Mineralization of phenol by Ce(IV)-mediated electrochemical oxidation in methanesulphonic acid medium: a preliminary study

The mediated electrochemical oxidation (MEO) process using cerium(IV) in methanesulphonic acid (MSA) as the oxidizing medium was employed for the mineralization of phenol in batch and continuous feeding modes. Although nitric acid was an extensively studied electrolyte for organic mineralization reactions in MEO processes it does possess the problem of NO(x) gas production during the reduction of nitric acid in the cathode compartment of the electrochemical cell. This problem could be circumvented by proper choice of the electrolyte medium such as MSA. The mediator cerium in MSA solution was first oxidized to higher oxidation state using an electrochemical cell. The produced Ce(IV) oxidant was then used for the destruction of phenol. It was found that phenol could be mineralized to CO2 by Ce(IV) in MSA. The evolved CO2 was continuously measured and used for the calculation of destruction efficiency. The destruction efficiency was observed to be 85% based on CO2 evolution for 1000 ppm phenol solution at 80 degrees C in continuous feed mode.     

Destruction of EDTA using Ce(IV) mediated electrochemical oxidation: a simple modeling study and experimental verification

Mediated electrochemical oxidation (MEO) is a recent development in the environmental research field for the complete destruction of organic pollutants. This study presents the destruction of EDTA by cerium(IV) MEO process in nitric acid medium. The destruction reaction was carried out in a continuous stirred tank reactor under various conditions. A simple kinetic model was developed to analyze and simulate the organic destruction in the MEO process. The model was based on the calculation of the total mass balance, the component mass balance, and the energy balance in the reactor and also in the heating jacket. The sensitivity to key operating conditions such as the initial EDTA concentration (50-200 mM), EDTA feeding time (30-180 min), reaction temperature (323-363 K), and the rate laws corresponding to zero-, first-, second-, and third-order reaction were analyzed. It was found that the model simulated agreed well with the experimental data for EDTA oxidation. The results obtained showed the suitability of the MEO process for the effective mineralization of high concentrations of EDTA.     

Effect of Fe-chelating complexes on a novel M2FC performance with ferric chloride and ferricyanide catholytes

As an effort to better utilize the microbial fuel cell (MFC) technology, we previously proposed an innovative MFC system named M2FC consisting of ferric-based MFC part and ferrous-based fuel cell (FC) part. In this reactor, ferric ion, the catholyte in the MFC part, was efficiently regenerated by the FC part with the generation of additional electricity. When both units were operated separately, the ferric-based MFC part produced approximately 1360 mW m⁻² of power density with FeCl₃ as catholyte and Fe-citrate as anolyte. The ferrous-based FC part with FeCl₃ as catholyte and Fe-EDTA as anolyte displayed the highest power density (1500 mW m⁻²), while that with ferricyanide as catholyte and Fe-noligand as anolyte had the lowest power density (380 mW m⁻²). The types of catholytes and chelating complexes as anolyte were found to play important roles in the reduction of ferric ions and oxidation of ferrous ion. Linear sweep voltammetry results supported that the cathode electrolytes were electrically active and these agreed well with the M2FC reactor performance. These results clearly showed that ligands played critical role in the efficiency and rate for recycling iron ion and thus the M2FC performance.     

Reduction of Ag(I), Au(III), Cu(II), and Hg(II) by Fe(II)/Fe(III) hydroxysulfate green rust

Green rusts are mixed Fe(II)/Fe(III) hydroxides that are found in many suboxic environments where they are believed to play a central role in the biogeochemical cycling of iron. X-ray absorption fine structure analysis of hydroxysulfate green rust suspensions spiked with aqueous solutions of AgCH(3)COO, AuCl(n)(OH)(4-n), CuCl(2), or HgCl(2) showed that Ag(I), Au(III), Cu(II), and Hg(II) were readily reduced to Ag(0), Au(0), Cu(0), and Hg(0). Imaging of the resulting solids from the Ag(I)-, Au(III)-, and Cu(II)-amended green rust suspensions by transmission electron microscopy indicated the formation of submicron-sized particles of Ag(0), Au(0), and Cu(0). The facile reduction of Ag(I), Au(III), Cu(II), and Hg(II) to Ag(0), Au(0), Cu(0), and Hg(0), respectively, by green rust suggests that the presence of green rusts in suboxic soils and sediments can have a significant impact on the biogeochemistry of silver, gold, copper, and mercury, particularly with respect to their mobility.     

Metal ion removal from water by sorption on paper mill sludge

Chromatographic columns packed with paper mill sludge are employed for metal ion recovery from water. The breakthrough curves show that cadmium, copper, lead and silver are removed from acid solutions (pH 2, 4); the affinity series is Pb(II)>Cu(II)>Ag(I)>Cd(II). Both the amount of metal retained and the metal-matrix interaction are pH dependent; the sorptive capacity increases with increasing pH. When the metals are present together at the same initial concentrations a competition among the different ions occurs although the affinity order remains unchanged. In metal recovery from the paper mill sludge column, the total amount of the cadmium and copper is displaced by HCl 1.0 M, 65% of the lead by HCl 0.1 M and 75% of the silver by HNO(3) 0.1 M. More than 95% of copper and lead and less than 20% of cadmium were recovered with HCl 0.1 M when the metals were present at the same time.     

Recovery of precious metals by an electrochemical deposition method

Conversion of soluble precious metals into a solid form for further reuse was studied by using an electrochemical deposition approach. It was found that the metal recovery followed a first-order reaction kinetics. The distance between the electrodes had no much impact on the recovery, while higher mixing led to faster kinetics. The presence of humic acid (HA) with lower concentration (<20mg l (-1)) did not have impact on the recovery. When its concentration was increased to 50 mg l (-1), it decreased the metal reduction. Presence of ethylene diamine tetraacetic acid (EDTA) and ionic strength slightly reduced the copper recovery rate. Around 50% removal of for HA and EDTA was achieved. In the competing environment, metal recovery was in the following order: silver>lead>copper. X-ray photoelectron spectroscopic and scanning electronic microscopic analysis of the reduced metals demonstrated that the depositions were composed of mainly elemental metals together with their oxides which were due to the oxidation.     

Electroassisted methods for waste destruction: silver(II) and peroxydisulfate reagents in the electrochemically mediated oxidation of polyaromatic sulfonates

The electrochemical oxidation is a promising process for organic pollutants which are recalcitrant to biological degradation. The anodic oxidation of 1,5-naphthalenedisulfonic acid, hereafter NDS, was evaluated at a Pt anode using in situ generated Ag(II) cation or peroxydisulfate [S2O(8)(2-)] anion as mediators. Kinetics of the direct chemical oxidation of NDS in the presence of Na2S2O8, and the identification of some oxidation intermediates are also reported. An analysis of the results shows that Ag(II) is characterized by a high-reaction rates, while [S2O(8)(2-)] performs the oxidation of NDS in a complete way.     

隔膜电解法回收利用电厂锅炉EDTA清洗废水研究

以涂Ir/Sn钛网板作阳极,以不锈钢网板作阴极,采用隔膜电解法处理电厂锅炉EDTA清洗废水.实验结果表明,电流、阴极电解液初始pH值和Fe/EDTA摩尔比对粉末铁析出速率影响较大,粉末铁电解析出的适宜条件是电解电流为1.0 A、阴极电解液初始pH值为5.6、阴极电解液Fe/EDTA摩尔比足够高.采用隔膜电解结合反渗透膜系统处理电厂锅炉EDTA清洗废水,可同时高效回收纳米级粉末铁和EDTA.     

Electrokinetic remediation of a Cu-Zn contaminated red soil by controlling the voltage and conditioning catholyte pH

Electrokinetics is an innovative technique for treating heavy metals contaminated soil, especially low pH soils such as the Chinese red soil (Udic Ferrisols). In this paper, a Cu-Zn contaminated red soil is treated by electrokinetics. When the Cu-Zn contaminated red soil was treated without control of catholyte pH during the electrokinetic treatment, the soil pH in the soil sections near cathode after the experiment was high above 6, which resulted in accumulation of large amounts of Cu and Zn in the soil sections with such high pH values. Compared to soil Cu, soil Zn was more efficiently removed from the soil by a controlled electrokinetic method. Application of lactic acid as catholyte pH conditioning solution caused an efficient removal of Cu and Zn from the soil. Increasing the electrolyte strength (salt concentration) of the conditioning solution further increased Cu removal, but did not cause a significant improvement for soil Zn. Soil Cu and Zn fractions after the electrokinetic treatments were analyzed using sequential extraction method, which indicated that Cu and Zn precipitation in the soil section closest to the cathode in the treatments without catholyte pH control limited their removal from the soil column. When the catholyte pH was controlled by lactic acid and CaCl(2), the soil Cu and Zn removal percentage after 554 h running reached 63% and 65%, respectively. Moreover, both the residual soil Cu and Zn concentrations were lower than 100 mg kg(-1), which is adequate and meets the requirement of the Chinese soil environmental quality standards.     

Factors influencing silver recovery and power generation in bio-electrochemical reactors

The recovery of silver from Ag⁺ solution coupled with power generation was investigated in bio-electrochemical system (BES). In this system, chemical energy existing in the organic matter in the anode chamber can be converted biologically to electrical energy which can be used for the reduction of Ag⁺ ions in the cathode chamber. Results showed that type of substrate influenced the metabolic pathway and affected the cell voltage progression, and columbic efficiency. Silver recovery was not affected by increasing initial pH (2.0 to 7.0) and Ag⁺ concentration (100 to 1000 mg/L) in the catholyte, whereas power generation was improved. A maximum power density of 8258 mW/m³ and a columbic efficiency of 21.61% could be achieved with 1000 mg/L of Ag⁺. Ag⁺ ions were reduced to form metallic deposits as Ag⁰ crystals on the cathode surface, which were then confirmed by scanning electron microscope (SEM) image and energy dispersive X-ray (EDX) spectrum. The BES reactor had high silver removal (i.e., >96%) after 24 h of operation. When considering the crossover of Ag⁺ ions through the cation exchange membrane, the removal was in the range of 83.73–92.51%. This crossover was not considerable as compared to the Ag⁺ initial concentration. At higher initial Ag⁺ concentration (2000 mg/L), the silver removal decreased to 88.61% and the maximum power density decreased to 5396 mW/m³. This study clearly showed that BES can be employed for silver recovery, wastewater treatment, and also electricity generation.     

Roles of oxidant,activator, and surfactant on enhanced electrokinetic remediation of PAHs historically contaminated soil

Electrokinetic (EK) remediation technology can enhance the migration of reagents to soil and is especially suitable for in situ remediation of low permeability contaminated soil. Due to the long aging time and strong hydrophobicity of polycyclic aromatic hydrocarbons (PAHs) from historically polluted soil, some enhanced reagents (oxidant, activator, and surfactant) were used to increase the mobility of PAHs, and remove and degrade PAHs in soil. However, under the electrical field, there are few reports on the roles and combined effect of oxidant, activator, and surfactant for remediation of PAHs historically contaminated soil. In the present study, sodium persulfate (PS, oxidant, 100 g L^?1) or/and Tween 80 (TW80, surfactant, 50 g L^?1) were added to the anolyte, and citric acid chelated iron(II) (CA-Fe(II), activator, 0.10 mol L^?1) was added to catholyte to explore the roles and contribution of enhanced reagents and combined effect on PAHs removal in soil. A constant voltage of 20 V was applied and the total experiment duration was 10 days. The results showed that the removal rate of PAHs in each treatment was PS + CA-Fe(II) (21.3%) > PS + TW80 + CA-Fe(II) (19.9%) > PS (17.4%) > PS + TW80 (11.4%) > TW80 (8.1%) > CK (7.5%). The combination of PS and CA-Fe(II) had the highest removal efficiency of PAHs, and CA-Fe(II) in the catholyte could be transported toward anode via electromigration. The addition of TW80 reduced the electroosmotic flow and inhibited the transport of PS from anolyte to the soil, which decreased the removal of PAHs (from 17.4 to 11.4% with PS, from 21.3 to 19.9% with PS+CA-Fe(II)). The calculation of contribution rates showed that PS was the strongest enhancer (3.3~9.9%), followed by CA-Fe(II) (3.9~8.5%) (with PS), and the contribution of TW80 was small and even negative (?1.4~0.6%). The above results indicated that the combined application of oxidant and activator was conducive to the removal of PAHs, while the addition of surfactant reduced the EOF and the migration of oxidant and further reduced the PAHs removal efficiency. The present study will help to further understand the role of enhanced reagents (especially surfactant) during enhanced EK remediation of PAHs historically contaminated soil.

     

Development of a hybrid microbial fuel cell (MFC) and fuel cell (FC) system for improved cathodic efficiency and sustainability: the M2FC reactor

In an effort to improve the efficiency and sustainability of microbial fuel cell (MFC) technology, a novel MFC reactor, the M2FC, was constructed by combining a ferric-based MFC with a ferrous-based fuel cell (FC). In this M2FC reactor, ferric ion, the catholyte in the MFC component, is regenerated by the FC system with the generation of additional electricity. When the MFC component was operated separately, the electricity generation was maintained for only 98 h due to the depletion of ferric ion in the catholyte. In combination with the fuel cell, however, the production of power was sustained because ferric ion was continually replenished from ferrous ion in the FC component. Moreover, the regeneration process of ferric ion by the FC produced additional energy. The M2FC reactor yielded a power density of up to 2 W m⁻² (or time-averaged value of approximately 650 mW m⁻²), density up to 20 times (or approximately six times based on time-averaged value) higher than the corresponding MFC system.     

A two-stage process using electrokinetic remediation and electrochemical degradation for treating benzo[a]pyrene spiked kaolin

An innovative process that combines soil electrokinetic remediation and liquid electrochemical oxidation for the degradation of organic compounds present in a polluted soil was developed and evaluated by using benzo[a]pyrene spiked kaolin. In order to increase benzo[a]pyrene solubility during electrokinetic treatment, the addition of a co-solvent or surfactant, such as ethanol or Brij 35, as flushing solution was tested. The research carried out demonstrated the influence of the desorption agent employed on benzo[a]pyrene remediation from the kaolin matrix. Thus, if the flushing solution was ethanol at 40%, there was no presence of contaminant in either chamber. On the contrary, when a solution of surfactant Brij 35 was used, benzo[a]pyrene was transported towards the cathode chamber, where it was collected. Moreover, the extent of this recovery depends on the pH profile on the soil. When no pH control was used, around 17% of initial contaminant was detected in the cathode chamber; however, when pH control was applied, the recovery of benzo[a]pyrene could be higher than 76%, when the pH control in the anode chamber was set at 7.0.In order to obtain the total degradation of mobilised benzo[a]pyrene from the contaminated soil, the liquid collected by electrokinetic remediation was oxidised by electrochemical treatment. This oxidation was accomplished via an electrochemical cell with a working volume of 0.4 L, and graphite as electrode material. The benzo[a]pyrene was almost totally degraded in 1 d, reaching a degradation of about 73% in 16 h.     

An electrogenerative process for the recovery of gold from cyanide solutions

Traditional methods for the recovery of gold from electronic scrap by hydrometallurgy were cyanidation followed by adsorption on activated carbon or cementation onto zinc dust and by electrowinning. In our studies, a static batch electrochemical reactor operating in an electrogenerative mode was used in gold recovery from cyanide solutions. A spontaneous chemical reaction will take place in the reactor and generate an external flow of current. In this present work, a static batch cell with an improved design using three-dimensional cathodes namely porous graphite and reticulated vitreous carbon (RVC) and two-dimensional cathode materials, copper and stainless steel plates were coupled with a zinc anode. The electrogenerative system was demonstrated and the performance of the system using various cathode materials for gold recovery was evaluated. The system resulted in more than 90% gold being recovered within 3h of operation. Activated RVC serves as a superior cathode material having the highest recovery rate with more than 99% of gold being recovered in 1h of operation. The morphology of gold deposits on various cathode materials was also investigated.     

Removal of chromium from abrasive blast media by leaching and electrochemical precipitation

Water is effective in leaching out Cr6+ from a mixture of paint powders and abrasive blast media. However, acids such as HNO3, HCl, and H2SO4 significantly enhance the leaching procedure. Cr ions in the leaching solutions are successfully removed by electrochemical precipitation. The consumable Fe electrodes generate ferrous ions to cause the reduction of Cr6+ to Cr3+. Cr3+ ions along with Fe2+ and Fe3+ are then removed mainly by precipitation as Cr(OH)3, Fe(OH)2, and Fe(OH)3 near the cathode where OH- ions are generated by water electrolysis. The electrochemical process is capable of discharging low levels of Cr6+, less than 1 mg/L, without pH adjustment.     

Evidence for trans-cuticular uptake of HNO3 vapor by foliage of Eastern white pine (Pinus strobus L.)

Forest declines in Europe and the northeastern United States are widely believed to be associated with deposition of air pollutants, perhaps including nitric acid vapor. The experiments presented here, which were conducted in indoor chambers, involved measurement of steady-state rates of nitric acid deposition on foliage of seedlings of eastern white pine. Nitric acid concentrations ranged from 37 to 1260 ppb, but were mostly in the 130-180 ppb range. Between 130 and 180 ppb, much of the deposited nitric acid could be removed by washing leaf surfaces with water. Amounts of nitrate removed by washing increased with exposure duration to a maximum of 7.6 nmol cm(-2) after about 8 h. Although nitrate concentrations in the washings remained constant after 8 h, nitric acid deposition nonetheless continued at a steady-state rate. We have termed this steady-state deposition 'trans-cuticular' on the assumption that the nitric acid diffuses through the cuticle. Resistance to trans-cuticular uptake (69 m(2) s mol(-1)) far exceeded resistance to diffusion across the unstirred layer at the surface of the leaf (5 m(2) s mol(-1)). High concentrations used in these experiments preclude quantitative extrapolation to ambient conditions; however, we have demonstrated that the white pine cuticle is both a major storage pool and a major barrier to uptake of deposited nitric acid.     

A combination of ion exchange and electrochemical reduction for nitrate removal from drinking water. Part II: electrochemical treatment of a spent regenerant solution.

The process of electrochemical treatment of a solution after strong basic anion exchanger regeneration was studied. The goal of the study was to reduce the nitrate content in the solution to allow its use in a closed loop. Diaphragmless, flow-through cells in a recirculation mode with and without a fluidizing bed of inert particles in the interelectrode space equipped with copper (Cu) cathodes and activated titanium anodes were used. The temperature was maintained at 20 degrees C. To assess the influence of recirculation of the regenerant solution on the quality of the treated water, the effect of the addition of copper ions to the solution, postelectrolysis cathode treatment, and enhanced mass transfer on the electrolysis results with respect to current efficiency and residual nitrate and nitrite concentration were investigated using an artificial solution. On the basis of the experimental results, a laboratory-scale unit for selective nitrate removal was designed and constructed that integrated ion exchange and electrochemical cell to one assembly. The process of recirculation of regenerant solution was tested using groundwater.     

阴极液及底物浓度对AFB-MFC同步废水处理及产电性能影响

为了提高厌氧流化床微生物燃料电池（AFB-MFC）的性能,并为双室MFC寻找价廉、易得、无污染的阴极液,在曝气量16～24 L/h、温度（35±2）℃、回流量10.2 L/h、阴极底边距阴极室内底部17.3 cm、外电阻250 Ω、水力停留时间（HRT）14.0～14.9 h以及进水pH 7.81～8.37下,研究了阴极液及底物浓度对系统产电及废水处理性能的影响。结果表明,使用缓冲溶液、阳极室出水和自来水作阴极液时,自来水的产电性能最佳,阴极液种类不影响系统有机基质的去除。以自来水为阴极液时,阴极液pH及电导率随运行时间增加而增加,COD去除率为80.11%～89.29%,输出电压及功率密度开始随运行时间增加而增加,之后稳定在440～452 mV和48.40～51.08 mW/m²之间。增加底物浓度对COD去除率影响不大,而输出电压及功率密度随底物浓度增加而下降;底物COD浓度由3 307.09 mg/L增至9 520 mg/L时,COD去除率在85.77%～94.44%之间,输出电压及功率密度则分别由449 mV和50.40 mW/m²下降至406 mV和41.21 mW/m²。自来水作阴极液可避免二次污染及阴极液对阳极室微生物的影响,并得到高的产电能力。     

洗相废水中银回收技术研究

采用电解法和离子交换法回收洗相废水中的银.结果表明,电解法对高浓度含银洗相废水的银回收处理是一种行之有效的方法.对于中低浓度洗相废水中的银的回收,采用4%硫酸再生IRA-68离子交换树脂,树脂的交换能力可以增加4倍,再生时由于已交换的银被直接固定在树脂上,结果使得再生剂处置和银回收过程更加简单方便.IRA-68离子交换树脂回收中低浓度洗相废水中银的技术具有银回收效率更高、离子交换运行时间更长和操作更为简便等优点,使得传统的离子交换技术得到极大的改进和提高.     

模拟阳光下Ag/I-TiO_2光催化预处理山核桃加工废水

研究了在模拟太阳光下,采用银修饰的碘掺杂二氧化钛光催化剂(Ag/I-TiO2)对某食品厂山核桃加工废水进行光催化预处理的效果。结合X射线衍射(XRD)、比表面积分析(BET)、紫外-可见漫反射光谱(UV-Vis)的表征结果,来分析催化剂结构对于废水处理效果的影响。探讨了Ag含量、废水初始pH(pHi)和光照时间等因素对化学需氧量(COD)去除及水质可生化性(B/C)提高的影响。并得出适宜的反应参数为:3%Ag含量;pHi为6;光照时间为240 min。在最佳条件下,COD去除率45%,废水B/C比由0.17上升到0.31。光催化氧化法能够有效降低山核桃加工废水的COD含量,并达到显著提高废水可生化性的目的。