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.     

纳米Fe3O4/CeO2-H2O2非均相类Fenton体系对3,4-二氯三氟甲苯的降解

以浸渍法制备的新型纳米Fe3O4/Ce O2为催化剂,3,4-二氯三氟甲苯(3,4-DCBTE)为目标污染物,在Fe3O4/Ce O2-H2O2非均相类Fenton体系中对目标污染物的降解进行研究,考察催化剂的催化效果和温度、p H、H2O2投加量等因素对催化剂催化效果的影响.结果表明,以纳米Fe3O4/Ce O2作为催化剂的非均相类Fenton体系对3,4-二氯三氟甲苯的处理效果极佳;随着温度的升高,纳米Fe3O4/Ce O2的催化效果不断提高;在偏酸性环境中,p H越低催化效果越好,p H=2时反应去除效率可达96.67%;随着H2O2投加量的增加,3,4-二氯三氟甲苯的降解效率先提高后降低,投加量为15 mg·L-1时去除效果最好可达99.47%;随着催化剂投加量的增加,同样出现了处理效果先升高后降低的现象,投加量为0.5 g·L-1时催化效果最好可达99.64%.在以纳米Fe3O4/Ce O2为催化剂的非均相类Fenton体系中,3,4-二氯三氟甲苯的降解符合一级反应动力学,反应所需活化能较低只需30.26 k J·mol-1.     

二价铁活化过氧化钙提高剩余活性污泥的脱水性能

采用Fe²⁺活化过氧化钙（Fe²⁺/CaO₂）提高剩余污泥的脱水性能,考察初始pH值、Fe²⁺和CaO₂投加量对污泥脱水性能的影响,并进一步探究了实现污泥深度脱水的内在机制.结果表明,初始pH值为中性,Fe²⁺和CaO₂投加量（以VSS计）分别为3.31 mmol·g^-1和3.68 mmol·g^-1时,污泥的脱水效果最好,污泥比阻（SRF）和含水率（W_C）分别由20.99×10¹² m·kg^-1和86.61%降低至3.91×10¹² m·kg^-1和76.15%.Fe²⁺/CaO₂的氧化使污泥微生物细胞裂解,胞内有机物释放,胞外聚合物（EPS）降解;同时,Fe³⁺促使污泥颗粒再絮凝形成致密、多孔的絮体结构,有利于EPS结合水释放,实现污泥深度脱水.从技术和经济角度来看,Fe²⁺/CaO₂工艺经济实用,在提高剩余污泥脱水能力方面具有一定的应用前景.     

Photochemical degradation of nonylphenol in aqueous solution：The impact of pH and hydroxyl radical promoters

The degradation of nonylphenol (NP) in aqueous solution with UV, H₂O₂/UV, and Fenton/photo-Fenton processes was studied. The efficacy of direct and hydrogen peroxide photolysis proved to be dependent on the pH value. The addition of H₂O₂ to UV treatment improved NP degradation. The application of UV photolysis and the H₂O₂/UV system at pH 7 resulted in low pseudo first-order rate constants at 10^-4 sec^-1. In the experiments at elevated pH values the pseudo-first order rate constants increased to 10^-3 sec^-1. The efficacy of the Fenton process was lower in comparison with UV and hydrogen peroxide photolysis. The addition of UV irradiation to the H₂O₂/Fe²⁺ system substantially improved NP degradation efficacy. In terms of performance, the photo-Fenton process was similar to the H₂O₂/UV process. The most favourable process for complete nonylphenol degradation considering both operational cost and treatment efficacy was H₂O₂/UV at pH 11 and 250 mol/L H₂O₂.     

Fe0/海藻酸钙微球还原-Fenton氧化协同降解酸性红B

以海藻酸钠为固定基质制备了Fe~0/海藻酸钙微球,探讨基于Fe~0/海藻酸钙微球对染料还原-Fenton氧化协同降解转化的特性及机制.通过FT-IR、SEM、BET、XPS等方法对材料进行了表征,考察了不同还原氧化体系、Fe~0/海藻酸钙微球投加量、溶液p H等因素对酸性红B(ARB)降解效果的影响,以及Fe~0/海藻酸钙微球还原-氧化过程中Fe~0的稳定性和海藻酸钙微球重复催化性能.结果表明,Fe~0/海藻酸钙微球的多级孔道结构对染料有一定的吸附作用.在Fe~0/海藻酸钙微球还原染料阶段中,Fe~0投加量为0. 24 g·L-1,溶液初始p H为2. 96时,180 min后ARB的色度去除率可达到96. 8%.在后续的Fenton氧化阶段,加入10. 75 mmol·L-1H2O2后,ARB色度去除率达到99%,矿化程度提高至64. 7%.与Fe~0/海藻酸钙微球还原体系和Fe3+/海藻酸钙微球Fenton氧化体系相比,Fe~0/海藻酸钙微球还原-Fenton氧化协同体系能够实现ARB的有效脱色和矿化.由于海藻酸钙中羧基对Fe2+/Fe3+的配位作用,Fe离子从微球中转移到溶液中的量为微球中总铁量的3. 9%左右.由于Fe离子能够较好地固定在海藻酸钙微球中,在p H较高条件下,减少了Fe氢氧化物的生成,Fenton反应能够在较宽p H范围内进行,含有Fe2+/Fe3+的海藻酸钙微球表现出较好的重复催化氧化性能.因此,Fe~0/海藻酸钙微球还原-Fenton氧化协同技术为染料废水的处理提供了一种较好的解决方案.     

One-pot synthesis of Fe/Cu-SSZ-13 catalyst and its highly efficient performance for the selective catalytic reduction of nitrogen oxide with ammonia

Series of Fe/Cu-SSZ-13 catalysts with different Fe loading content were synthesized by simple one-pot strategy. The obtained catalysts were subjected to selective catalytic reduction (SCR) of NO_x with NH₃ and were characterized by various techniques. The results show that Fe_0.63/Cu_1.50-SSZ-13 catalyst with proper Fe content exhibits excellent catalytic activity with widest operation temperature window from 160 to 580°C, excellent hydrothermal stability as well as good resistance to sulfur poisoning when compared with Cu-SSZ-13, signifying its great potential for practical applications. Further characterizations reveal that the synthesized Fe/Cu-SSZ-13 catalysts present typical chabazite (CHA) structure with good crystallinity, while isolated Cu²⁺ and monomeric Fe³⁺ are revealed as the predominant copper and iron species. At low temperatures, isolated Cu²⁺ species act as primary active sites for SCR reaction, while monomeric Fe³⁺ species provide sufficient active sites for sustain the SCR activity at high temperature. Moreover, Fe over doping would lead to the damage of zeolite structure, destruction of isolated Cu²⁺ site, as well as the formation of highly oxidizing Fe₂O₃, thus causing deterioration of catalytic performances.     

双极电化学氧化降解水中苯胺

采用钛基氧化物涂层材料（Ti/SnO2-Sb2O5）为阳极,石墨为阴极,在含Fe2＋和不含Fe2＋2种电解质条件下研究了苯胺的电化学氧化降解效率和机制.结果表明,Ti/SnO2-Sb2O5阳极氧化降解有机物的电位约2.0 V±0.1 V,而石墨阴极还原O2生成H2 O2的优化电位为-0.65 V.H2 O2单独作用不能...     

类芬顿调理污泥用于微生物电解池产氢与磷回收的研究

为提高微生物电解池(MEC)利用剩余污泥产氢气和磷回收的效率,采用Fe~(3+)、原儿茶酸(PCA)和H_2O_2体系预调理污泥,探究中性PCA/Fe~(3+)/H_2O_2体系的试剂投加量对污泥液相总磷含量和溶解性化学需氧量(SCOD)的影响.在单因素试验的基础上,通过表面响应法(RSM)优化得到Fe~(3+)和H_2O_2投加量分别为12.96 mmol·L~(-1)和0.45 mol·L~(-1),液相总磷含量和SCOD含量实际值分别为(60.14±0.08) mg·L~(-1)和(3357.67±66.37) mg·L~(-1),模拟效果显著.与未处理的剩余污泥MEC反应器出水相比,经过调理后的剩余污泥MEC反应器出水中的总化学需氧量(TCOD)、多糖和蛋白质的去除率分别提高了30.03%、50.16%和97.31%,氢气转化率提升了1.31倍,有效提升了MEC产氢效率.通过鸟粪石结晶回收MEC污泥上清液中的磷,发现在初始pH值为10、Mg~(2+)浓度为0.056 mol·L~(-1)和NH~+_4浓度为0.08 mol·L~(-1)时效果最佳.鸟粪石晶体质量浓度最高可达7.6 g·L~(-1),晶体纯度最大为88.30%,上清液中77.55%的磷以鸟粪石的形式得到回收.在本研究最优化条件下进行中性PCA/Fe~(3+)/H_2O_2体系调理剩余污泥微生物电解池产氢与磷回收全过程中产出经济价值达到2.36元.实验研究最终表明,经过Fe~(3+)/PCA/H_2O_2体系调理污泥可促进污泥中磷的释放和MEC处理污泥的产氢效率,为探究污泥资源化提供了新的研究思路.     

Enhanced dewaterability of waste activated sludge by UV assisted ZVI-PDS oxidation

Ultraviolet（UV） assisted zero-valent iron（ZVI）-activated sodium persulfate（PDS） oxidation（UV-ZVI-PDS） was used to treat waste activated sludge（WAS） in this study.The dewaterability performance and mechanism of WAS dewatering were analyzed.The results showed that UV-ZVI-PDS can obtain better sludge dewatering performance in a wide pH range（2.0-8.0）.When the molar ratio of ZVI/PDS was 0.6,UV was 254 nm,PDS dosage was 200 mg/g TS（total solid）,pH was 6.54,reaction time was 20 min,the CST（capillary s...     

Photodegradation of amoxicillin by catalyzed Fe3+/H2O2 process

Three oxidation processes of UV-Fe³⁺(EDTA)/H₂O₂ (UV: ultraviolet light; EDTA: ethylenediaminetetraacetic acid), UV-Fe³⁺/H₂O₂ and Fe³⁺/H₂O₂ were simultaneously investigated for the degradation of amoxicillin at pH 7.0. The results indicated that, 100% amoxicillin degradation and 81.9% chemical oxygen demand (COD_Cr) removal could be achieved in the UV-Fe³⁺ (EDTA)/H₂O₂ process. The treatment efficiency of amoxicillin and COD_Cr removal were found to decrease to 59.0% and 43.0% in the UV-Fe³⁺/H₂O₂ process; 39.6% and 31.3% in the Fe³⁺/H₂O₂ process. Moreover, the results of biodegradability (biological oxygen demand (BOD₅)/COD_Cr ratio) revealed that the UV-Fe³⁺ (EDTA)/H₂O₂ process was a promising strategy to degrade amoxicillin as the biodegradability of the effluent was improved to 0.45, compared with the cases of UV-Fe³⁺/H₂O₂ (0.25) and Fe³⁺/H₂O₂ (0.10) processes. Therefore, it could be deduced that EDTA and UV light performed synergetic catalytic effect on the Fe³⁺/H₂O₂ process, enhancing the treatment efficiency. The degradation mechanisms were also investigated via UV-Vis spectra, and high performance liquid chromatography-mass spectra. The degradation pathway of amoxicillin was further proposed.     

Ce3+与Cu2+协同强化芬顿体系氧化苯酚的效能与机制研究

研究了Ce~(3+)与Cu~(2+)协同强化芬顿体系在不同初始条件下对水中苯酚的氧化效能与机制.结果表明,在p H适用范围的宽度和H_2O_2浓度变化方面,Ce~(3+)/Cu~(2+)/Fe~(2+)/H_2O_2体系比传统的芬顿体系更具有优势,该体系在p H=5.0、H_2O_2浓度为2.0mmol·L-1的条件下,仍可以对苯酚保持相对较高的氧化效能;Cu~(2+)可能会借助反应过程中的中间产物(醌类物质)生成Cu+,Cu+催化H_2O_2分解生成·OH,Ce~(3+)可能促进体系内醌类物质的形成,加快Fe~(3+)与Fe~(2+)的循环效能,在一定程度上提高了芬顿体系中H_2O_2分解生成·OH的速率,说明Cu~(2+)与Ce~(3+)对芬顿体系的强化作用具有协同性;自由基终止剂依然可以抑制Ce~(3+)、Cu~(2+)强化的芬顿体系对苯酚的降解,由此说明体系中起到氧化作用的活性物种仍然是羟基自由基(·OH).     

树脂负载草酸铁光助类芬顿降解水中孔雀石绿

为了强化多相类芬顿反应的速率,在可见光下采用以草酸盐为配体的三价铁草酸络合物(Fe~(3+)C_2O_4/R)为催化剂催化过氧化氢降解水中孔雀石绿.结果表明,与Fe~(3+)/R相比催化剂Fe~(3+)C_2O_4/R具有更强的催化活性,能强化羟基自由基(·OH)的产生. 过氧化氢的初始浓度越高,反应速率越快,反应遵循一级反应动力学,反应速率常数与过氧化氢浓度具有很好的相关性.在pH值3～9的范围内,催化剂Fe~(3+)C_2O_4/R都能有效地对MG进行降解,最佳pH值为6.随着催化剂投量的增加,MG的去除效率明显提高.随着MG初始浓度的增加,MG的去除也由吸附为主转化为以氧化为主,但总体影响不大.催化剂重复使用后仍然具有较好的催化活性,说明铁在树脂表面负载比较牢固,催化剂具有反复使用的能力.反应中的氧化活性物种是羟基自由基和高价态铁同时共存.     

Kinetics and corrosion products of aqueous nitrate reduction by iron powder without reaction conditions control

Although considerable research has been conducted on nitrate reduction by zero-valent iron powder (Fe0), these studies were mostly operated under anaerobic conditions with invariable pH that was unsuitable for practical application. Without reaction conditions (dissolved oxygen or reaction pH) control, this work aimed at subjecting the kinetics of denitrification by microscale Fe0 (160–200 mesh) to analysis the factors affecting the denitrification of nitrate and the composition of iron reductive products c...     

Electrolyte effects on aqueous atmospheric oxidation of sulphur dioxide by hydrogen peroxide

The rate of oxidation of sulphur dioxide by hydrogen peroxide in the presence of various supporting electrolytes has been determined by the stopped flow method. In a sodium perchlorate medium (chosen as reference electrolyte) first-order kinetics were observed with respect to HSO₃⁻, H₂O₂ and H⁺. The influence of the ionic strength was investigated and the third-order rate constant was calculated at infinite dilution. The rate constants of the reaction are shown to be far higher when chloride or ammonium ions are added to the solution.The effect of temperature and traces of metals ions (Mn²⁺, Fe²⁺, Fe³, Cu²⁺, Cr³⁺) was studied. The oxidation reaction is virtually insensitive to the effects of Mn²⁺, Fe³⁺, Cu²⁺ and Cr³⁺. Catalytic activity is observed with Fe²⁺.     

Decontamination of alachlor herbicide wastewater by a continuous dosing mode ultrasound/Fe2+/H2O2 process

We used a ultrasound/Fe2+/H2O2 process in continuous dosing mode to degrade the alachlor.Experimental results indicated that lower pH levels enhanced the degradation and mineralization of alachlor. The maximum alachlor degradation(initial alachlor concentration of 50 mg/L) was as high as 100% at pH 3 with ultrasound of 100 Watts, 20 mg/L of Fe2+, 2 mg/min of H2O2 and 20℃ within60 min reaction combined with 46.8% total organic carbon removal. Higher reaction temperatures inhibited the degradation of alachlor. Adequate dosages of Fe2+and H2O2 in ultrasound/Fe2+/H2O2process not only enhance the degradation efficiency of alachlor but also save the operational cost than the sole ultrasound or Fenton process. A continuous dosing mode ultrasound/Fe2+/H2O2 process was proven as an effective method to degrade the alachlor.     

Effect of Al2O3 doping on the structure and performance of an Al2O3/Fe2O3 catalyst for mercury oxidation

In this study,the thermal stability of a Fe_2 O_3 catalyst for mercury oxidation was significantly improved by doping with Al_2 O_3.After 1 hr,the catalyst doped with 10 wt.% Al_2 O_3 still exhibited a mercury conversion efficiency of 70.9%,while the undoped sample even lost its catalytic activity.Doping with Al_2 O_3 retarded the collapse of the catalyst mesoporous structure during high-temperature calcination,and the doped samples maintained a higher specific surface area,smaller pore size,and narrower pore size distribution.Transmission electron microscope images revealed that after calcination at 350℃,the average size of the catalyst grains in Fe_2 O_3 was 23.4 nm;however,the corresponding values for 1%Al_2 O_3/Fe_2 O_3,3%Al_2 O_3/Fe_2 O_3,and 10%Al_2 O_3/Fe_2 O_3 were only 13.3,7.1,and 4.7 nm,respectively.Results obtained from X-ray diffraction and thermogravimetry coupled with differential scanning calorimetry confirmed that doping with Al_2 O_3 also retards the crystallization of the catalysts at high temperature,constraining catalyst grains to a smaller size.     

缺氧酸化联合零价铁-过氧化氢改善污泥脱水性能的研究

为探讨缺氧酸化联合零价铁(ZVI)-过氧化氢(H_2O_2)调理对污泥脱水性能的影响,本文通过单因素试验,以污泥比阻(SRF)作为参考指标,系统考察了调理条件对污泥脱水性能的影响.同时,在试验的最佳调理条件下,分析了污泥各层胞外聚合物(EPS)有机物质量浓度及荧光光谱强度以阐明该联合作用机理.结果表明,当初始pH为2,ZVI投加量为280 mg·g~(-1)(以干污泥量(DS)计,下同),缺氧时间为4 h,H_2O_2投加量为30 mg·g~(-1)(以DS计,下同),类芬顿反应时间为10 min时,SRF降低了90.39%,处理效果较单独类芬顿处理提升了1倍.机理探究试验表明,在缺氧条件下,酸化处理可加速污泥的水解,溶解得到更多的二价铁离子,促使EPS结构发生改变;ZVI-H_2O_2调理可有效地氧化部分EPS,使得紧密结合胞外聚合物(TB-EPS)破解转化至松散结合胞外聚合物(LB-EPS)和上清液胞外聚合物(SB-EPS).EPS分析结果表明,蛋白质的减少能有效提高污泥脱水性能,腐殖酸和富里酸类有机物的产生能提高污泥疏水性能.此外,ZVI的再次利用效率高,重复利用仍能使SRF降低率达到82.04%.因此,缺氧酸化联合ZVI-H_2O_2处理能实现污泥的水解、氧化和絮凝过程,达到改善污泥脱水性能的目的.     

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.      

厌氧氨氧化污泥中氨氧化的潜在电子受体

通过接种亚硝酸盐型厌氧氨氧化污泥,投加潜在电子受体(亚硝酸盐、Fe~(3+)和硫酸盐)研究了厌氧条件下氨氮氧化的潜在电子受体.结果表明,亚硝酸盐是厌氧氨氧化最适合的电子受体,能够与氨氮在短暂的时间内完全反应;在亚硝酸盐缺乏的情况下,厌氧氨氧化污泥中微生物利用自身细胞有机物将产物硝酸盐转化为亚硝酸盐参与氨氮转化;Fe~(3+)与硫酸盐在氨氮氧化后期出现转化,但是直接还是间接参与还需进一步研究.厌氧氨氧化污泥对氨氮产生过量氧化之前必须以亚硝酸盐为电子受体进行微生物活性激活,并且好氧氨氧化菌和亚硝化菌出现增长,推测微生物产生了H_2O_2.该现象并不可长久持续.虽然其氧化速率较慢,但是过量氧化现象较为明显.因此厌氧氨氧化污泥中肯定存在氨氮过量氧化的现象.厌氧氨氧化污泥对电子的利用顺序是亚硝酸盐、硝酸盐、Fe~(3+)和硫酸盐.     

Fe/Zn-TMS体系吸收去除催化裂化干气中H2S的性能

本研究采用FeCl3·6H2O、ZnCl2和环丁砜(TMS)复配形成的Fe/Zn-TMS体系脱除催化裂化(FCC)干气中的H2S,并用30%H2O2氧化再生Fe/Zn-TMS体系.同时,研究了各活性成分比例、吸收液体积浓度、吸收液pH值等对脱硫效率的影响,以及H2O2用量、吸收富液pH值对Fe2+氧化率的影响.结果表明,n(FeCl3·6H2O)∶n(ZnCl2)∶n(TMS)为0.45∶0.55∶1,吸收液pH为0.75,体积浓度(W)为50%的条件下能长时间高效脱硫,最高脱硫率达99.9%;在n(Fe2+)∶n(H2O2)为2∶1,吸收富液pH为0.65的条件下,Fe2+氧化率达96.7%.体系可循环使用3次,且能耗低、操作简单.