Effects of different sludge disintegration methods on sludge moisture distribution and dewatering performance

A key step in sludge treatment is sludge dewatering. However, activated sludge is generally very difficult to be dewatered. Sludge dewatering performance is largely affected by the sludge moisture distribution. Sludge disintegration can destroy the sludge structure and cell wall, so as change the sludge floc structure and moisture distribution, thus affecting the dewatering performance of sludge. In this article, the disintegration methods were ultrasound treatment, K₂FeO₄ oxidation and KMnO₄ oxidation. The degree of disintegration (DD_COD), sludge moisture distribution and the final water content of sludge cake after centrifuging were measured. Results showed that three disintegration methods were all effective, and K₂FeO₄ oxidation was more efficient than KMnO₄ oxidation. The content of free water increased obviously with K₂FeO₄ and KMnO₄ oxidations, while it decreased with ultrasound treatment. The changes of free water and interstitial water were in the opposite trend. The content of bounding water decreased with K₂FeO₄ oxidation, and increased slightly with KMnO₄ oxidation, while it increased obviously with ultrasound treatment. The water content of sludge cake after centrifuging decreased with K₂FeO₄ oxidation, and did not changed with KMnO₄ oxidation, but increased obviously with ultrasound treatment. In summary, ultrasound treatment deteriorated the sludge dewaterability, while K₂FeO₄ and KMnO₄ oxidation improved the sludge dewaterability.     

Effects of different sludge disintegration methods on sludge moisture distribution and dewatering performance

A key step in sludge treatment is sludge dewatering. However, activated sludge is generally very difficult to be dewatered. Sludge dewatering performance is largely affected by the sludge moisture distribution. Sludge disintegration can destroy the sludge structure and cell wall, so as change the sludge floc structure and moisture distribution, thus affecting the dewatering performance of sludge. In this article, the disintegration methods were ultrasound treatment, K₂FeO₄ oxidation and KMnO₄ oxidation. The degree of disintegration (DDCOD), sludge moisture distribution and the final water content of sludge cake after centrifuging were measured. Results showed that three disintegration methods were all effective, and K₂FeO₄ oxidation was more efficient than KMnO₄ oxidation. The content of free water increased obviously with K₂FeO₄ and KMnO₄ oxidations, while it decreased with ultrasound treatment. The changes of free water and interstitial water were in the opposite trend. The content of bounding water decreased with K₂FeO₄ oxidation, and increased slightly with KMnO₄ oxidation, while it increased obviously with ultrasound treatment. The water content of sludge cake after centrifuging decreased with K₂FeO₄ oxidation, and did not changed with KMnO₄ oxidation, but increased obviously with ultrasound treatment. In summary, ultrasound treatment deteriorated the sludge dewaterability, while K₂FeO₄ and KMnO₄ oxidation improved the sludge dewaterability.     

Fenton氧化/混凝协同处理焦化废水生物出水的研究

对Fenton氧化/混凝协同处理焦化废水生物出水的方法进行了研究,在综合考虑经济性和去除效果的前提下,提出了反应的最佳条件:H₂O₂投加量为220 mg/L,Fe²⁺投加量为180 mg/L,聚丙烯酰胺投加量为4.5 mg/L,反应时间为0.5h,pH=7.最终COD去除率可达44.5%,色度可以降为35倍,出水符合国家污水排放二级标准.同时,通过分析分子量分布和小分子有机物组成,揭示了Fenton氧化/混凝协同处理焦化废水生物出水的污染物变化规律.结果表明焦化废水经过Fenton氧化/混凝协同处理后,其出水可达到国家二级排放标准,并且处理成本相对较低,具有实际应用的前景.     

Effect of phosphate on heterogeneous Fenton oxidation of catechol by nano-Fe3O4: Inhibitor or stabilizer?

The effect of phosphate on adsorption and oxidation of catechol, 1,2-dihydroxybenzene, in a heterogeneous Fenton system was investigated. In situ attenuated total reflectance infrared spectroscopy (ATR-FTIR) was used to monitor the surface speciation at the nano-Fe₃O₄ catalyst surface. The presence of phosphate decreased the removal rate of catechol and the abatement of dissolved organic compounds, as well as the decomposition of H₂O₂. This effect of phosphate was mainly due to its strong reaction with surface sites on the iron oxide catalyst. At neutral and acid pH, phosphate could displace the adsorbed catechol from the surface of catalyst and also could compete for surface sites with H₂O₂. In situ IR spectra indicated the formation of iron phosphate precipitation at the catalyst surface. The iron phosphate surface species may affect the amount of iron atoms taking part in the catalytic decomposition of H₂O₂ and formation of hydroxyl radicals, and inhibit the catalytic ability of Fe₃O₄ catalyst. Therefore, phosphate ions worked as stabilizer and inhibitor in a heterogeneous Fenton reaction at the same time, in effect leading to an increase in oxidation efficiency in this study. However, before use of phosphate as pH buffer or H₂O₂ stabilizer in a heterogeneous Fenton system, the possible inhibitory effect of phosphate on the actual removal of organic pollutants should be fully considered.     

H2O2预氧化对负载铁制备污泥炭基催化剂效能的影响

以城市污水厂二沉池污泥为原料,考察了不同H_2O_2投加量下污泥预氧化对铁负载污泥形成前驱体及其热解后制得炭基催化剂性能的影响,研究了污泥预氧化对强化铁负载制备均一分散型污泥炭基催化剂的机理.结果表明,污泥预氧化促进了污泥细胞破解,降低了絮体颗粒粒径和表面Zeta电位,使铁负载量增加、铁活性位点在污泥载体上的分散性明显增强,形成炭基催化剂保持着高催化活性,其稳定性显著增加.对模拟含铬黑T染料废水的多相芬顿降解试验说明,当污泥预氧化H_2O_2投加量为2.25%时制备的炭基催化剂,其反应120 min后铬黑T的降解率为91%,略低于未预氧化时污泥炭基催化剂的降解效率(96%);但未预氧化炭基催化剂其反应后溶液中铁离子的溶出量(18.9%)远高于预氧化后形成的催化剂(2.5%),且后者循环3次对铬黑T的降解率仍可达到86%,表现出较强的稳定性.     

Toluene decomposition performance and NOx by-product formation during a DBD-catalyst process

Characteristics of toluene decomposition and formation of nitrogen oxide (NOx) by-products were investigated in a dielectric barrier discharge (DBD) reactor with/without catalyst at room temperature and atmospheric pressure. Four kinds of metal oxides, i.e., manganese oxide (MnOx), iron oxide (FeOx), cobalt oxide (CoOx) and copper oxide (CuO), supported on Al₂O₃/nickel foam, were used as catalysts. It was found that introducing catalysts could improve toluene removal efficiency, promote decomposition of by-product ozone and enhance CO₂ selectivity. In addition, NOx was suppressed with the decrease of specific energy density (SED) and the increase of humidity, gas flow rate and toluene concentration, or catalyst introduction. Among the four kinds of catalysts, the CuO catalyst showed the best performance in NOx suppression. The MnOx catalyst exhibited the lowest concentration of O₃ and highest CO₂ selectivity but the highest concentration of NOx. A possible pathway for NOx production in DBD was discussed. The contributions of oxygen active species and hydroxyl radicals are dominant in NOx suppression.     

高铁酸钾破解剩余污泥的水解效能分析

为了有效提高污泥水解效率、缩短厌氧消化时间,以K₂FeO₄为氧化剂破解剩余污泥,考察K₂FeO₄投加量（50~500 g/kg,以干质量计）对污泥破解率的影响,分析水解液各项特征指标并对其可生化性能进行预测,探究该方法作为污泥厌氧预处理的可行性.结果表明:污泥水解效率随着K₂FeO₄投加量的增加而升高,当搅拌速率为500 r/min、反应时间为2 h、K₂FeO₄投加量为500 g/kg的条件下,可实现最高的污泥破解率（34.6%）.污泥水解液中有机物以多糖、蛋白质为主,并有少量挥发性有机酸;污泥破解过程也伴随着P和NH₄+-N的释放,上清液中ρ（TP）最高可达496 mg/L,且以正磷酸盐为主（约310 mg/L）,可对其进行回收.采用三维荧光体积积分的方法对污泥水解液的可生化性能进行预测,发现污泥经K₂FeO₄预处理后,水解液中RB（易降解有机质）和PB（难降解有机质）荧光强度均明显增加,当K₂FeO₄投加量为50 g/kg时,F_digestion（生物可降解性指数）达到最大值（4.75）,预测此时污泥的可生化性能最佳.以K₂FeO₄为氧化剂预处理污泥可有效提升污泥水解效率,但若作为厌氧消化预处理,应综合考虑污泥破解率和可生化性能.研究显示,搅拌速率为500 r/min、反应时间为2 h、K₂FeO₄投加量为50 g/kg预处理条件下污泥的可生化性能最佳.      

Enhanced activation of peroxydisulfate by strontium modified BiFeO3perovskite for ciprofloxacin degradation

A series of Sr-doped BiFeO₃ perovskites (Bi_1-xSr_xFeO₃, BSFO) fabricated via sol-gel method was applied as peroxydisulfate (PDS) activator for ciprofloxacin (CIP) degradation. Various technologies were used to characterize the morphology and physicochemical features of prepared BSFO samples and the results indicated that Sr was successfully inserted into the perovskites lattice. The catalytic performance of BiFeO₃ was significantly boosted by strontium doping. Specifically, Bi_0.9Sr_0.1FeO₃ (0.1BSFO) exhibited the highest catalytic performance for PDS activation to remove CIP, where 95% of CIP (10 mg/L) could be degraded with the addition of 1 g/L 0.1BSFO and 1 mmol/L PDS within 60 min. Moreover, 0.1BSFO displayed high reusability and stability with lower metal leaching. Weak acidic condition was preferred to neutral and alkaline conditions in 0.1BSFO/PDS system. The boosted catalytic performance can be interpreted as the lower oxidation state of Fe and the existence of affluent oxygen vacancies generated by Sr doping, that induced the formation of singlet oxygen (¹O₂) which was confirmed as the dominant reactive species by radical scavenging studies and electron spin resonance (ESR) tests. The catalytic oxidation mechanism related to major ¹O₂ and minor free radicals was proposed. Current study opens a new avenue to develop effective A-site modified perovskite and expands their application for PDS activation in wastewater remediation.     

铁负载污泥炭的表征及其促进PAM调理高级厌氧消化污泥的效能研究

本研究首先分析了铁负载污泥炭的物理化学性质,评估了铁负载污泥炭与有机高分子（聚丙烯酰胺,PAM）联合调理改善高级厌氧消化污泥脱水性的效能,研究了联合调理过程中污泥絮体特性与胞外聚合物（EPS）的变化特征.结果表明,单独投加污泥炭可以通过铁的电中和作用降低污泥颗粒间的静电排斥力,同时充当骨架材料改善污泥的脱水性能.此外,铁负载污泥炭可以有效去除污泥体系中大分子溶解性有机物,从而改善污泥的过滤性能.污泥炭和有机絮凝剂在污泥调理过程中表现出明显的协同作用,污泥碳和PAM的最佳投加量分别为250 mg·g^-1（以TSS计）和8 mg·g^-1（以TSS计）.激光共聚焦显微镜分析表明,PAM主要与污泥絮体中的蛋白质分子作用,从而促使污泥颗粒凝聚.     

芬顿污泥制备磁性生物炭回用于对硝基苯酚的去除及机制

芬顿/絮凝组合工艺在处理难降解有机物废水时会产生大量的芬顿污泥,会提高废水处理成本,同时也会对环境构成威胁,迫切需要开发一种绿色可持续的方法实现芬顿污泥资源化利用.该研究通过将处理PNP(对硝基苯酚)废水产生的芬顿污泥和污水厂生化污泥共热解,原位制备具有高催化活性的MBC(磁性生物炭),并作为多相芬顿催化剂用于去除PNP,实现“以废治废”.结果表明：当芬顿污泥和生化污泥质量比为1∶1、热解温度为800℃时,制备得到的MBC-800-3催化性能最佳;合适的混合比例可有效避免颗粒聚集,高温形成缺陷结构和多种铁相,为MBC-800-3提供了丰富的反应活性位点;当废水初始pH为3、H₂O₂浓度为60 mmol/L、MBC-800-3投加量为0.4 g/L时,PNP和TOC(总有机碳)的去除率均最高,在催化反应100 min时分别达到98%和62%;酸性条件下,MBC活化H₂O₂产生·OH和·O₂-催化降解废水的有机物,其中,·OH作为主要活性物种,其来源包括均相芬顿反应和非均芬顿相反应...     

Feasibility of bioleaching combined with Fenton oxidation to improve sewage sludge dewaterability

A novel joint method of bioleaching with Fenton oxidation was applied to condition sewage sludge. The specific resistance to filtration (SRF) and moisture of sludge cake (MSC) were adopted to evaluate the improvement of sludge dewaterability. After 2-day bioleaching, the sludge pH dropped to about 2.5 which satisfied the acidic condition for Fenton oxidation. Meanwhile, the SRF declined from 6.45 × 10¹⁰ to 2.07 × 10¹⁰ s²/g, and MSC decreased from 91.42% to 87.66%. The bioleached sludge was further conditionedwith Fenton oxidation. From an economical point of view, the optimal dosages of H₂O₂ and Fe2+ were 0.12 and 0.036 mol/L, respectively, and the optimal reaction time was 60 min. Under optimal conditions, SRF, volatile solids reduction, and MSC were 3.43 × 10⁸ s²/g, 36.93%, and 79.58%, respectively. The stability and settleability of sewage sludge were both improved significantly. Besides, the results indicated that bioleaching-Fenton oxidation was more efficient in dewatering the sewage sludge than traditional Fenton oxidation. The sludge conditioningmechanisms by bioleaching-Fenton oxidationmight mainly include the flocculation effects and the releases of extracellular polymeric substances-bound water and intercellular water.     

Feasibility of bioleaching combined with Fenton oxidation to improve sewage sludge dewaterability

A novel joint method of bioleaching with Fenton oxidation was applied to condition sewage sludge. The specific resistance to filtration (SRF) and moisture of sludge cake (MSC) were adopted to evaluate the improvement of sludge dewaterability. After 2-day bioleaching, the sludge pH dropped to about 2.5 which satisfied the acidic condition for Fenton oxidation. Meanwhile, the SRF declined from 6.45 × 10¹⁰ to 2.07 × 10¹⁰ s²/g, and MSC decreased from 91.42% to 87.66%. The bioleached sludge was further conditioned with Fenton oxidation. From an economical point of view, the optimal dosages of H₂O₂ and Fe^2 + were 0.12 and 0.036 mol/L, respectively, and the optimal reaction time was 60 min. Under optimal conditions, SRF, volatile solids reduction, and MSC were 3.43 × 10⁸ s²/g, 36.93%, and 79.58%, respectively. The stability and settleability of sewage sludge were both improved significantly. Besides, the results indicated that bioleaching-Fenton oxidation was more efficient in dewatering the sewage sludge than traditional Fenton oxidation. The sludge conditioning mechanisms by bioleaching-Fenton oxidation might mainly include the flocculation effects and the releases of extracellular polymeric substances–bound water and intercellular water.     

Potassium ferrate pretreatment promotes short chain fatty acids yield and antibiotics reduction in acidogenic fermentation of sewage sludge

During the acidogenic fermentation converting waste activated sludge (WAS) into short-chain fatty acids (SCFA), hydrolysis of complex organic polymers is a limiting step and the transformation of harmful substances (such as antibiotics) during acidogenic fermentation is unknown. In this study, potassium ferrate (K₂FeO₄) oxidation was used as a pretreatment strategy for WAS acidogenic fermentation to increase the hydrolysis of sludge and destruct the harmful antibiotics. Pretreatment with K₂FeO₄ can effectively increase the SCFA production during acidogenic fermentation and change the distribution of SCFA components. With the dosage of 0.2 g/g TS, the maximum SCFA yield was 4823 mg COD/L, which is 28.3 times that of the control group; acetic acid accounts for more than 90% of the total SCFA. The higher dosage (0.5 g/g TS) can further increase the proportion of acetic acid, but inhibit the overall performance of SCFA production. Apart from the promotion of hydrolysis and acidogenesis, K₂FeO₄ pretreatment can also simultaneously oxidizes and degrades part of the antibiotics in the sludge. When the dosage is 0.5 g/g TS, the degradation efficacy of antibiotics is the most significant, and the contents of ofloxacin, azithromycin, and tetracycline in the sludge are reduced by 69%, 42%, and 50%, respectively. In addition, K₂FeO₄ pretreatment can also promote the release of antibiotics from sludge flocs, which is conducive to the simultaneous degradation of antibiotics in the subsequent biological treatment process.     

基于酸化与Fenton试剂处理的焦化污泥脱水过程及其重金属迁移研究

焦化废水污泥作为典型的危险废物,含有氰类、酚类、稠环芳烃与多环芳烃等有毒成分,严重影响人类健康与生态环境安全,焦化污泥减量化是其处理处置中重要一环.针对焦化废水污泥高有机物、高油含量特点,采用酸化+Fenton试剂进行复合调理改性,改性后污泥毛细吸水时间(Capillary Suction Time,CST)、比阻(Specific Resistance to Filtration,SRF)分别达到51.2 s和0.043×10¹³ m·kg^-1,药剂投加量通过响应表面法(Response Surface Method,RSM)进行优化,在实验室板框脱水实验中得到30%硫酸投加量为37.8 mL·L^-1,FeSO₄、H₂O₂和生石灰投加量分别为47.93、34.29和143.21 mg·g^-1DS时,脱水后泥饼含水率为55.82%,滤液pH为6.66,达到污泥深度脱水目标.采用酸化+Fenton试剂复合处理可使焦化废水污泥有效减量化,其良好的深度脱水效果能为后续的无害化处置奠定基础,并有效降低处置费用.     

Porous FeOx/BiVO4-δS0.08：Highly efficient photocatalysts for the degradation of Methylene Blue under visible-light illumination

Porous S-doped bismuth vanadate with an olive-like morphology and its supported iron oxide （y wt.% FeOx/BiVO4-δS0.08, y = 0.06, 0.76, and 1.40） photocatalysts were fabricated using the dodecylamine-assisted alcohol-hydrothermal and incipient wetness impregnation methods, respectively. It is shown that the y wt.% FeOx/BiVO4-δS0.08 photocatalysts contained a monoclinic scheetlite BiVO4 phase with a porous olive-like morphology, a surface area of 8.8-9.2 m^2/g, and a bandgap energy of 2.38-2.42 eV. There was co-presence of surface Bi^5＋, Bi^3＋, V^5＋, V^3＋, Fe^3＋, and Fe^2＋ species in y wt.% FeOx/BiVO4-δS0.08. The 1.40 wt.% FeOx/BiVO4-δS0.08 sample performed the best for Methylene Blue degradation under visible-light illumination. The photocatalytic mechanism was also discussed. We believe that the sulfur and FeOx co-doping, higher oxygen adspecies concentration, and lower baudgap energy were responsible for the excellent visible-light-driven catalytic activity of 1.40 wt.% FeOx/BiVO4-δS0.08.     

Toluene decomposition performance and NOx by-product formation during a DBD-catalyst process

Characteristics of toluene decomposition and formation of nitrogen oxide (NO_x) by-products were investigated in a dielectric barrier discharge (DBD) reactor with/without catalyst at room temperature and atmospheric pressure. Four kinds of metal oxides, i.e., manganese oxide (MnOx), iron oxide (FeOx), cobalt oxide (CoOx) and copper oxide (CuO), supported on Al₂O₃/nickel foam, were used as catalysts. It was found that introducing catalysts could improve toluene removal efficiency, promote decomposition of by-product ozone and enhance CO₂ selectivity. In addition,NO_xwas suppressedwith the decrease of specific energy density (SED) and the increase of humidity, gas flow rate and toluene concentration, or catalyst introduction. Among the four kinds of catalysts, the CuO catalyst showed the best performance in NO_x suppression. The MnOx catalyst exhibited the lowest concentration of O₃ and highest CO₂ selectivity but the highest concentration of NOx. A possible pathway for NOx production in DBD was discussed. The contributions of oxygen active species and hydroxyl radicals are dominant in NOx suppression.     

Fe—C微电解法＋H2O2组合工艺处理硝基苯废水的实验研究

利用废铁屑对硝基苯废水进行预处理,可以使废水中的硝基苯转化为苯胺,然后在废水中加入H2O2,使H2O2与废水中的Fe^2＋构成Fenton试剂,反应生产OH·自由基,OH·自由基具有强烈的氧化性,将苯胺和硝基苯中的苯环打开,形成断链,再进一步将其矿化分解。     

芬顿试剂氧化对污泥脱水性能的影响

利用芬顿试剂调理污泥,以W_C(污泥滤饼含水率)和CST(毛细吸水时间)作为评价污泥脱水性能的指标,通过分析污泥中各层ρ(EPS)(EPS为胞外聚合物)和上清液中小分子有机物质量浓度来阐明污泥脱水性能的变化. 结果表明:芬顿试剂调理可促进EPS氧化分解,TB-EPS(紧密结合的胞外聚合物)破解转化为LB-EPS(松散结合的胞外聚合物)和S-EPS(上清液层胞外聚合物),大幅降低W_C和CST. 试验中当pH为4,w(H₂O₂)和 w(Fe2+)均为40 mg/g时,ρ(EPS)降低了33.04%,W_C和CST分别降至63.36%和28.7 s. Pearson相关性分析表明,ρ(TB-EPS)与W_C和CST均存在显著的正相关性(P＜0.01),是影响污泥脱水性能的重要因素,而ρ(LB-EPS)和ρ(S-EPS)与污泥脱水性能的相关性较低. 液相色谱分析表明,随着芬顿试剂投加量的增大,EPS等有机物分解程度增大,污泥上清液中小分子有机物种类明显增多,其质量浓度显著升高,ρ(甲酸)和ρ(乙酸)分别由原污泥的52.72、15.99 mg/L升至446.05、522.36 mg/L.      

Reuse of Fenton sludge as an iron source for NiFe2O4 synthesis and its application in the Fenton-based process

The potentially hazardous iron-containing sludge from the Fenton process requires proper treatment and disposal, which often results in high treatment cost. In this study, a novel method for the reuse of Fenton sludge as an iron source for the synthesis of nickel ferrite particles(NiFe_2O_4) is proposed. Through a co-precipitation method followed by sintering at 800°C, magnetic NiFe_2O_4 particles were successfully synthesized, which was confirmed by powder X-ray diffraction(XRD), scanning electronic microscopy(SEM), energy dispersive spectroscopy(EDS), Fourier transform infrared spectroscopy(FT-IR) and Raman spectroscopy. The synthesized NiFe_2O_4 could be used as an efficient catalyst in the heterogeneous Fenton process. In phenol degradation with H_2O_2 or NiFe_2O_4 alone, the phenol removal efficiencies within the reaction time of 330 min were as low as 5.9% ± 0.1% and 13.5% ±0.4%, respectively. However, in the presence of both NiFe_2O_4 and H_2O_2, phenol removal efficiency as high as 95% ± 3.4% could be achieved, indicating the excellent catalytic performance of NiFe_2O_4 in the heterogeneous Fenton process. Notably, a rapid electron exchange between_Ni II and_Fe III ions in the NiFe_2O_4 structure could be beneficial for the Fenton reaction. In addition, the magnetic catalyst was relatively stable, highly active and recoverable, and has potential applications in the Fenton process for organic pollutant removal.     

铜铈复合氧化物上石化行业典型VOCs的氧化行为与动力学

采用共沉淀法和等体积浸渍法制备了CuCeO x复合催化剂,对材料的物化性质进行了XRD、低温N2吸脱附、H2-TPR和O2-TPD表征.以石化行业典型VOCs(苯、甲苯和正己烷)为探针污染物,研究了污染物组成与浓度、反应空速、O2浓度、H2O浓度和催化剂种类对其氧化行为的影响,并对反应动力学参数进行了模型拟合.共沉淀得到的催化剂具有均匀的活性相、好的低温可还原性能和较多的活性表面氧物种.甲苯氧化率随着污染物浓度升高而降低,高转化率下苯浓度与其氧化率无相关性,正己烷的氧化率与入口浓度呈正比.苯能够显著抑制甲苯的氧化,而甲苯加入有利于苯的氧化.正己烷对苯氧化的影响较小,但能够促进甲苯的转化,苯系物对正己烷氧化有明显的抑制作用.低空速和高氧浓度都有利于污染物的氧化,氧浓度的变化对正己烷和苯的氧化影响较小.水汽对甲苯的氧化有明显的抑制作用,而对苯和正己烷氧化有明显的促进作用.共沉淀催化剂具有更好的甲苯和苯氧化性能,而无水条件下浸渍催化剂具有更好的正己烷氧化性能.拟一级动力学模型能够很好地模拟不同条件下污染物的氧化行为.