Two-stage Sequential Electrochemical Treatment of Nitrate Brine Wastes

Nitrates in concentrated brines can be electrochemically reduced in the cathodic chamber of a split-cell electrochemical reactor with formation of ammonium (and small amounts of nitrite). Fortunately, ammonium may be electrochemically oxidized to nitrogen gas in the anodic reaction chamber if a coupled sequential process is used. The presence of chloride in the brine waste is an important consideration in oxidative electrochemical processes, however, because it cycles through oxidized and reduced states at the electrode surfaces and in the bulk solution. Electrochemical oxidation converts chloride ions to “active chlorine” species with additional oxidizing capability (chlorine, hypochlorous acid and hypochlorite – essentially bleach), as well as to chlorates, depending on the reaction conditions. The production of these active species improves treatment performance in the ammonium oxidation phase since oxidation is no longer limited to the electrode surface. However, the process must be engineered to minimize loss of process efficiency due to parasitic side reactions (chloramines and chlorate). In this study, two-stage batch electrolysis was conducted using a three-electrode (copper anode, platinum-coated titanium cathode, silver/silver chloride reference) electrochemical cell, with the anodic and cathodic chambers separated by a Nafion 117 membrane. Treatment of nitrate and ammonium was tested with and without the presence of chloride in the waste. No significant difference was observed in cathodic nitrate reduction with chloride present or absent. However, the presence of chloride in the solution favored overall soluble nitrogen elimination upon oxidation. Increasing applied current increased production of undesirable byproducts (especially chlorate).     

Cr(VI) reduction in aqueous solutions by using copper smelter slag

The ability of Copper Smelter Slag (CSS) to reduce Cr(VI) in aqueous solutions has been investigated. The extent of reduction is dependent on the amounts of acid and reductant, contact time, Cr(VI) concentration, temperature of the solution and particle size of CSS. The amount of acid is the most important variable affecting the reduction process. When twice the amount of acid required with respect to Cr(VI) was used, Cr(VI) in 100 ml solution (100 mg/l) was completely reduced in a contact period less than 5 min by a 10 g/l dosage of CSS. Reduction efficiency increased with increase in temperature of solution, showing that the process is endothermic. Reduced chromium, and iron and other metals dissolved from CSS were effectively precipitated by using NaOH or calcinated carbonatation sludge from sugar plant.     

Removal of Cr(VI) from contaminated soil by electrokinetic remediation

A new process for the removal of hexavalent chromium [Cr(VI)] contaminated soil is described. The process provides for an efficient removal of anionic chemicals from contaminated soils. Chromate anions were removed from the soil to the anodic reservoir by the moving force of electromigration. In this process, the chromate anions that accumulate in the anodic reservoir are simultaneously eliminated by using a column packed adsorbent. The adsorbent (immobilized tannin) used was chemically incorporated into cellulose. Cr(VI) was found to be adsorbed to this adsorbent efficiently. In the electrokinetic process, the pH of the aqueous solution in the anodic reservoir was decreased by the electrolysis of water. In the present study, the pH of the solution in the anodic reservoir is maintained at pH 6 by the addition of an aqueous alkaline solution during the electrokinetic process. The advantage of pH control is that it promotes the release of Cr(VI) from the soil by electromigration, thus permitting the maximum adsorption of Cr(VI) on the immobilized tannin. Simultaneous collection of Cr(VI) from the anodic reservoir leads to the protection from secondary contamination with Cr(VI).     

Model of technological alternatives of production of sodium chromate (VI) with the use of chromic wastes

This article presents a mathematical model which describes the sodium chromate (VI) production process with the use of chromic waste as a substitution of natural raw materials. This model is a function of selected process parameters common for all of the examined alternatives and based on equations of material balance. Optimization of the elaborated technological alternatives of the production process with use of recycling of chromic waste has been evaluated by determining the extreme value of the quality indicator WJ. This indicator defines the quantity of waste created in the process. Optimization results enabled the selection of the optimal technological solution from all of the alternatives possible for use in industrial practice. Negative values of the indicator prove that there is the possibility of introducing to the process a larger quantity of waste than the one obtained in the process and transported to the storage heaps.     

Evidence of Al-Cr interactions affecting Cr-leaching from waste incineration ashes

Leaching tests on flue gas ashes from waste incineration showed low leaching of Cr from ashes that under moist anaerobic conditions also produced hydrogen gas. In some cases, also the redox levels (aerobic/anaerobic conditions) during the leaching test affected Cr leaching. Aerobic ashes tested in an open batch leaching test leached Cr up to 2-3 orders of magnitude more than the ashes kept moist under anaerobic conditions and tested in a closed leaching test. Model experiments showed that metallic Al could reduce Cr and at the same time produce H(2). The hydrogen gas per se could not reduce Cr. Laboratory experiments with ashes provided evidence that metallic Al, present naturally in the ashes or amended, could reduce Cr under moist anaerobic, but not under aerobic storage. Significant Cr reduction was linked to, but not caused by hydrogen formation. The reduced Cr seemed to be partially reoxidizable upon aeration or drying. The observations presented provide a basis for understanding the complexity of Cr leaching from waste incineration ashes, as for example, why some chemical stabilization methods increase Cr leaching, and point out the need for standardizing leaching test conditions with respect to Cr.     

铁矿石烧结烟气脱硫灰处理含铬废水

在分析铁矿石烧结烟气脱硫灰成分的基础上,利用脱硫灰中的亚硫酸盐还原废水中的Cr(Ⅵ),再加碱中和,通过沉淀去除铬。在初始废水pH 1.0、脱硫灰加入量0.06 g/mg(以Cr(Ⅵ)计)、振荡转速160 r/min、振荡时间25 min、中和pH 7.5的最佳工艺条件下处理模拟含铬废水,Cr(Ⅵ)质量浓度由10.00 mg/L降至0.18 mg/L,去除率达98.2%。最佳工艺条件下处理3种实际含铬废水,处理后出水的Cr(Ⅵ)和总铬的质量浓度及pH均满足GB 8978—1996《污水综合排放标准》。实现了对脱硫灰的综合利用、化害为利和以废治废的目标。     

Molten carbonate fuel cells fed with biogas: Combating H2S

The use of biomass and waste to produce alternative fuels, due to environmental and energy security reasons, is a high-quality solution especially when integrated with high efficiency fuel cell applications. In this article we look into the coupling of an anaerobic digestion process of organic residues to electrochemical conversion to electricity and heat through a molten carbonate fuel cell (MCFC). In particular the pathway of the exceedingly harmful compound hydrogen sulphide (H₂S) in these phases is analysed. Hydrogen sulphide production in the biogas is strongly interrelated with methane and/or hydrogen yield, as well as with operating conditions like temperature and pH. When present in the produced biogas, this compound has multiple negative effects on the performance and durability of an MCFC. Therefore, there are important issues of integration to be solved.Three general approaches to solve the sulphur problem in the MCFC are possible. The first is to prevent the formation of hydrogen sulphide at the source: favouring conditions that inhibit its production during fermentation. Secondly, to identify the sulphur tolerance levels of the fuel cell components currently in use and develop sulphur-tolerant components that show long-term electrochemical performance and corrosion stability. The third approach is to remove the generated sulphur species to very low levels before the gas enters the fuel cell.     

Bioremediation of Chromate by Sulfate-Reducing Bacteria, Cytochromes c3 and hydrogenases

The treatment of soils and ground waters polluted by heavy metals is of economical and environmental interest. Reduction of Cr(VI) to the less toxic Cr(III) associated to its precipitation is a potentially useful process for bioremediation. In order to develop ecological processes using micro-organisms, we have compared various sulfate-reducing bacteria for enzymatic reduction of chromate. The best Cr(VI) reductase activity was obtained with Desulfomicrobium norvegicum. Despite morphological changes induced by the presence of chromate, this strain can grow in the presence of up to 500 M Cr(VI) and can decontaminate waters polluted by Cr(VI) when seeded in bioreactors. We have demonstrated the ability of several metalloenzymes (cytochromes c ₃ and hydrogenases) to reduce chromate. Biophysical investigations of the chromate/protein interaction in order to get further informations on the mechanism of metal reduction by cytochromes c ₃ are under the way.     

Leaching behaviour of a chromium smelter waste heap

This paper reports the results of geochemical sampling and modelling of leachates from a chromite ore processing residue (C.O.P.R.) pile under rainwater infiltration. The waste pile is located in the north of England and consists of 800,000 m3 of waste. The pH of fresh leachate is similar to that of a solution in equilibrium with portlandite Ca(OH)2, which is a major constituent of the waste. The in-gassing of CO2(g) causes the pH of the leachates to drop along the drainage ditch and calcite precipitation to occur. The extent of in-gassing is dependent upon the flow rate within the drainage ditch. The dissolution of solid solutions containing residual chromate is likely to control chromate concentrations within the leachate.     

Preparation of MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript> from waste tannery solution and effect of sulfate,chloride, and calcium on leachability of chromium

This paper presents a study regarding the preparation of MgCr₂O₄ from waste tannery solution, and chromium leaching behavior is also investigated with varying amounts of sulfate, chloride and calcium. The phase transformation, crystallinity index and crystallite diameter were characterized using XRD, FT-IR and thermal analysis. A well-crystallized MgCr₂O₄ was successfully prepared at 1400 °C. The sintering temperature had a major impact on the formation of MgCr₂O₄ compared with sintering time. The MgCr₂O₄ phase was observed initially at 400 °C and its crystallite diameter increased with increasing temperature. The concentration of total chromium leached and Cr(VI) decreased gradually with increasing temperature. The considerable amount of Cr(VI) was found in the leachate at 300–500 °C caused by Cr(VI) intermediary products. Sulfate and chlorine could impact the transformation efficiency of chromium adversely, and chlorine has a more significant effect than sulfate. The presence of calcium disturbed the formation of MgCr₂O₄ and new chromium species (CaCrO₄) appeared, which resulted in a sharp increase in the concentration of leached Cr(VI). Incorporating Cr(III) into the MgCr₂O₄ spinel for reusable products reduced its mobility significantly. This was demonstrated to be a promising strategy for the disposal of chromium containing waste resource.     

中孔活性炭对水溶液中Cr3+的吸附

采用模板法和氢氧化钾化学活化法制备出不同中孔率的中孔活性炭并用于水中Cr3+的静态吸附,探讨了中孔活性炭吸附Cr3+的影响因素.实验结果表明,当溶液pH为6.0、吸附温度为50℃、吸附时间为120min、活性炭加入量为2.0g/L以及活性炭中孔率为80.0％～90.0％时.中孔活性炭对溶液中Cr3+的去除率达到98.5％.分别采用Langmuir和Freundlich方程拟合活性炭对Cr3+吸附的等温线,发现Langmuir等温吸附模型对活性炭吸附Cr3+拟合程度更好.活性炭中孔率的增大有利于提高Cr3+的平衡吸附量,但同时还受到活性炭表面酸总量的影响.吸附Cr3+前、后活性炭的FTIR谱图表明,Cr3+与活性炭表面含氧官能团发生了离子交换反应.     

Waste plastics recycling process using coke ovens

The Japan Iron and Steel Federation (JISF), as its voluntary energy-saving action plan, proposed a 10% energy reduction by 2010 with 1990 as the basis. Further, it has suggested an additional 1.5% energy saving by the use of waste plastics as a metallurgical raw material. The amount of processing of waste plastics which corresponds to this amount of energy conversion is about 1 million t scale during 1 year. Conventional known methods for recycle-processing of waste plastics include, for example, the method of injection into a blast furnace to use waste plastics as an iron-ore reducing agent instead of coal. On the other hand, the coking process is considered to be suitable as a waste plastic recycling facility because the process involves coal carbonization in a high-temperature and reducing atmosphere. Carbonization tests with mixed waste plastics were conducted with laboratory equipment and in actual coke ovens. As a result, it was confirmed that the waste plastics recycling process using coke ovens is feasible. Therefore, a waste plastics recycling process using coke ovens was started as a chemical recycling technology at Nippon Steel.     

Central Composite Design Model to Study Swelling of GrA-cl-poly(AAm) hydrogel and Kinetic Investigation of Colloidal Suspension

In the present study, the flocculation behavior of crosslinked copolymer GrA-cl-poly(AAm) hydrogel has been studied for the removal of turbidity from waste water. Sodium borohydride has been used for the reduction of the Gum rosin acids by which it gets converted into rosin alcohols. The reduced Gum rosin alcohol was crosslinked by the use of MBA and copolymerized with acrylamide using KPS as a redox initiator. Synthesized sample was then optimized for reaction conditions like reaction time, reaction temperature and the amount of solvent, monomer concentration, initiator concentration and pH of the reaction medium in order to get maximum percentage swelling. Synthesized samples were characterized using Fourier transform infrared spectroscopy, scanning electron of microscopy and X-ray diffraction techniques. Response surface methodology (RSM) based central composite design was used to study the effect of pH of swelling medium and temperature to maximize the percentage swelling. A statistical model (ANOVA) predicted pH 7.0 and temperature 40?°C as optimum operating conditions in order to get maximu swelling. GrA-cl-poly(AAm) hydrogel was found to be pH and temperature sensitive. Kaolin has been employed as a coagulant. The flocculation efficiency of the synthesized polymer was studied as a function of polymer dose, temperature and pH of the solution. GrA-cl-poly(AAm) observed to show maximum flocculation efficiency (95%) with 70mgL^?1 polymer dose in pH 5.0 at 30?°C. The adsorption capacity of malachite green dye removal (95%) was also studied with this synthesized polymer. The results validate that GrA-cl-poly(AAm) hydrogel has significant flocculation and dye removal properties and can be employed as an effective and low-cost material for removal of impurities from waste water.     

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。     

Evaluation of leachate emissions from crushed rock and municipal solid waste incineration bottom ash used in road construction

Three years of leachate emissions from municipal solid waste incineration bottom ash and crushed rock in a full-scale test road were evaluated. The impact of time, construction design, and climate on the emissions was studied, and the predicted release from standard leaching tests was compared with the measured release from the road. The main pollutants and their respective concentrations in leachate from the roadside slope were Al (12.8-85.3 mg l(-1)), Cr (2-125 microg l(-1)), and Cu (0.15-1.9 mg l(-1)) in ash leachate and Zn (1-780 microg l(-1)) in crushed rock leachate. From the ash, the initial Cl(-) release was high ( approximately 20 g l(-1)). After three years, the amount of Cu and Cl(-) was in the same range in both leachates, while that of Al and Cr still was more than one order of magnitude higher in ash leachate. Generally, the release was faster from material in the uncovered slopes than below the pavement. Whether the road was asphalted or not, however, had minor impacts on the leachate quality. During rain events, diluted leachates with respect to, e.g., salts were observed. The leaching tests failed to simulate field leaching from the crushed rock, whereas better agreement was observed for the ash. Comparisons of constituent release from bottom ash and conventional materials solely based on such tests should be avoided.     

氧化沟工艺在处理有机废水中的应用

以河南省某制革企业综合有机废水处理工程为实例,根据排放废水的水质水量及处理要求进行工程分析,对含铬废水的处理提出工艺流程;对综合有机废水处理工艺各构筑物的功能和设计进行了详细阐述.     

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.     

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。     

凹凸棒土/苯胺-邻氨基酚复合吸附剂的制备及其对Cr(Ⅵ)的吸附性能

采用原位聚合法制备了凹凸棒土/苯胺-邻氨基酚（ATP/PANOAP）复合吸附剂,对其进行了SEM和FTIR表征,并通过吸附实验考察了ATP/PANOAP对水中Cr（Ⅵ）的吸附性能。实验结果表明,ATP/PANOAP对水中Cr（Ⅵ）具有良好的去除效果,在Cr（Ⅵ）初始质量浓度为50 mg/L、溶液pH为6、吸附剂加入量为0.375 g/L、温度为298 K的条件下,Cr（Ⅵ）去除率达93.39%。ATP/PANOAP对Cr（Ⅵ）的吸附动力学过程符合准二级动力学模型,吸附热力学过程符合Langmuir单层吸附模型,该吸附过程以化学吸附为主,且为自发进行的吸热反应。     

Real time alteration of a nuclear waste glass and remobilization of lanthanide into an interphase

The development of predictive models for the long term evolution of nuclear waste glass requires the complete knowledge of the glass dissolution at the laboratory scale. A new approach was developed to determine the initial reaction during the first steps of experience, a new concept was developed, based on the combination of dynamic leaching test and the characterization of the altered materials. With this experimental set-up it is possible to follow in real time the glass alteration process at a fine temporal scale. The results put in evidence a singular behaviour of the lanthanide, shown by a concentration peak of La, Nd and Ce after 2 h and a quick decrease of their concentration measured on line in the solution during the leaching test. This fact is directly linked to the development of an interphase (altered layer which differs from the initial solid by its texture, structure and chemical composition) at the interface of the glass surface and the leaching solution. This work is an attempt to integrate the formation of the alteration products (here the interphase) during leaching into the dissolution mechanisms of a nuclear waste glass. A model is proposed and discussed.