepwise selection, were given as: F1 and F2 + F3 + F4 for Ni; F1, F2 + F3 and F4 for Cu; and F3 + F4 for Pb. The results of this study demonstrate that the sequential extraction procedure, in conjunction with multiple regression models using a combination of correlated fractions as an independent variable, may be useful for the prediction of plant absorption of trace metals in soils.