2-氯酚在超临界水-NaOH体系中的脱氯特性

研究了2-氯酚在超临界水-NaOH体系中的脱氯特性,考察了NaOH添加对2-氯酚转化率、Cl-生成率、脱氯选择性等的影响。实验结果表明,NaOH的添加能够显著提高2-氯酚的转化率、Cl-的生成率和脱氯选择性。2-氯酚的转化率随着NaOH添加量的增大而增大,460℃、25 MPa条件下,NaOH添加量与2-氯酚的摩尔比为1∶1时,停留时间27 s时可实现2-氯酚的完全转化。     

超临界水无害化共处理PVC和医疗垃圾焚烧飞灰的可行性探讨

采用超临界水氧化降解PVC同时无害化处理医疗垃圾焚烧飞灰,利用PVC脱氯形成的中间产物盐酸提取医疗垃圾焚烧飞灰中的重金属,达到飞灰无害化的目的。结果显示,超临界水可以将飞灰颗粒打碎,从而提高盐酸提取重金属的速率和效果,但是在超临界水中还存在重金属的固定过程,过长的反应时间和过高的反应温度都会降低重金属的提取效率。在提取过程中,Cu和Zn优先于Pb被盐酸浸出,而Pb被浸出后很容易被超临界水进一步固定。综合考虑重金属在超临界水中的变化特性,总结出超临界水处理飞灰和PVC的最佳条件为:PVC与飞灰质量比0.5:1,温度400℃,提取时间90 min。处理后的飞灰再次经过水洗后,其重金属浸出浓度低于USEPA规定的限制值。本研究为飞灰的无害化处理提供一条新的思路。     

Reductive dechlorination for remediation of polychlorinated biphenyls

Technologies such as thermal, oxidative, reductive, and microbial methods for the remediation of polychlorinated biphenyls (PCBs) have previously been reviewed. Based on energy consumption, formation of PCDD/F, and remediation efficiency, reductive methods have emerged as being advantageous for remediation of PCBs. However, many new developments in this field have not been systematically reviewed. Therefore, reductive technologies published in the last decade related to remediation of PCBs will be reviewed here. Three categories, including catalytic hydrodechlorination with H₂, Fe-based reductive dechlorination, and other reductive dechlorination methods (e.g., hydrogen-transfer dechlorination, base-catalyzed dechlorination, and sodium dispersion) are specifically reviewed. In addition, the advantages of each remediation technology are discussed. In this review, 108 articles are referenced.     

Minimization of cobalt nuclide emissions in supercritical water oxidation of spent resin

A rapid and complete destruction of organics in the supercritical water oxidation (SCWO) of the Co-exchanged resin was found experimentally. Due to an extremely low solubility of CoSO4 salt formed and separated effectively in the SCWO process, a minimal release of the nuclide Co would be warranted. In addition, recycling of Co nuclides is also possible by decomposition of the CoSO4 species at elevated temperatures (> 1040 K).     

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     

Effect of groundwater geochemistry on pentachlorophenol remediation by smectite-templated nanosized Pd0/Fe0

Zero-valent iron holds great promise in treating groundwater, and its reactivity and efficacy depend on many surrounding factors. In the present work, the effects of solution chemistry such as pH, humic acid (HA), and inorganic ions on pentachlorophenol (PCP) dechlorination by smectite-templated Pd(0)/Fe(0) were systematically studied. Smectite-templated Pd(0)/Fe(0) was prepared by saturating the negatively charged sites of smectite clay with Fe(III) and a small amount of Pd(II), followed by borohydride reduction to convert Fe(III) and Pd(II) into zero-valent metal clusters. Batch experiments were conducted to investigate the effects of water chemistry on PCP remediation. The PCP dechlorination rate critically depends on the reaction pH over the range 6.0~10.0; the rate constant (k (obs)) increases with decreasing the reaction pH value. Also, the PCP remediation is inhibited by HA, which can be attributed to the electron competition of HA with H(+). In addition, the reduction of PCP can be accelerated by various anions, following the order: Cl(-) > HCO (3) (-) > SO (4) (2-) ~no anion. In the case of cations, Ca(2+) and Mg(2+) (10 mM) decrease the dechlorination rate to 0.7959 and 0.7798 from 1.315 h(-1), respectively. After introducing HA into the reaction systems with cations or/and anions, the dechlorination rates are similar to that containing HA alone. This study reveals that low pH and the presence of some anions such as Cl(-) facilitate the PCP dechlorination and induce the rapid consumption of nanosized zero-valent iron simultaneously. However, the dechlorination rate is no longer correlated to the inhibitory or accelerating effects by cations and anions in the presence of 10 mg/L HA.     

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     

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     

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%。     

Efficient dehalogenation of automobile shredder residue in NaOH/ethylene glycol using a ball mill

We investigated the effectiveness of sodium hydroxide/ethylene glycol (NaOH/EG) for dehalogenation of automobile shredder residue (ASR) using a ball mill. Efficient dehalogenation was achieved at atmospheric pressure by combining the use of EG (196 degrees C b.p.) as a replacement solvent for NaOH with ball milling, which improved contact between ASR and OH(-) in solution. Moderate NaOH concentrations and increased ball mill rotation speeds produced high dechlorination that was not significantly affected by the weight ratio of ASR to EG. NaOH/EG dechlorination increased with temperature with an apparent activation energy of 50 kJ mol(-1) confirming that the reaction proceeded under chemical reaction control. The modified shrinking-core model was appropriate to explain the dechlorination process. Low chloro levels in our NaOH/EG-treated ASR suggested that this material could be used for feedstock recycling and the wet process may be applicable for dehalogenation of other important waste streams.     

Technology for recovering phosphorus from incinerated wastewater treatment sludge.

A bench-top study of phosphorus-recovering technology from ash associated with incinerated wastewater (sewage) treatment sludge was conducted by adding sulfuric acid to ashes for the elution of phosphorus. With the exception of lead, which is insoluble in sulfuric acid, when the pH of the ash fell below 2.0, phosphorus and various heavy metals in the ash were extracted. The study found that, when alkalis were added to adjust the pH of the ash extract to 4.0, phosphorus was subsequently recovered via filtration. Furthermore, when alkalis were added to adjust the pH to 10, the recovery of various heavy metals was observed. In addition, disposal of the remaining solution (wastewater), which consists of a relatively low concentration of salts, is not considered to be a significant issue since it is within wastewater discharge standards and has been found to be useful as an acid-treating substance.     

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.     

Electrochemical reduction of organohalogen compound by noble metal sintered electrode

1,2,3-Trichlorobenzene (1,2,3-TCB) was used as a model sample of persistent organic pollutants (POPs) which was dechlorinated by a closed electrochemical reduction system under an inert gas atmosphere. The effect of the electrode material was examined in the reaction. Dechlorination yields in different type of cathode electrodes using sintered RuO2 (major)/Pt/PdO, sintered Pt(major)/IrO2/RuO2, sintered RuO2, sintered PdO, sintered Pt, sintered PdO/Pt, sintered Pd/Pt and plain Pd plate were 91%, 81%, 59%, 96%, 53%, 97%, 82% and 70% respectively, at reaction times of 60 or 120 min. The reaction was exothermic after initially starting at room temperature. This electrochemical reduction system was friendly technology for environment using cation exchange membrane, supplying sodium ions from sodium hydroxide solution as anolyte. Trace amounts of dichlorobenzene, as products of stepwise dechlorination, were observed with different pathways, depending on the electrode material. Electrodes with Ru and Pd were selective mainly for meta-position dechlorination, while those with Pt groups selective mainly for ortho-position (o-position) dechlorination. A PdO sintered electrode had an especially high selectivity for meta-position (m-position) dechlorination. The results suggest that dechlorination is an electrocatalytic reduction in this cation supply system.     

Control of ammonia toxicity to Hyalella azteca by sodium, potassium and pH

The toxicity of ammonia to Hyalella azteca at constant pH in artificial media was controlled by sodium and potassium, and not by calcium, magnesium, or anions. Small increases in the LC50 for total ammonia (from 0.15 to 0.5 mM) occurred as sodium was increased from 0.1 to 1 mM and above, but major increases in the LC50 (to over 10 mM total ammonia) required the addition of potassium. Potassium was, however, more effective at reducing ammonia toxicity at high (1 mM) sodium than at low (0.1 mM) sodium. Ammonia toxicity was independent of pH at low sodium and potassium concentrations, when ammonia toxicity appeared to be associated primarily with aqueous ammonium ion concentrations. At high sodium and potassium concentrations, the toxicity of ammonia was reduced to the point where un-ionized ammonia concentrations also affected toxicity, and the LC50 became pH dependent. A mathematical model was produced for predicting ammonia toxicity from sodium and potassium concentrations and pH.     

Comparison of PCE and TCE disappearance in heated volatile organic analysis vials and flame-sealed ampules

The rates of hydrolysis reported for tetrachloroethylene (PCE) and trichloroethylene (TCE) at elevated temperatures range over two orders-of-magnitude, where some of the variability may be due to the presence of a gas phase. Recent studies suggest that volatile organic analysis (VOA) vials provide a low-cost and readily available zero headspace system for measuring aqueous-phase hydrolysis rates. This work involved measuring rates of PCE and TCE disappearance and the corresponding appearance of dechlorination products in water-filled VOA vials and flame-sealed ampules incubated at 21 and 55 °C for up to 95.5 days. While PCE and TCE concentrations readily decreased in the VOA vials to yield first-order half lives of 11.2 days for PCE and 21.1 days for TCE at 55 °C, concentrations of anticipated dechlorination products, including chloride, remained constant or were not detected. The rate of PCE disappearance was 34 times faster in VOA vials at 55 °C compared to values obtained with flame-sealed ampules containing PCE-contaminated water. In addition, the concentration of TCE increased slightly in flame-sealed ampules incubated at 55 °C, while a decrease in TCE levels was observed in the VOA vials. The observed losses of PCE and TCE in the VOA vials were attributed to diffusion and sorption in the septa, rather than to dechlorination. These findings demonstrate that VOA vials are not suitable for measuring rates of volatile organic compound hydrolysis at elevated temperatures.     

A practical approach to the degradation of polychlorinated biphenyls in transformer oil

A practical and efficient disposal method for hydrodechlorination of polychlorinated biphenyls (PCBs) in transformer oil is reported. Transformer oil containing PCBs was treated by nanometric sodium hydride (nano-NaH) and transition metal catalysts. High destruction and removal efficiency (89.8%) can be attained by nano-NaH alone under mild conditions. The process exhibits apparent characteristics of a first order reaction. The reductive ability of nano-NaH was enhanced by the addition of transition metal catalysts. In the presence of TiCl4, 99.9% PCBs was hydrodechlorinated. The complex reducing reagents, Ni(OAc)2+i-PrONa, show extra hydrodechlorinating activity for di-chlorinated biphenyls.     

Effect of a base-catalyzed dechlorination process on the genotoxicity of PCB-contaminated soil

We evaluated the genotoxicity of dichloromethane (DCM) extracts of PCB-contaminated soil before and after the soil had been treated by a base-catalyzed dechlorination process. The treatment process involves heating a mixture of the soil, polyethylene glycol (or hydrocarbons with boiling points of 310–387°C), and sodium hydroxide to 250–350°C. Dechlorination reduced by >99% the PCB concentration of the soil, which was initially 2,200 ppm. The DCM extracts of both control and treated soils were not mutagenic in strain TA100 of Salmonella, but they were mutagenic in strain TA98. Based on results in strain TA98, the base-catalyzed dechlorination process reduced the mutagenic potency of the soil by approximately one-half. The DCM extracts of the soils before and after treatment were equally genotoxic in a prophage-induction assay in . , which detects some chlorinated organic carcinogens that are not detected by the Salmonella mutagenicity assay. These results suggest that treatment of PCB-contaminated soil by base-catalyzed dechlorination reduced the mutagenicity of the soil slightly.     

Low-temperature dechlorination of hexachlorobenzene on solid supports and the pathway hypothesis

The dechlorination of HCB was carried out under low-temperature and oxygen deficient conditions on different solid supports such as SiO(2), CaO, CaSiO(3), cement and treated fly ash (tFA). All the tested supports except SiO(2) showed a HCB dechlorination potential. The dechlorination efficiencies (D(1)) of HCB by CaO, CaSiO(3), tFA and cement reached 64.62%, 76.15%, 79.97% and 32.21% at 350 degrees C for 4h, respectively. It was thought electrons in the vacancies originated from the unsaturated metallic ions and O(2-) on the crystal surfaces made the D(1) different between SiO(2), CaO and CaSiO(3). Comparing the D(1) by tFA and cement, the high dechlorination potential of tFA was due to the more free electrons from the crystal defects and the transition metals, and the more active points for the gas-solid phase reaction, which both had positive effects on dechlorination reaction. The effect of Cu addition (0.2-5.0%) on HCB dechlorination might result from the Ullmann coupling which was not notable in enhancing the dechlorination reaction. From the study, we can draw the conclusion that the dechlorination potential mainly depends on the support characteristic rather than the transition metal content. Based on this study and previous references, the dechlorination/polymerization induced by the electron transfer mode was thought to be the dominant pathway while the hydrogen transfer mode was minor. The electron was originated from the crystal defects or induced by transition metals, and the dissociation of a chloride ion happened forming a radical, and then the polymerization of radicals led to the formation of high-molecular-weight compounds which seemed to cause the material imbalance.     

Dechlorination of pentachloroethane by commercial Fe and ferruginous smectite

Short-term experiments were conducted to investigate the effect of a commercial Fe and an iron-bearing clay mineral, ferruginuous smectite (SWa-1), on the degradation of pentachloroethane (PCA). After 3 h of contact time, SWa-1 catalyzed PCA dehydrochlorination to tetrachloroethene (PCE, 65% conversion), whereas commercial Fe promoted PCA stepwise dechlorination via dehydrochlorination (approximately 40% conversion) and subsequent PCE hydrogenolysis to trichloroethene (TCE). The addition of unaltered SWa-1 to commercial Fe led to a complete inhibition on TCE production, whereas the addition of reduced SWa-1 barely resulted in a 30% decrease.