Impact of Cathode Conditions on Coupled Electrochemical Treatment of Nitrate Brine Concentrates

Simulated concentrated nitrate brine waste was treated in a two-stage electrolysis process, where reduction of nitrate in a cathodic chamber was coupled with oxidation of ammonium (produced in the previous stage) in an anodic chamber. The influence of operating conditions such as applied potential, electrolyte composition, and initial concentration on conversion of nitrate to ammonium in the cathodic chamber was investigated. The effects of chloride and current density on the two-stage treatment process were also examined. More negative potential at the cathode (?2.0 vs. ?1.7 and ?1.5 V) and higher current density (33 vs. 22 and 13.9 mA/cm²) favored ammonium as the product of nitrate reduction at a copper cathode and increased the overall amount of nitrate conversion. Faster reduction was seen when nitrate concentration was lower (0.01 vs. 0.02 N), but total mass conversion of nitrate in the same time period was higher for 0.02 N. The reduction of nitrate was not sensitive to sulfate or chloride concentration in the ranges studied (0–2 and 1–1.5 mg/L, respectively), but the oxidation of ammonium was noticeably higher when chloride was present. Only small amounts of ammonium and nitrate remained in the second-stage effluent after coupled treatment.     

氯酸钠氧化盐酸酸洗废液制备聚氯化铁

钢材在深加工过程中通常使用盐酸对其表面进行酸洗除锈,从而产生大量废液。为了实现盐酸酸洗废液的资源化处理,以氯酸钠作为氧化剂制备聚氯化铁,考察了氧化剂加入量、浓盐酸加入量、反应时间、反应温度等因素对Fe²⁺转化率的影响。实验得到的最佳工艺条件为：每处理100 mL废液需加入7.0 g氯酸钠、12 mL浓盐酸（12 mol/L）、0.3 g磷酸二氢钾,反应温度30 ℃,反应时间30 min,搅拌转速5 r/s。该条件下,Fe²⁺转化率可达98.51%,得到的聚氯化铁产品符合《水处理剂 聚氯化铁》（HG/T 4672—2014）标准。     

Laboratory waste minimization by recovery of silver as nano-silver colloidal dispersion from waste silver chloride

The use of cyclic experiments, where the product of one reaction becomes the starting material for the next experiment, was proposed as an effective protocol for waste minimization in an educational lab. A simple, cheap and pollution-free method was developed for recovering silver as nano-silver colloidal dispersion from waste silver chloride in the laboratories of the Faculty of Health, Safety and Environment. Silver nanoparticles of the size 5–18 nm were recovered in the presence of sodium borohydride as a reducing agent and polyvinylpyrrolidone as a stabilizer agent. The nano-silver particles were studied for their formation, structure, stability and size using UV–Vis spectroscopy, transmission electron microscopy and dynamic light scattering techniques. The antibacterial assays of nanoparticles showed satisfactory results for Escherichia coli ATCC25922, Staphylococcus aureus ATCC 29213, and Acinetobacter baumanii (Clinical isolate). A laboratory experiment was designed in which students synthesize yellow colloidal silver solution from chemical waste silver chloride and estimate particle size using visible spectroscopy.     

用硝酸银消除高浓度氯离子对COD测定的干扰及测定废液中银的回收

分析了氯离子的干扰机理,提出了用硝酸银代替硫酸汞消除氯离子干扰测定高氯离子水样COD的分析方法,同时对COD废液的处理及废液中银的回收利用进行了研究。实验结果表明,该法具有较好的准确性和重复性,其相对误差均在国家规定的允许范围内;COD废液中的银经分离后,用Zn—H2SO4体系还原回收,银回收率为94．8％,回收的银粉纯度为99．6％,且可实现COD废液中银的循环使用。     

电化学氧化处理生物难降解有机废水的研究进展

综述了电化学氧化技术的特点,通过电极材料、溶液pH、溶液中的离子等方面阐述了电化学氧化的作用机理和运行的最佳反应条件,并简单介绍电化学氧化与其他高级氧化、催化技术的协同作用,同时对今后的研究方向提出展望.     

Microbial nitrogen transformation potential in surface run-off leachate from a tropical landfill

Ammonium is one of the major toxic compounds and a critical long-term pollutant in landfill leachate. Leachate from the Jatibarang landfill in Semarang, Indonesia, contains ammonium in concentrations ranging from 376 to 929 mg N L⁻¹. The objective of this study was to determine seasonal variation in the potential for organic nitrogen ammonification, aerobic nitrification, anaerobic nitrate reduction and anaerobic ammonium oxidation (anammox) at this landfilling site. Seasonal samples from leachate collection treatment ponds were used as an inoculum to feed synthetic media to determine potential rates of nitrogen transformations. Aerobic ammonium oxidation potential (<0.06 mg N L⁻¹ h⁻¹) was more than a hundred times lower than the anaerobic nitrogen transformation processes and organic nitrogen ammonification, which were of the same order of magnitude. Anaerobic nitrate oxidation did not proceed beyond nitrite; isolates grown with nitrate as electron acceptor did not degrade nitrite further. Effects of season were only observed for aerobic nitrification and anammox, and were relatively minor: rates were up to three times higher in the dry season. To completely remove the excess ammonium from the leachate, we propose a two-stage treatment system to be implemented. Aeration in the first leachate pond would strongly contribute to aerobic ammonium oxidation to nitrate by providing the currently missing oxygen in the anaerobic leachate and allowing for the growth of ammonium oxidisers. In the second pond the remaining ammonium and produced nitrate can be converted by a combination of nitrate reduction to nitrite and anammox. Such optimization of microbial nitrogen transformations can contribute to alleviating the ammonium discharge to surface water draining the landfill.     

废硅电池片表面银的回收

采用氨-肼联合还原法回收废硅电池片上的银,优化了回收的工艺条件。实验得到的最佳回收工艺条件为：室温下采用硝酸2次浸取废硅电池片上的银,其中硝酸质量分数30%,硝酸浸取时间6 min;氯化银粉体用氨水和水合肼还原,n（Ag）∶n（N₂H₄）=0.5,水合肼还原反应温度50 ℃。回收的银粉纯度很高,结晶性较好,无需提纯。     

A chemox treatment for urea‐ and ammonium‐contaminated groundwater

In a pilot project performed at a fertilizer manufacturing facility, a one‐step chemical oxidation technique successfully treated urea‐ and ammonium‐contaminated groundwater. The oxidation reaction occurred in an 1,100‐gallon batch reactor. The contaminated inflow was buffered by the metered addition of sodium bicarbonate solution and subsequently treated with sodium hypochlorite in an 8:1 weight ratio of Cl₂:N. In an instantaneous reaction, the urea and ammo‐nium‐N were completely oxidized to nitrogen gas that was vented to the atmosphere during mixing. The pH of the reactor discharge was ?6.5. Sodium sulfite was used to reduce residual hypochlorite in the reactor effluent to chloride to provide process water with characteristics suitable for discharge. Oxidation rates were similar with different strengths of hypochlorite; however, a 5 to 6 percent sodium hypochlorite (as Cl₂) solution was the most stable. © 2005 Wiley Periodicals, Inc.     

电化学氧化-臭氧氧化联合方法处理罗丹明B模拟染料废水

采用碳黑-聚四氟乙烯（C-PTFE）为阴极的电化学氧化-臭氧氧化联合方法处理罗丹明B模拟染料废水,考察了初始pH、电解质浓度、电流和臭氧流量对废水处理效果的影响。实验结果表明：联合体系可高效处理罗丹明B废水,在初始pH为6、Na₂SO₄浓度为0.050 mol/L、电流为300 mA、臭氧流量为873 mg/h的条件下,反应3 min时废水的脱色率可达99.64%,120 min时废水COD去除率为83.17%,分别是同条件下单一臭氧氧化和电化学氧化的9.7倍和21.7倍;COD去除过程符合一级反应动力学模型。臭氧通过破坏发色基团实现罗丹明B的降解,然后由体系产生的·OH实现废水的深度氧化处理。     

次氯酸钠氧化—磷酸铵镁沉淀法处理草甘膦废水并回收磷

针对草甘膦废水处理与磷回收难题,研究了次氯酸钠氧化草甘膦与磷酸铵镁沉淀法回收磷工艺的可行性。实验结果表明,次氯酸钠氧化草甘膦的最佳工艺条件为:次氯酸钠加入量109 g/L,溶液pH为9.0,氧化时间20 min。次氯酸钠氧化草甘膦的主要降解途径为:C—N键断裂生成羟基乙酸和乙酸;C—P键断裂生成磷酸(主要反应)。正交实验得到的磷酸铵镁沉淀法回收磷的最佳工艺条件为溶液pH 9.0、镁磷摩尔比1.2、氮磷摩尔比1.4、反应时间15 min,在此条件下磷酸盐回收率达99.3%。XRD图谱证实所得固体主要成分为磷酸铵镁。     

Electrodeposition of rare-earth elements from neodymium magnets using molten salt electrolysis

Rare-earth element is an important target for recycling in Japan. In our previous work, we demonstrated the selective leaching of rare-earth elements from waste neodymium magnets using chloride molten salt electrolysis. In this study, we investigated the electrodeposition of rare-earth elements using liquid metal as a cathode. The reduction potential obtained using a liquid-zinc electrode was higher than that obtained using a solid molybdenum electrode. A zinc–rare-earth alloy was formed as the electrodeposit. The total rare-earth element content of the electrodeposit was more than 99.8 mass% without zinc and other composition of electrolysis. The activity of rare-earth elements decreased upon alloy formation, suggesting that the oxidation rate of electrodeposited alloy will be decreased.     

活性炭纤维电极法烟气脱硫研究

用活性炭纤维做电极,对烟气进行吸附氧化脱硫研究。探讨了活性炭纤维电极的吸附性能及化学氧化过程中SO2的转化规律。试验表明,活性炭纤维电极具有良好的导电性与吸附性,脱硫率达到95％,其中77％的SO2经电化学氧化为硫酸,同时这一过程可使活性炭纤维再生,延长其使用周期。     

电化学工艺处理有机废水的研究进展

综述了目前国内外学者在二维电极和三维电极的开发和改进方面的研究成果,指出了电化学氧化技术和电极材料的主要研究方向和发展趋势.提出为解决电化学水处理技术中提高电催化效率和延长电极寿命的问题,当前研究的主要方向应集中在阳极材料、反应器结构和处理工艺方面.     

Biodegradation of Slow-Release Fertilizers (Methyleneureas) in Soil

The biodegradation of urea and condensation products thereof (ureaforms or methyleneureas), their nitrification, and their influence on the respiratory rate of soil was studied over periods of up to 100 days. The total methyleneurea content of the soil was determined after its acidic extraction, using a convenient colorimetric assay, and an HPLC protocol was established to analyze for specific components of methyleneureas. Urea, unfractionated methyleneureas, and hot-water soluble methyleneureas were rapidly metabolized to ammonium, which accumulated to high concentrations and was consequently oxidized to nitrate; an accumulation of nitrite was observed during urea but not during methyleneurea degradation. Hot water-insoluble methyleneureas were degraded much more slowly, and ammonium formed from these compounds was oxidized to nitrate without being released in significant amounts. These results suggest that the use of methyleneureas of optimized composition with regard to their water solubility may help to resolve problems such as the toxicity of ammonia to plant growth as well as nitrogen loss by leaching of nitrate, denitrification and volatilization.     

高温氧化-定向转化法处理草甘膦生产含磷废料

根据草甘膦生产含磷废料的成分特点,先进行预处理及指标调节,然后采用高温氧化-定向转化法进行氧化、聚合反应,得到高品质的磷酸盐产品。实验结果表明:控制预处理后含磷废料中杂质氯化钠质量分数不超3%、p H在7~9,雾化后进入高温氧化-定向转化反应器,在750~800℃下反应50~60 min,产物中焦磷酸钠质量分数达97%以上,含磷废料的COD去除率达99%以上,杂质氯化钠分解率不超0.8%。该方法工艺条件稳定,工程化简单,可以直接得到附加值较高的焦磷酸钠、三聚磷酸钠、六偏磷酸钠等磷酸盐产品,回收产品的经济性较好,推广应用前景广阔。     

聚结晶紫膜修饰电极的制备及对水中对苯二酚和邻苯二酚的测定

通过电化学的方法将结晶紫聚合在玻碳电极表面制备聚结晶紫(PCV)膜修饰电极,并研究了对苯二酚和邻苯二酚在PCV膜修饰电极上的电化学行为。PCV膜修饰电极对对苯二酚和邻苯二酚的氧化有良好的电催化作用。在最佳的实验条件下,氧化峰电流在对苯二酚和邻苯二酚的浓度为4.0×10-6~2.8×10-4mol/L之间呈良好线性关系,对苯二酚和邻苯二酚的线性相关系数分别为0.9991和0.9823,检出限分别为6.2×10-7mol/L和9.0×10-7mol/L。PCV膜修饰电极具有良好的灵敏度、重现性和稳定性,可以应用于实际水样中两种物质的同时测定。     

Influence of poly(bisphenol A carbonate) and poly(ethylene terephthalate) on poly(vinyl chloride) dehydrochlorination

Recycling of poly(vinyl chloride) (PVC) waste is a serious problem because of its high chlorine content. Dehydrochlorination of PVC-containing polymer waste produces solid residue char, for which conversion to pyrolysis oil in a petrochemical plant seems to be an attractive way of recycling PVC waste. Unfortunately, some polymer admixtures react with HCl and cause formation of chloroorganic compounds in a char. This article describes the influence of polycarbonates and poly(ethylene terephthalate) on thermal feedstock recycling of PVC wastes using a two-stage method. It was found that the presence of polycarbonate causes the formation of small amounts of benzyl chloride and other chloroaryl or chloroalkylaryl compounds. Poly(ethylene terephthalate) interacts with HCl forming significant amounts of various chlorocompounds – mainly chloroethyl esters of terephthalic and benzoic acids, but derivatives possessing chlorine directly connected to the aromatic ring are also formed.     

硫酸亚铁的综合利用

以工业废弃物硫酸亚铁为原料,加入碳酸氢铵和氯化钾,通过一系列化学反应和过滤、蒸发、煅烧等步骤,可制得硫酸钾、氯化铵、氧化铁红和液态二氧化碳.原料中各主要成分的利用率均达94%以上.     

吸附—电化学法组合工艺处理废乳化液

以季铵盐改性硅藻土为吸油剂,采用吸附—电化学组合工艺处理拉丝废乳化液,优化了工艺条件。实验结果表明,在乳化液pH为5.0、吸油剂加入量为20 g/L、反应温度为25 ℃的最优条件下吸附除油15 min,然后在清液pH为8.5、阳极电流密度为4 A/dm²的最优条件下电化学反应4 h后,废水无色无味,COD为43 mg/L,ρ（NH₃-N）=0,ρ（Cu）= 1.6 mg/L,ρ（Zn）= 3.7 mg/L,浊度为1.1 NTU,达到GB 8978—1996污水综合排放标准。     

Electrochemical reduction of Cr(VI) in the decontamination process ELDECON

One of ABB Atom's methods, ELDECON, is an electrochemical process for decontamination of components used in nuclear power plants. ELDECON removes radioactive species while producing small amounts of waste. However, the waste sludge that is produced in the ELDECON process contains chrornate (Cr(VI)). According to the US Cod of Feguration, 40 CFR 261, if a process in any step creates chromate, the final waste has to be tested in a toxicity characteristic leachate procedure. In order to pass the test, the chromate has to be reduced to chromium (Cr(III)). Electrochemistry has proven to be a valuable tool. When incorporating indirect electrolysis into the ELDECON concept, the chromate ions are reduced. This is done by the use of an electrochemical cell (reactor bed). The method involves ferric nitrate as a reagent which, besides converting the chromate completely, also decreases the reaction time. The reaction time and the amount of solution treated in the cell have a close to linear relationship (i.e. the reaction time is proportional to the amount of solution). This makes the test cell feasible to scale up and use in the industry.