活性焦和活性炭负载纳米铁处理TNT红水中的二硝基甲苯磺酸钠

以活性焦和活性炭为载体,采用液相还原法制备了负载纳米铁,比较了两种负载纳米铁对TNT红水中难降解物质二硝基甲苯磺酸钠(包括2,4-DNT-3-SO3Na和2,4-DNT-5-SO3Na)的去除能力。实验结果表明,作为负载材料活性焦的相对有效比表面积与孔体积要优于活性炭,而且有利于更好地发挥出负载纳米铁的优势。单位面积活性焦负载纳米铁去除2,4-DNT-5-SO3Na的能力明显高于活性炭负载纳米铁,单位面积活性焦负载纳米铁去除2,4-DNT-3-SO3Na的能力在较小投加量条件下高于活性炭负载纳米铁,但均随投加量的增加而下降;而对于活性炭负载纳米铁,其单位面积去除能力基本不受投加量的影响,而且对二硝基甲苯磺酸钠的去除率高于活性焦负载纳米铁。耦合混凝沉淀的总去除效果表明,单位面活性焦负载纳米铁对2,4-DNT-5-SO3Na的去除能力高于活性炭负载纳米铁,而对2,4-DNT-3-SO3Na的去除能力则低于活性炭负载纳米铁。     

纳米零价铁的制备及其去除水中对氯硝基苯的研究

通过FeSO4与KBH4反应,利用液相还原法制备纳米零价铁颗粒(NZVI),用XRD、SEM和BET对其性能进行表征。在常温常压下利用纳米铁还原废水中的对氯硝基苯(p-CNB),探讨了反应条件对还原率的影响。结果表明,制备过程中碱性物质(NaOH)的添加可以明显减小颗粒粒径,增大比表面积,提高纳米铁还原反应的效率。NZVI对于对氯硝基苯有很好的去除效果,NZVI用量、p-CNB初始浓度和pH值均对其去除效率产生影响。在纳米铁投加量为1 g/L,pH=2的条件下,添加NaOH的纳米铁能在120 min内将质量浓度为50 mg/L的对氯硝基苯基本完全降解,降解率为98.8%。此外,还对NZVI还原对氯硝基苯的机理进行了初步探讨。     

Effect of ethylenediamine-N,N′-disuccinic acid on Fenton and photo-Fenton processes using goethite as an iron source: optimization of parameters for bisphenol A degradation

The main disadvantage of using iron mineral in Fenton-like reactions is that the decomposition rate of organic contaminants is slower than in classic Fenton reaction using ferrous ions at acidic pH. In order to overcome these drawbacks of the Fenton process, chelating agents have been used in the investigation of Fenton heterogeneous reaction with some Fe-bearing minerals. In this work, the effect of new iron complexing agent, ethylenediamine-N,N'-disuccinic acid (EDDS), on heterogeneous Fenton and photo-Fenton system using goethite as an iron source was tested at circumneutral pH. Batch experiments including adsorption of EDDS and bisphenol A (BPA) on goethite, H₂O₂ decomposition, dissolved iron measurement, and BPA degradation were conducted. The effects of pH, H₂O₂ concentration, EDDS concentration, and goethite dose were studied, and the production of hydroxyl radical (^?OH) was detected. The addition of EDDS inhibited the heterogeneous Fenton degradation of BPA but also the formation of ^?OH. The presence of EDDS decreases the reactivity of goethite toward H₂O₂ because EDDS adsorbs strongly onto the goethite surface and alters catalytic sites. However, the addition of EDDS can improve the heterogeneous photo-Fenton degradation of BPA through the propagation into homogeneous reaction and formation of photochemically efficient Fe-EDDS complex. The overall effect of EDDS is dependent on the H₂O₂ and EDDS concentrations and pH value. The high performance observed at pH 6.2 could be explained by the ability of O ₂ ^?? to generate Fe(II) species from Fe(III) reduction. Low concentrations of H₂O₂ (0.1 mM) and EDDS (0.1 mM) were required as optimal conditions for complete BPA removal. These findings regarding the capability of EDDS/goethite system to promote heterogeneous photo-Fenton oxidation have important practical implications for water treatment technologies.     

沼渣生物炭基Fenton催化剂的制备及其高效降解吡虫啉农药废水的研究

以废弃物沼渣和含铁剩余污泥为原料,采用一步热解法制备沼渣生物炭基Fenton催化剂(以下简称催化剂),构建了非均相Fenton反应体系处理含吡虫啉模拟废水,考察了H2 O2和催化剂用量对吡虫啉去除率的影响.结果表明,非均相Fenton反应体系中,H2 O2最佳投加量为0.50 g/L,催化剂最佳投加量为1.00 g/L...     

Enhanced removal of pentachlorophenol by a novel composite: nanoscale zero valent iron immobilized on organobentonite

Nanoscale zero valent iron (NZVI) was immobilized on the organobentonite (CTMA-bent), so as to enhance the reactivity of NZVI and prevent its aggregation. This novel composite (NZVI/CTMA-Bent) was characterized by transmission electron microscope and X-ray diffraction. Good dispersion of NZVI particles on the bentonite was observed. Its performance on removing pentachlorophenol (PCP) was investigated by batch experiments. Results showed NZVI/CTMA-Bent could rapidly and completely dechlorinate PCP to phenol with an efficiency of 96.2%. It was higher than the sum (54.5%) of reduction by NZVI (31.5%) and adsorption by CTMA-Bent (23.0%) separately. The kinetic studies indicated the removal rate of PCP was positively related to the adsorption. We proposed that the adsorption of PCP by CTMA-Bent enhanced the mass transfer of PCP from aqueous to iron surface. Besides, NZVI/CTMA-Bent exhibited good stability and reusability, and CTMA-Bent could also reduce the amount of iron ions released into the solution.     

非均相UV/Fenton氧化法降解水中六氯苯的研究

采用超声辐照促进浸渍法制备了非均相UV/Fenton催化剂Fe/Al2O3,并对其进行了表征.以制备的催化剂对水中六氯苯进行非均相UV/Fenton法氧化降解.考察了铁的负载量、初始pH、H2O2投加量、催化剂投加量和反应时间对六氯苯降解效果的影响,并探讨了六氯苯的降解动力学规律.结果表明,制备的催化剂表面活性组分分散均匀,对六氯苯具有较高的催化活性和重复利用性.非均相UV/Fenton法降解六氯苯的最佳实验条件为:铁的负载量为2%,废水初始pH为3,H2O2和Fe/Al2O3催化剂的投加量分别为34 mg/L和150 mg/L,反应时间为20 min.在此条件下,浓度为500μg/L的六氯苯降解效率达94.5%.HCB的降解反应动力学规律可用Langmuir-Hinshwood方程很好地描述.六氯苯在催化剂表面的吸附常数为1.962 L/mg,表面反应速率常数为0.08 mg/(L·min).     

微波诱导AC/Cu、AC/Fe催化非均相Fenton 反应催化降解垃圾渗滤液

采用活性炭载体负载Cu、Fe为催化剂,在微波诱导作用下,对垃圾渗滤液污染物进行降解。实验结果表明,活性炭负载金属前经适当浓度硝酸浸泡处理后,催化剂对COD去除率提高可超过15%,过高硝酸盐浓度对COD去除有不利影响;催化剂对COD去除率随Cu、Fe金属负载量增加呈先增加后降低的趋势,催化剂对Cu、Fe的最佳负载量分别为质量百分比2.11%和1.12%。对于AC-Cu体系,在初始pH=3,H2O2投加量为4.98×103mg/L,催化剂用量为5.0×103mg/L,420 W功率下微波辐射10 min时,垃圾渗滤液COD去除率可达到84.13%;对于AC-Fe体系,当H2O2投加量为0.33×103mg/L,催化剂AC-Fe用量为2.0×104mg/L,420 W功率下微波作用10 min时,垃圾渗滤液COD去除率为60.16%。分析2种催化剂对COD去除差异的原因,可能是催化剂AC-Cu表面单分子分布的阈值比AC-Fe高。降解液的pH值对AC-Cu体系、AC-Fe体系COD去除影响存在拐点,最高COD去除率点对应的降解液pH值为3。微波辐射功率较低时,体系COD去除率随辐射功率增加而增加;辐射功率较高时,高温下垃圾渗滤液中有机硫化物分解成小分子硫化物,对催化剂活性存在一定抑制作用。     

Synthesis of nanoscale zero-valent iron/ordered mesoporous carbon for adsorption and synergistic reduction of nitrobenzene

Nanoscale zero-valent iron (NZVI) supported on ordered mesoporous carbon (OMC) was synthesized through liquid phase reduction route. The NZVI/OMC composite was characterized by X-ray diffraction, N(2) adsorption/desorption and transmission electron microscopy. Results reveal that the composite possesses ordered mesostructure with NZVI distributing homogeneously on the surface of OMC support. The removal effects of nitrobenzene (NB) in water with OMC, NZVI/OMC and non-supported NZVI were evaluated. Results indicate that NZVI/OMC shows enhanced removal efficiency, which is attributed to its adsorption and synergistic reduction for NB. The transformation process of NB was further investigated by HPLC. Nitrosobenzene and phenylhydroxylamine were detected as intermediate products and aniline was the final reductive product.     

Heterogeneous Fenton oxidation of Direct Black G in dye effluent using functional kaolin-supported nanoscale zero iron

This study investigated kaolin-supported nanoscale zero-valent iron (nZVI/K) as a heterogeneous Fenton-like catalyst for the adsorption and oxidation of an azo dye, Direct Black G (DBG). New findings suggest that kaolin as a support material not only reduced the aggregation of nanoscale zero-valent iron (nZVI) but also improved the adsorption of DBG. It consequently improved Fenton oxidation by increasing the local concentration of DBG in the vicinity of nZVI. This was confirmed by scanning electron microscopy and X-ray diffraction for the surface morphology of nZVI/K before and after the Fenton-like reaction. Furthermore, nZVI/K proved to be a catalyst for the heterogeneous Fenton-like oxidation of the DBG process in the neutral pH range. More than 87.22 % of DBG was degraded, and 54.60 % of total organic carbon was removed in the optimal conditions: 0.6 g/L dosage of nZVI/K, 33 mM H₂O₂, 100 mg/L initial DBG concentration, temperature of 303 K and pH of 7.06. Finally, it was demonstrated that nZVI/K removed DBG from dye wastewater through the processes of adsorption and oxidation.     

非均相Fenton和非均相US-Fenton体系中甲基橙降解动力学

在初始pH=3的条件下研究了甲基橙在非均相Fenton体系和非均相US-Fenton体系中的降解动力学。研究内容包括表观动力学方程和活化能。研究表明,超声的引入可以提高甲基橙的降解效率和降解速率。对比非均相Fenton和非均相US-Fenton体系中的表观动力学方程表明超声的引入可以提高反应速率常数,此外,还可以提高H2O2的利用率。通过对比分析,超声的引入可以降低反应所需的活化能,在超声的存在下,甲基橙的氧化活化能为25.12 kJ/mol,而在没有超声的条件下,需要的活化能为41.49 kJ/mol。     

Microbial reduction of nitrate in the presence of nanoscale zero-valent iron

Microbial reduction of nitrate in the presence of nanoscale zero-valent iron (NZVI) was evaluated to assess the feasibility of employing NZVI in the biological nitrate treatment. Nitrate was completely reduced within 3 d in a nanoscale Fe(0)-cell reactor, while only 50% of the nitrate was abiotically reduced over 7 d at 25 °C. The removal rate of nitrate in the integrated NZVI-cell system was unaffected by the presence of high amounts of sulfate. Efficient removal of nitrate by Fe(II)-supported anaerobic culture in 14 d indicated that Fe(II), which is produced during anaerobic iron corrosion in the Fe(0)-cell system, might act as an electron donor for nitrate. Unlike abiotic reduction, microbial reduction of nitrate was not significantly affected by low temperature conditions. This study demonstrated the potential applicability of employing NZVI iron as a source of electrons for biological nitrate reduction. Use of NZVI for microbial nitrate reduction can obviate the disadvantages associated with traditional biological denitrification, that relies on the use of organic substrates or explosive hydrogen gas, and maintain the advantages offered by nano-particle technology such as higher surface reactivity and functionality in suspensions.     

铁碳微电解-Fenton法预处理苯胺基乙腈生产废水

采用铁碳微电解-Fenton法对苯胺基乙腈生产废水进行预处理实验。通过静态实验确定铁碳微电解最佳条件为铁屑投加量300 g/L,Fe/C质量比为2∶3,反应75 min,不需要调节进水pH;Fenton反应最佳条件为铁碳微电解出水pH=4,30%H2O2投加量15 mL/L,在搅拌条件下反应60 min;然后沉淀反应时调节pH为9,混凝沉淀75 min。在上述条件下通过动态实验得到系统连续反应在48 h内废水的COD和苯胺去除率在50%和70%以上,可生化性BOD5/COD也保持在0.3以上,为后续生物处理创造了良好条件。     

Magnetite/mesocellular carbon foam as a magnetically recoverable fenton catalyst for removal of phenol and arsenic

A magnetite-loaded mesocellular carbonaceous material, Fe₃O₄/MSU-F-C, exhibited superior activity as both a Fenton catalyst and an adsorbent for removal of phenol and arsenic, and strong magnetic property rendering it separable by simply applying magnetic field. In the presence of hydrogen peroxide, the catalytic process by Fe₃O₄/MSU-F-C completely oxidized phenol and As(III) under the conditions where commercial iron oxides showed negligible effects. Notably, the decomposition of H₂O₂ by Fe₃O₄/MSU-F-C was not faster than those by commercial iron oxides, indicating that hydroxyl radical produced via the catalytic process by Fe₃O₄/MSU-F-C was used more efficiently for the oxidation of target contaminants compared to the other iron oxides. The homogeneous Fenton reaction by the dissolved iron species eluted from Fe₃O₄/MSU-F-C was insignificant. At relatively high doses of Fe₃O₄/MSU-F-C, total concentration of arsenic decreased to a significant extent due to the adsorption of arsenic on the catalyst surface. The removal of arsenic by adsorption was found to proceed via preoxidation of As(III) into As(V) and the subsequent adsorption of As(V) onto the catalyst.     

Fe(III)–EDDS complex in Fenton and photo-Fenton processes: from the radical formation to the degradation of a target compound

The present work compares the efficiency of homogenous Fenton and photo-Fenton processes in the presence of Fe(III)–EDDS complex under different experimental conditions. 4-tert-Butylphenol (4-t-BP), which is one of the endocrine disrupting chemicals, was used as a model pollutant to investigate the Fenton and photo-Fenton application. The efficiency of homogenous photo-Fenton process was significantly much higher than homogenous Fenton process, which is due to the rapid formation of Fe²⁺ under UV irradiation of the iron complex and the photochemical formation of HO^? from the photolysis of the complex Fe(III)–EDDS. Through the degradation of 4-t-BP, the effect of Fe(III)–EDDS concentration, H₂O₂ concentration, pH, and oxygen was investigated in both processes. Such trend was also correlated with pH calculating the polychromatic Fe²⁺ quantum yield formation at pH 4.0, 6.0, and 8.6. The results showed that at high Fe(III)–EDDS and H₂O₂ concentrations, a negative effect was found. By the way, the Fenton process was found to be enhanced at basic pH. These results can be very useful for the use and optimization of such iron complex in water treatment process as function of different physico-chemical conditions.     

Selective redox degradation of chlorinated aliphatic compounds by Fenton reaction in pyrite suspension

Selective redox degradation of chlorinated aliphatics by Fenton reaction in pyrite suspension was investigated in a closed system. Carbon tetrachloride (CT) was used as a representative target of perchlorinated alkanes and trichloroethylene (TCE) was used as one of highly chlorinated alkenes. Degradation of CT in Fenton reaction was significantly enhanced by pyrite used as an iron source instead of soluble Fe. Pyrite Fenton showed 93% of CT removal in 140 min, while Fenton reaction with soluble Fe(II) showed 52% and that with Fe(III) 15%. Addition of 2-propanol to the pyrite Fenton system significantly inhibited degradation of TCE (99% to 44% of TCE removal), while degradation of CT was slightly improved by the 2-propanol addition (80-91% of CT removal). The result suggests that, unlike oxidative degradation of TCE by hydroxyl radical in pyrite Fenton system, an oxidation by the hydroxyl radical is not a main degradation mechanism for the degradation of CT in pyrite Fenton system but a reductive dechlorination by superoxide can rather be the one for the CT degradation. The degradation kinetics of CT in the pyrite Fenton system was decelerated (0.13-0.03 min⁻¹), as initial suspension pH decreased from 3 to 2. The formation of superoxide during the CT degradation in the pyrite Fenton system was observed by electron spin resonance spectroscopy. The formation at initial pH 3 was greater than that at initial pH 2, which supported that superoxide was a main reductant for degradation of CT in the pyrite Fenton system.     

Influence of operational key parameters on the photocatalytic decolorization of Rhodamine B dye using Fe2+/H2O2/Nb2O5/UV system

The present research deals with the development of a new heterogeneous photocatalysis and Fenton hybrid system for the removal of color from textile dyeing wastewater as Rhodamine B (RhB) solutions by using Fe²⁺/H₂O₂/Nb₂O₅ as a photocatalytic system. The application of this photocatalytic system for the decolorization of dye contaminants is not reported in the literature yet. Different parameters like dye concentration, Nb₂O₅/Fe²⁺ catalyst amount, pH, and H₂O₂ concentration have been studied. The optimum conditions for the decolorization of the dye were initial concentration of 10 mg L^?1 of dye, pH 4, and Nb₂O₅/Fe²⁺ catalyst concentration of 0.5 g L^?1/50 mg L^?1. The optimum value of H₂O₂ concentration for the conditions used in this study was 700 mg L^?1. Moreover, the efficiency of the Nb₂O₅/photo-Fenton hybrid process in comparison to photo-Fenton alone and a dark Fenton process as a control experiment to decolorize the RhB solution has been investigated. The combination of photo-Fenton and Nb₂O₅ catalysts has been proved to be the most effective for the treatment of such type of wastewaters. The results revealed that the RhB dye was decolorized in a higher percent (78 %) by the Nb₂O₅/photo-Fenton hybrid process (Fe²⁺/H₂O₂/Nb₂O₅/UV) than by the photo-Fenton process alone (37 %) and dark Fenton process (14 %) after 120 min of treatment. Moreover, the Nb₂O₅ catalyst as a heterogeneous part of the photocatalytic system was demonstrated to have good stability and reusability.     

微电解-Fenton联合工艺预处理煤层气井压裂废水

利用Fenton强化微电解工艺对煤层气井压裂废水展开预处理研究,以COD去除率和可生化性(B/C)为考察指标,单独工艺正交实验结果表明pH为3、反应时间为90 min、铁碳体积比为1.5∶1和pH为4、反应时间为80 min、H2O2投加量为4 mL/L分别是微电解与Fenton反应的最优条件,各可获得48.1%和44.9%的COD去除率。在最优条件下进行微电解-Fenton联合运行实验,连续61 h内COD去除率均稳定在65%以上,B/C由0.158上升到0.3以上,有利于后续生化处理的运行。     

Fe/活性炭多相类Fenton法湿式氧化罗丹明B废水的研究

采用自制的Fe/活性炭（Fe/AC）为催化剂,H₂O₂为氧化剂,组成多相类Fenton试剂催化降解罗丹明B染料废水。实验结果表明,在催化剂加入量为0.8 g/L,H₂O₂体积分数为0.3%,废水pH值为13,反应时间为30 min的条件下,质量浓度为200 mg/L的罗丹明B染料废水的脱色率达100%。反应动力学研究表明,罗丹明B脱色反应近似为一级反应,30℃时反应速率常数为0.02675 min^-1,表观活化能为69.47 kJ/mol。     

Heterogeneous Fenton degradation of bisphenol A catalyzed by efficient adsorptive Fe3O4/GO nanocomposites

A new method for the degradation of bisphenol A (BPA) in aqueous solution was developed. The oxidative degradation characteristics of BPA in a heterogeneous Fenton reaction catalyzed by Fe₃O₄/graphite oxide (GO) were studied. Transmission electron microscopic images showed that the Fe₃O₄ nanoparticles were evenly distributed and were ～6 nm in diameter. Experimental results suggested that BPA conversion was affected by several factors, such as the loading amount of Fe₃O₄/GO, pH, and initial H₂O₂ concentration. In the system with 1.0 g L^?1 of Fe₃O₄/GO and 20 mmol L^?1 of H₂O₂, almost 90 % of BPA (20 mg L^?1) was degraded within 6 h at pH 6.0. Based on the degradation products identified by GC–MS, the degradation pathways of BPA were proposed. In addition, the reused catalyst Fe₃O₄/GO still retained its catalytic activity after three cycles, indicating that Fe₃O₄/GO had good stability and reusability. These results demonstrated that the heterogeneous Fenton reaction catalyzed by Fe₃O₄/GO is a promising advanced oxidation technology for the treatment of wastewater containing BPA.     

Reduction of dinitrotoluene sulfonates in TNT red water using nanoscale zerovalent iron particles

Purpose

This research was designed to investigate the feasibility of converting the dinitrotoluene sulfonates (DNTS) in TNT red water into the corresponding aromatic amino compounds using nanoscale zerovalent iron (NZVI).

Methods

NZVI particles were simultaneously synthesized and stabilized by sodium borohydride reduction in a nondeoxygenated system. The morphology, elemental content, specific surface area, and crystal properties of the NZVI were characterized before and after the reaction by environmental scanning electron microscope; energy dispersive X-ray; Brunauer, Emmett, and Teller; and X-ray diffraction, respectively. The reduction process was conducted at pH?=?6.3 at ambient temperature. The efficiency of the NZVI-mediated DNTS reduction process was monitored by HPLC, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy analyses.

Results

The properties of the NZVI particles prepared were found to be similar to those obtained through oxygen-free preparation and inert stabilization processes. Both 2,4-DNT-3-sulfonate (2,220?mg?L^?1) and 2,4-DNT-5-sulfonate (3,270?mg?L^?1) in TNT red water underwent a pseudo-first-order transformation when mixed with NZVI at room temperature and near-neutral pH. Their observed rate constants were 0.11 and 0.30?min^?1, respectively. Within 1?h of processing, more than 99% of DNTS was converted by NZVI-mediated reduction into the corresponding diaminotoluene sulfonates.

Conclusions

NZVI can be simultaneously prepared and stabilized in a nondeoxygenated system. NZVI reduction is a highly efficient method for the conversion of DNTS into the corresponding diaminotoluene sulfonates under near-neutral pH conditions. Therefore, NZVI reduction may be useful in the treatment of TNT red water and subsequent recovery of diaminotoluene from explosive wastewater.