Recovery and reuse of floc sludge for high-performance capacitors

• The feasibility of facile fabrication of capacitor from floc sludge is discussed. • The porous carbon composites are obtained by acidification and KOH activation. • The as-prepared 3D structure has large surface area and optimal pore size. • Admirable specific capacitance and outstanding cycling stability are obtained. In this paper, floc sludge was transformed into porous carbon matrix composites by acidification and KOH activation at high temperature and used as an electrode material for application in capacitors. The effects of different treatment processes on the electrochemical properties of sludge materials were compared. The results of electrochemical tests showed that the sludge electrode exhibited excellent energy storage performance after HNO₃ acidification and KOH activation with a mass ratio of 3:1 (KOH/C). The specific capacitance of the sludge electrode reached 287 F/g at a current density of 1 A/g. In addition, the sludge electrode material showed excellent cycle stability (specific capacity retained at 93.4% after 5000 cycles at 5 A/g). Based on XRD, FTIR, SEM, TEM, and BET surface analysis, the morphology of sludge electrode materials can be effectively regulated by chemical pretreatment. The best-performing material showed a 3D porous morphology with a large specific surface area (2588 m²/g) and optimal pore size distribution, improving ion channels and charge conductivity. According to the life cycle assessment of floc sludge utilization, it reduced the resource consumption and toxicity risk by more than 90% compared with ordinary sludge disposal processes. This work provided a cost-effective and eco-friendly sludge reuse method and demonstrated the application potential of sludge-based materials in high-performance supercapacitors.     

Novel synthetic approaches and TWC catalytic performance of flower-like Pt/CeO2

A novel Ultrasonic Assisted Membrane Reduction （UAMR）-hydrothermal method was used to prepare flower-like Pt/CeO2 catalysts. The texture, physical/chemical properties, and reducibility of the flower-like Pt/CeO2 catalysts were characterized by X-Ray Diffraction （XRD）, Scanning Electron Microscope （SEM）, Transmission Electron Microscope （TEM）, N2 adsorption, and hydrogen temperature programmed reduction （HE-TPR） techniques. The catalytic performance of the catalysts for treating automobile emission was studied relative to samples prepared by the conventional wetness impregnation method. The Pt/CeO2 catalysts fabricated by this novel method showed high specific surface area and metal dispersion, excellent three-way catalytic activity, and good thermal stability. The strong interaction between the Pt nanoparticles and CeO2 improved the thermal stability. The Ce4＋ ions were incorporated into the surfactant chains and the Pt nanoparticles were stabilized through an exchange reaction of the surface hydroxyl groups. The SEM results demonstrated that the Pt/CeO2 catalysts had a typical three-dimensional （3D） hierarchical porous struc- ture, which was favorable for surface reaction and enhanced the exposure degree of the Pt nanoparticles. In brief, the flower-like Pt/CeO2 catalysts prepared by UAMR-hydrothermal method exhibited a higher Pt metal dispersion, smaller particle size, better three-way catalytic activity, and improved thermal stability versus conven- tional materials.     

Simultaneous leaching and carbon sequestration in constrained aqueous solutions

The behavior of metal ions’ leaching and precipitated mineral phases of metal-rich fly ash (FA) was examined in order to evaluate microbial impacts on carbon sequestration and metal immobilization. The leaching solutions consisted of aerobic deionized water (DW) and artificial eutrophic water (AEW) that was anaerobic, organic- and mineral-rich, and higher salinity as is typical of bottom water in eutrophic algae ponds. The Fe- and Ca-rich FAs were predominantly composed of quartz, mullite, portlandite, calcite, hannebachite, maghemite, and hematite. After 86 days, only Fe and Ca contents exhibited a decrease in leaching solutions while other major and trace elements showed increasing or steady trends in preference to the type of FA and leaching solution. Ca-rich FA showed strong carbon sequestration efficiency ranging up to 32.3 g CO₂/kg FA after 86 days, corresponding to almost 65% of biotic carbon sequestration potential under some conditions. Variations in the properties of FAs such as chemical compositions, mineral constituents as well as the type of leaching solution impacted CO₂ capture. Even though the relative amount of calcite increased sixfold in the AEW and the relative amount of mineral phase reached 37.3 wt% using Ca-rich FA for 86 days, chemical sequestration did not accomplish simultaneous precipitation and sequestration of several heavy metals.     

全聚苯胺太阳能电池材料的制备和性能

采用电化学和化学的方法制备了硫酸掺杂的p型导电聚苯胺和萘钠掺杂的n型导电聚苯胺,采用扫描电镜、X衍射分析、红外、紫外-可见分光光度计和和四探针法等手段对各种聚苯胺的形貌、结构和导电性等能进行了分析;将p型和n型导电聚苯胺组装成太阳能电池,研究了材料的结构、性能、电池的组装方式对太阳能电池性能的影响.结果表明:制备的p型和n型导电聚苯胺呈球形,堆砌结实,平均粒径在30—50nm,结晶度较大,导电性优异,在可见光区有强烈的吸收;由两者组成的双层太阳能电池性能优异,其开路电压为1.65V,短路电流为1.66mA.cm-2,填充因子为0.35,光电转换效率为2.96%.     

Swelling related to ettringite crystal formation in chromite ore processing residue

Several million tons of Chromite Ore Processing Residue (COPR) were deposited at two sites in New Jersey and Maryland, USA, and over time they exhibited extensive heaving phenomena. Ettringite, a needle-shaped mineral and an expansive mineral commonly recognized in the literature concerning cement- and soil, has been identified extensively in numerous COPR samples collected from these sites. It was therefore believed that ettringite formation and its crystal growth are strongly associated with COPR heaving. We investigated the correlation between ettringite and the heaving phenomena in COPR materials that contained no initial ettringite. Two identical COPR samples were exposed to a 4% w/w sulfate solution (25°C, 50°C) in a confined swell test apparatus. Both swell test samples were analyzed by means of X-ray powder diffraction. The peak intensities of newly formed ettringite were more pronounced in the sample tested at 50°C, and swell development was only observed in this sample. Scanning electron microscopy analyses revealed well-crystallized ettringite needles exceeding 40 μm in length for this sample, while ettringite crystals less than 15 μm in length formed in the sample tested at 25°C. Therefore, the results suggest that the quantity of ettringite and the extent of crystallization play a key role in the heave of COPR.     

Fate of proteins of waste activated sludge during thermal alkali pretreatment in terms of sludge protein recovery

Maillard reaction between reducing sugars and amides happened during pretreatment. Over 90 min of TAH at the optimal condition, 67.59% sludge proteins was solubilized. 15.84% soluble proteins broke down to materials with small molecular weight. Proteins are the major organic component s of waste activated sludge (WAS); the recovery of sludge proteins is economically valuable. To efficiently recover sludge proteins, WAS should undergo hydrolysis pretreatment to fully release proteins from sludge flocs and microbial cells into aqueous phase. One of the most widely used chemical methods for that is thermal alkali hydrolysis (TAH). Here, the soluble protein concentration achieved the highest level over 90 min of TAH pretreatment at 80°C; the sludge floc disintegration and microbial cell destruction were maximized according to the content profiles of bound extracellular polymeric substance (EPS) and ribonucleic acid (RNA) of sludge. Both less proteins broken down to materials with small molecular weight and less melanoidin generated were responsible. TAH pretreatment at 80°C for 90 min resulted in the solubilization of 67.59% of sludge proteins. 34.64% of solubilized proteins was present in soluble high molecular; 1.55% and 4.85% broke down to polypeptides and amino acids. The lost proteins via being converted to ammonium and nitrate nitrogen accounted for 9.44% of solubilized proteins. It was important to understand the fate of sludge proteins during TAH pretreatment in terms of protein recovery, which would be helpful for designing the downstream protein separation method and its potential application.     

Metal inclusion in expanded clays

The possibility to include in expanded clay little amounts of metallic ions present in waste material, without significant influence on the environment, was investigated. In this article, known quantities of cadmium(II), lead(II), chromium(III), and chromium(VI) were added to a mixture of raw pit clay, adding a small amount of mineral oil. The resultant paste was heated at 1200°C, in conditions to provide the commercial product with the best characteristics of lightness. The obtained pellets were analyzed in two ways. A sample of expanded clay was crushed, added to with KNaCO₃ and melted. The melted mass, after cooling, was dissolved in HCl or in water and analyzed. The composition of the raw pit clay was analyzed as a blank. In parallel, pellets were subjected to a leaching process and the eluate was analyzed for the added cations. The concentration of the metal ions in the leached water is negligible compared with that generally admitted in drinking water.     

Role of salps in the flux of organic matter to the bottom of the Ligurian Sea

Sediment-trap samples were collected during and after the occurrence of a salp (Salpa fusiformis) bloom in the Bay of Villefranche, Mediterranean Sea, in April/May 1985. Large amounts of organic aggregates and faecal pellets were collected during the bloom. The aggregates were rich in carbohydrates and mineral grains and had similar rates of sedimentation (900 to 2 100 m d^-1) to those of the faecal pellets (1 000 to 2 000 m d^-1). The results of mineralogical and organic chemical analyses indicate the potential effect of these mucus-rich aggregates on local biogeochemical fluxes.     

Increasing the performance of anaerobic digestion: Pilot scale experimental study for thermal hydrolysis of mixed sludge

The performance of a pilot plant operation combining thermal hydrolysis (170°C, 30 min) and anaerobic digestion (AD) was studied, determining the main properties for samples of fresh mixed sludge, hydrolyzed sludge, and digested sludge, in order to quantify the thermal pretreatment performance (disintegration, solubilisation, and dewaterability) and its impact on the anaerobic digestion performance (biodegradability, volatile solids reduction, and digester rheology) and end product characteristics (dewaterability, sanitation, organic and nitrogen content). The disintegration achieved during the thermal treatment enhances the sludge centrifugation, allowing a 70% higher total solids concentration in the feed to anaerobic digestion. The digestion of this sludge generates 40% more biogas in half the time, due to the higher solids removal compared to a conventional digester. The waste generated can be dewatered by centrifugation to 7% dry solids without polymer addition, and is pathogen free.     

Ce0.7Zr0.3O2纳米棒的制备及其对柴油车尾气碳颗粒的催化净化性能

本研究以硝酸铈、硝酸锆为原料使用溶剂热合成法,制备了CeO₂-ZrO₂纳米棒催化剂(Ce_0.7Zr_0.3O₂(NR)),并用于柴油车尾气碳颗粒催化净化.催化活性检测证实:Ce_0.7Zr_0.3O₂(NR)纳米棒催化剂可有效净化柴油车尾气碳烟颗粒.在Ce_0.7Zr_0.3O₂(NR)存在下,碳颗粒净化率为10%、50%和90%时,所需温度分别仅为375℃、414℃和455℃,比商用Ce_0.7Zr_0.3O₂和Ce0.3Zr0.7O2催化剂性能更优.采用氮吸附-脱附、X射线光电子能谱(XPS)、H2程序升温还原(H₂-TPR)、X射线衍射(XRD)、拉曼光谱(Raman)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等技术对催化剂进行表征.XRD和Raman结果证实,Ce_0.7Zr_0.3O₂(NR)主要由立方相CeO₂构成,并掺杂了少量四方相氧化锆.SEM和TEM结果则显示,Ce_0.7Zr_0.3O₂(NR)催化剂颗粒明显由纳米棒堆积而成,特定的纳米形貌会影响其对碳颗粒的催化氧化活性.XPS结果证明Ce_0.7Zr_0.3O₂(NR)催化剂主要具有晶格氧、化学氧和表面吸附氧等氧物种;晶格氧是碳颗粒氧化的活性氧物种,其溢流到催化剂表面可与碳颗粒接触从而提高反应活性;化学氧和表面吸附氧均为表面氧物种,极易与表面固体碳颗粒直接接触,从而可在较低温度下促进碳颗粒的净化.H₂-TPR结果进一步证实了XPS结果,Ce_0.7Zr_0.3O₂(NR)催化剂的低温还原温度比商用Ce_0.7Zr_0.3O₂催化剂更低,且含有更多的易还原氧物种,这些低温易还原氧物种可以在较低温度下参与催化反应,促进柴油车尾气颗粒物的低温催化净化.     

Two-step hydrothermal conversion of biomass waste to humic acid using hydrochar as intermediate

Converting biomass materials to humic acid is a sustainable method for humic acid production and achieve biomass valorization. A two-step hydrothermal treatment method was adopted in this study to produce humic acid from corn stalks. In the first step of the process, hydrochar was prepared at different hydrothermal temperatures and pH values. Their chemical properties were then analyzed, and the hydrochar-derived humic acids were produced under alkaline hydrothermal conditions (denoted as HHA_alk). The hydrochar, prepared under high temperature (200 °C) and strong acidic (pH 0) conditions, achieved high HHA_alk yields (i.e., 67.9 wt% and 68.8 wt% calculated based on weight of hydrochar). The sources of HHA_alk formation were as follows: 1) production in the hydrochar preparation stage, and 2) increment under the alkaline hydrothermal treatment of hydrochar. The degree of hydrochar unsaturation was suggested as an indicator for evaluating the hydrochar humification potential under alkaline hydrothermal conditions. This study provides an important reference for the preparation of suitable hydrochar with high hydrothermal humification potential.     

六方水钠锰矿对罗丹明B的去除效果及机理

六方水钠锰矿作为环境中一种具有较强氧化与吸附能力的氧化锰矿物,对环境中的有机染料有着一定的去除作用。采用常压回流法一步合成纳米六方水钠锰矿,运用X射线衍射(XRD)、电感耦合等离子体光谱仪(ICP-AES)、BET氮气吸附法、场发射扫描电镜(FESEM)和透射电镜(TEM)对其矿物晶体结构、化学组成、比表面积、孔径分布和微观形貌进行表征,选用罗丹明(RB)作为目标有机染料,研究反应条件对纳米六方水钠锰矿对RB的去除效果的影响(包括pH值、六方水钠锰矿浓度、染料浓度和温度)。进而研究六方水钠锰矿对RB的去除机制,通过在反应后的溶液中加入盐酸羟胺,使矿物溶解,吸附在矿物上的染料重新释放到溶液中,以区分吸附去除率和氧化去除率。结果表明,降低反应pH、增加六方水钠锰矿浓度、减小染料浓度以及提高温度均有利于六方水钠锰矿对罗丹明B(RB)的去除。其中影响最大的pH,反应体系pH为2.87时,RB的去除率达到99.9%,而pH为10.29时,RB的去除率仅为8.33%。通过去除机制实验结果表明,在pH为4.5时,RB的氧化去除率是36.3%,吸附去除率为4.6%,六方水钠锰矿去除RB以氧化去除为主。纳米六方水钠锰矿材料的重复利用效果很好,重复使用3次去除率,RB的去除率仅从90.6%降至85.9%。合成的纳米六方水钠锰矿有着很好的去除有机染料的效果,并且有一定的重复利用性,机制的研究也有利于提升对有机染料的去除效果。     

碱矿渣胶凝材料固化重金属污泥的研究

主要原材料为高炉矿渣的碱矿渣胶凝材料(HAS)、掺3%沸石的HAS、掺5%沸石的HAS、水泥等4种固化材料被用来固化人工合成含铅、镉、铬等重金属的污泥。污泥固化体中污泥与固化材的掺和比例为4:1。实验结果表明,HAS固化剂对重金属污泥的固化效果要好于水泥,其污泥固化体的无侧限抗压强度高于水泥固化体,同时其固化体的重金属浸出量明显低于水泥。沸石的掺入使HAS固化体的重金属浸出量减小,且随着沸石掺加量的增大,HAS固化体的重金属浸出量相应的减少。     

A new polystyrene-latex-based and EPS-containing synthetic sludge

Since the living microorganisms in activated sludge continuously change, it is difficult to conduct controlled experiments and achieve reproducible results for evaluating sludge characteristics. Synthetic sludge, as a chemical surrogate to activated sludge, could be used to investigate the sludge physicochemical properties, and it is desirable to prepare synthetic sludge with similar structure and properties to real activated sludge to explore the flocculation and settlement processes in activated sludge systems. In this work, a high-strength synthetic sludge was prepared with functional polystyrene latex particles as the framework and extracellular polymeric substances (EPS) to modify its surface. The flocculation and settling characteristics of the microspheres and the prepared synthetic sludge were tested. Compared with other three functional polystyrene latex microspheres, the synthetic sludge prepared with EPS-modified polystyrene latex microspheres showed good settling characteristics and a significantly higher strength. They could be used for studying the physicochemical properties of activated sludge.     

Variation in humic and fulvic acids during thermal sludge treatment assessed by size fractionation,elementary analysis,and spectroscopic methods

Thermal pretreatment can be applied to sludge anaerobic digestion or dewatering. To analyze the variation in humic substances during thermal sludge treatment, sludge humic and fulvic acids were extracted before and after 30-min thermal treatment at 180℃, and then their contents, molecular weight distributions, elementary compositions, and spectral characteristics were compared. The results showed that the total contents of humic and fulvic acids in the sludge almost remained constant during thermal treatment, but 35% ofhumic and fulvic acids were dissolved from the sludge solids. Moreover, both humic and fulvic acids were partly decomposed and 32% of humic acids were converted to fulvic acids. The median value of the molecular weights of humic acids decreased from 81 to 41 kDa and that of fulvic acids decreased from 15 to 2 kDa. Besides the reduction in molecular size, the chemical structures of humic and fulvic acids also exhibited a slight change, i.e. some oxygen functional groups disappeared and aromatic structures increased after thermal sludge treatment.     

熔盐法去除污泥焚烧灰中磷的效果及热动力学分析

利用碳还原剂和氯化钙熔盐药剂在1100℃下还原污泥焚烧灰中的磷酸盐为气态磷单质并去除,采用X射线衍射分析(XRD)残渣的组成和热重质谱(TGA-MS)分析反应过程.结果表明,添加氯化钙可显著提高污泥焚烧灰除磷效率,氯化钙的最优添加量为25%质量分数,此时污泥焚烧灰除磷效率为82%.XRD结果显示,污泥焚烧灰经熔盐处理后形成了氯磷灰石(chlorapatite),珍珠云母(margarite)等物质,其中氯磷灰石的形成有利于焚烧灰中磷的还原.对TGA-MS结果进行热解动力学反应拟合,结果显示,污泥焚烧灰除磷反应在添加少量氯化钙添加时为均相反应;污泥焚烧灰除磷反应在添加较多氯化钙时为固相扩散反应.固相反应的发生有利于降低磷酸盐还原反应温度并提高去除效率.     

Assessment of groundwater contamination caused by uncontrolled dumping in old gravel quarries in the Besòs aquifers (Barcelona,Spain)

The contamination of groundwater in the aquifer of the La Llagosta basin (Besòs river basin) due to waste disposal in quarries formerly used for the extraction of dry raw materials has led to the cessation of groundwater extraction for public water supply. The mobilization of pollutants was largely caused by fluctuations in piezometric levels, which led to the washing of buried waste. The hydrogeochemical processes associated with uncontrolled waste disposal in these landfilled areas of the La Llagosta basin aquifer were studied along a flow path that crosses the contaminated area. The PHREEQC code was used to establish the reactions associated with the different mineral phases through inverse modeling. This transport code, ionic exchange phenomena, surface reactions and balance (mineral phase) reactions were used to simulate the dilution phenomenon associated with the pollution after the potential removal of the sources of contamination. One-dimensional advective–dispersive modeling indicates a substantial reduction in Ca, Mg, Na and SO₄²⁻ within one year and stabilization within four years.     

Possible solutions for sludge dewatering in China

In China, over 1.43×10⁷ tons of dewatered sewage sludge, with 80% water content, were generated from wastewater treatment plants in 2007. About 60% of the COD removed during the wastewater treatment process becomes concentrated as sludge. Traditional disposal methods used by municipal solid waste treatment facilities, such as landfills, composting, or incineration, are unsuitable for sludge disposal because of its high water content. Disposal of sludge has therefore become a major focus of current environmental protection policies. The present status of sludge treatment and disposal methodology is introduced in this paper. Decreasing the energy consumption of sludge dewatering from 80% to 50% has been a key issue for safe and economic sludge disposal. In an analysis of sludge water distribution, thermal drying and hydrothermal conditioning processes are compared. Although thermal drying could result in an almost dry sludge, the energy consumption needed for this process is extremely high. In comparison, hydrothermal technology could achieve dewatered sewage sludge with a 50%–60% water content, which is suitable for composting, incineration, or landfill. The energy consumption of hydrothermal technology is lower than that required for thermal drying.     

Ca2+添加对微生物矿化固结Cd2+的影响

微生物诱导碳酸盐沉淀(MICP)可将游离的重金属离子转化为稳定的矿化物,在修复土壤重金属污染方面具有广阔的应用前景.本研究从铜陵矿区周边土壤中筛选得到1株产脲酶且耐镉矿化菌株CZW-1,16S rDNA鉴定为芽孢杆菌(Bacillus sp.),并将其利用于添加外源Ca²⁺的矿化固结Cd²⁺实验中.通过扫描电镜(SEM)、傅立叶红外光谱(FT-IR)以及X射线衍射(XRD)对矿化产物进行表征和分析.结果表明,添加一定浓度的Ca²⁺可促进细菌的生长,其最佳浓度为20 mmol·L^-1.且Ca²⁺的添加可提高细菌的最小抑制浓度和促进脲酶活性,提高对Cd²⁺的矿化率,加钙前后的矿化率由68.93%提高到75.95%.通过对矿化物的定性分析,可知加钙前后的矿物沉淀由单一CdCO₃变为CdCO₃和CaCO₃的复合沉淀,其表面也由严密紧实变成填满了小颗粒CdCO₃的多孔状.     

Potential application of sludge produced from coal mine drainage treatment for removing Zn(II) in an aqueous phase

Various analyses of physico-chemical characteristics and batch tests were conducted with the sludge obtained from a full-scale electrolysis facility for treating coal mine drainage in order to find the applicability of sludge as a material for removing Zn(II) in an aqueous phase. The physico-chemical analysis results indicated that coal mine drainage sludge (CMDS) had a high specific surface area and also satisfied the standard of toxicity characteristic leaching procedure (TCLP) because the extracted concentrations of certain toxic elements such as Pb, Cu, As, Hg, Zn, and Ni were much less than their regulatory limits. The results of X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) showed that the CMDS mainly consists of goethite (70%) and calcite (30%) as a weight basis. However, the zeta potential analysis represented that the CMDS had a lower isoelectric point of pH (pH(IEP)) than that of goethite or calcite. This might have been caused by the complexation of negatively charged anions, especially sulfate, which usually exists with a high concentration in coal mine drainage. The results of Fourier transform infrared (FT-IR) spectrometry analysis revealed that Zn(II) was dominantly removed as a form of precipitation by calcite, such as smithsonite [ZnCO?] or hydrozincite [Zn?(CO?)?(OH)?]. Recycling sludge, originally a waste material, for the removal process of Zn(II), as well as other heavy metals, could be beneficial due to its high and speedy removal capability and low economic costs.