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.     

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。     

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.     

Nanoscale zero-valent iron/AC as heterogeneous Fenton catalysts in three-dimensional electrode system

In the present work, nanoscale zero-valent iron/activated carbon (NZVI/AC) was investigated as heterogeneous Fenton catalyst in three-dimensional (3D) electrode system for methyl orange (MO) degradation. Some important operating parameters such as cathodic potential, pH, and O₂ flow rate were investigated, exhibiting good decolorization. The mineralization of MO was significantly improved by 20–35 % compared to two-dimensional (2D) AC system at the optimum conditions. Although the TOC removal of AC was higher than NZVI/AC due to its good adsorption capacity initially, heterogeneous Fenton catalysis played a more and more important roles in the following test. After eight runs, NZVI/AC still exhibited excellent catalytic properties with low iron leaching. Further, a relatively comprehensive mechanism of NZVI/AC as particle electrodes in 3D system was proposed.     

纳米零价铁颗粒去除污染土壤HCl浸提液中的Pb

主要研究了纳米零价铁颗粒对土壤HCl浸提液中重金属Pb的去除效果。通过批实验探讨HCl浓度、纳米零价铁投入量以及处理时间对Pb去除率的影响。实验结果表明,纳米零价铁颗粒对浸提液中Pb的去除反应符合langmuir和freundlich等温吸附方程;反应遵循准一级反应动力学方程,标准化后的反应速率常数KSA=0.018 mL/(m2.min);反应30 min时,0.5 g纳米零价铁对1.0 mol/L的HCl所提取Pb(51.7 mg/L)的去除率达到91.8%。研究结果表明,纳米零价铁对土壤HCl浸提液中Pb具有良好去除效果,但相对于处理水溶液中的Pb,反应速率偏低。     

PBTCA稳定零价纳米铁的制备及其去除水中Cr(Ⅵ)

以2-膦酸丁烷-1,2,4三羧酸(PBTCA)为稳定剂,通过FeCl3.6H2O与NaBH4反应,利用液相还原法制备稳定纳米级零价铁颗粒(P-NZVI),并用透射电子显微镜(TEM)、扫描电子显微镜(SEM)及X射线衍射(XRD)进行表征,颗粒平均粒径为73 nm。考察了Cr(Ⅵ)溶液初始浓度、pH、NZVI投加量、温度等条件对Cr(Ⅵ)去除效果的影响,并与同等条件下不加稳定剂制备的纳米铁(N-NZVI)进行对比。结果表明:Cr(Ⅵ)的去除率随温度和纳米铁投加量增加而升高,随pH和Cr(Ⅵ)溶液初始浓度升高而降低。在相同实验条件下,P-NZVI对Cr(Ⅵ)的去除效果明显优于N-NZVI,表明改性后纳米铁在地表水原位修复领域具有较好的应用前景。     

零价铁与厌氧微生物协同还原地下水中的硝基苯

通过间歇式实验,考察了零价铁与厌氧微生物协同还原地下水中硝基苯的效果。实验结果表明,由零价铁腐蚀为厌氧微生物提供H2电子供体还原硝基苯的效果明显优于零价铁和微生物单独作用,硝基苯去除率分别提高21.8%和57.0%。弱酸性条件有利于协同反应进行,当初始pH为5.0和6.0时,4 d后硝基苯去除率比初始pH为7.0时的提高74.4%和35.2%。增加零价铁投加量可提高协同还原的效果,零价铁最佳投加量为250 mg/L。零价铁腐蚀产生的Fe2+无法作为电子供体被微生物利用,但可作为无机营养元素促进协同过程。由于零价铁产H2速率受表面覆盖物影响不明显,在地下水修复过程中可保证协同效果并延长零价铁的使用寿命。     

PCE dissolution and simultaneous dechlorination by nanoscale zero-valent iron particles in a DNAPL source zone

While the capability of nanoscale zero-valent iron (NZVI) to dechlorinate organic compounds in aqueous solutions has been demonstrated, the ability of NZVI to remove dense non-aqueous phase liquid (DNAPL) from source zones under flow-through conditions similar to a field scale application has not yet been thoroughly investigated. To gain insight on simultaneous DNAPL dissolution and NZVI-mediated dechlorination reactions after direct placement of NZVI into a DNAPL source zone, a combined experimental and modeling study was performed. First, a DNAPL tetrachloroethene (PCE) source zone with emplaced NZVI was built inside a small custom-made flow cell and the effluent PCE and dechlorination byproducts were monitored over time. Second, a model for rate-limited DNAPL dissolution and NZVI-mediated dechlorination of PCE to its three main reaction byproducts with a possibility for partitioning of these byproducts back into the DNAPL was formulated. The coupled processes occurring in the flow cell were simulated and analyzed using a detailed three-dimensional numerical model. It was found that subsurface emplacement of NZVI did not markedly accelerate DNAPL dissolution or the DNAPL mass-depletion rate, when NZVI at a particle concentration of 10g/L was directly emplaced in the DNAPL source zone. To react with NZVI the DNAPL PCE must first dissolve into the groundwater and the rate of dissolution controls the longevity of the DNAPL source. The modeling study further indicated that faster reacting particles would decrease aqueous contaminant concentrations but there is a limit to how much the mass removal rate can be increased by increasing the dechlorination reaction rate. To ensure reduction of aqueous contaminant concentrations, remediation of DNAPL contaminants with NZVI should include emplacement in a capture zone down-gradient of the DNAPL source.     

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。     

Synthesis of magnetic CoFe2O4/ordered mesoporous carbon nanocomposites and application in Fenton-like oxidation of rhodamine B

CoFe₂O₄/ordered mesoporous carbon (OMC) nanocomposites were synthesized and tested as heterogeneous peroxymonosulfate (PMS) activator for the removal of rhodamine B. Characterization confirmed that CoFe₂O₄ nanoparticles were tightly bonded to OMC, and the hybrid catalyst possessed high surface area, pore volume, and superparamagnetism. Oxidation experiments demonstrated that CoFe₂O₄/OMC nanocomposites displayed favorable catalytic activity in PMS solution and rhodamine B degradation could be well described by pseudo-first-order kinetic model. Sulfate radicals (SO₄ ⁻·) were verified as the primary reactive species which was responsible for the decomposition of rhodamine B. The optimum loading ratio of CoFe₂O₄ and OMC was determined to be 5:1. Under optimum operational condition (catalyst dosage 0.05 g/L, PMS concentration 1.5 mM, pH 7.0, and 25 °C), CoFe₂O₄/OMC-activated peroxymonosulfate system could achieve almost complete decolorization of 100 mg/L rhodamine B within 60 min. The enhanced catalytic activity of CoFe₂O₄/OMC nanocomposites compared to that of CoFe₂O₄ nanoparticles could be attributable to the increased adsorption capacity and accelerated redox cycles between Co(III)/Co(II) and Fe(III)/Fe(II).

     

硝基苯对硫酸盐还原过程的影响

为了探明硝基苯(NB)对硫酸盐还原的影响,揭示相关过程机制,采用以丙酸盐为碳源和电子供体的序批式厌氧反应系统(水力停留时间为33 h),考察了碳硫比为0.63～5.0,NB浓度为2.5～50 mg/L条件下,系统的硫酸盐还原效能。研究结果表明,NB对硫酸盐还原过程存在抑制作用,当系统NB进水浓度低于30 mg/L时,NB对硫酸盐还原过程抑制并不显著,但当进水NB浓度达50 mg/L时,硫酸盐还原率由近100%迅速降至17%。对比实验结果进一步表明,NB初始浓度为16.5 mg/L条件下,硫酸盐的比还原速率和丙酸的比消耗速率分别为对照组的63%和52%。硫酸盐还原的抑制主要源自NB及其还原产物苯胺(AN)的生物毒性,但上述抑制作用可逆。     

TiO2/活性炭复合纳米纤维膜对亚甲基蓝的吸附研究

摘要以自制的TiO2/活性炭复合纳米纤维膜作为吸附剂,以亚甲基蓝为目标污染物,研究了亚甲基蓝初始浓度、温度、TiO2/活性炭复合纳米纤维膜投加量、pH等对TiO2/活性炭复合纳米纤维膜吸附去除亚甲基蓝的影响,并研究了TiO2/活性炭复合纳米纤维膜的Zeta电位、接触角、光催化再生性能.结果表明:(1)静态吸附时,随着亚...     

纳米铁-微生物耦合体系去除硝酸盐的影响因素研究

采用液相还原法制备出纳米铁粒子,并与自养反硝化细菌耦合,以解决单独使用生物反硝化和纳米铁还原法的不足。本实验在纳米铁-微生物耦合体系可以有效还原硝酸盐的基础上,研究了pH、温度和DO等环境因素对该耦合体系脱氮速率和产物的影响,以期通过优化参数达到最好的脱氮效果。结果表明,该体系在中性条件下能够快速将硝酸盐还原,随pH升高,氨氮比例无显著变化,均在40%左右,但还原速率有所下降;随温度的升高,氨氮比例有所上升,而反应速率明显升高,但该体系在5℃时仍能将硝酸盐完全去除;耦合体系中的DO过高或过低都会导致产物中氨氮比例的增加,0.4 mg/L左右为较适宜DO水平,但对硝酸盐还原速率的影响不大,当DO为0.8 mg/L时,硝酸盐仍可以在8 d内完全去除。因此,该耦合脱氮体系对pH、温度和DO的适应能力较强,有利于实际地下水的原位修复。     

单质硫改性介孔炭对水溶液中汞的吸附性能研究

对介孔炭CMK-3进行单质硫改性得到OMC-S,并通过静态吸附实验研究了该材料对水溶液中汞的吸附性能。研究结果表明：单质硫改性可以在介孔炭上负载12.33%的硫,从而使得介孔炭对汞的吸附容量从185 mg/g提高到476 mg/g;OMC-S具有较广的适用pH值范围,在pH 3～11.5范围内其对汞的吸附去除率均达到92%以上;氯离子对OMC-S的吸附性能具有一定的抑制作用,原因在于它能和汞离子络合形成一系列吸附性能较差的Hg-Cl络合物,而腐殖酸在所研究的范围内对OMC-S的吸附性能无明显影响。     

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.     

Organic-coated nanoparticulate zero valent iron for remediation of chemical oxygen demand (COD) and dissolved metals from tropical landfill leachate

The use of nanoparticulate zero valent iron (NZVI) in the treatment of inorganic contaminants in landfill leachate and polluted plumes has been the subject of many studies, especially in temperate, developed countries. However, NZVI’s potential for reduction of chemical oxygen demand (COD) and treatment of metal ion mixtures has not been explored in detail. We investigated the efficiency of NZVI synthesized in the presence of starch, mercaptoacetic, mercaptosuccinic, or mercaptopropenoic acid for the reduction of COD, nutrients, and metal ions from landfill leachate in tropical Sri Lanka. Synthesized NZVI were characterized with X-ray diffraction (XRD), transmission electron microscopy, X-ray photoelectron spectroscopy, scanning electron microscopy (SEM), thermal gravimetric analysis, Fourier transform infrared spectroscopy (FTIR) and Brunauer–Emmett–Teller. Of the samples tested, Starch-NZVI (S-NZVI) and mercaptoacetic-NZVI (MA-NZVI) performed well for treatment both COD and metal mixture. The removal percentages for COD, nitrate-nitrogen, and phosphate from S-NZVI were 50, 88, and 99 %, respectively. Heavy metal removal was higher in S-NZVI (>95 %) than others. MA-NZVI, its oxidation products, and functional groups of its coating showed the maximum removal amounts for both Cu (56.27 mg g^?1) and Zn (28.38 mg g^?1). All mercapto-NZVI showed well-stabilized nature under FTIR and XRD investigations. Therefore, we suggest mercapto acids as better agents to enhance the air stability for NZVI since chemically bonded thiol and carbonyl groups actively participation for stabilization process.     

顶空气相色谱测试水中苯系混合物在不同材料上的吸附行为

设计了正交实验对5种材料吸附模拟废水中苯系混合物(苯、甲苯、二甲苯)的条件进行优化,CD02硅藻土与X型纳米分子筛以2∶1(质量比)进行复合后,对苯系混合物去除效果最好.采用顶空气相色谱法测定8种不同材料对水中苯系混合物的去除情况,结果表明复合材料对苯系混合物具有良好的去除效果,仅次于活性炭.复合材料在pH为7、搅拌时间为25 min、用量为1.8g/L时,对苯系混合物质量浓度为4.0 mg/L模拟废水的平均去除率为87.56％.经过4次再生后,复合材料的再生率仍高达84.90％,对苯系混合物的平均去除率为91.49％.     

复合改性海泡石同步处理废水中的氮磷

采用盐热和稀土掺杂制备复合改性海泡石,研究了复合改性海泡石对废水中N、P的吸附特征和去除效果。结果表明,与海泡石原矿粉比较,复合改性海泡石的脱氮除磷能力分别提高49.71%和90.14%;复合改性海泡石对N、P的吸附可以用Langmuir吸附模型描述,获得的最大吸附量分别为1.165和1.121 mg/g;修正的Elovich模型能较好地描述复合改性海泡石吸附N、P的动力学过程;用NaOH溶液可以再生吸附材料,获得较好的脱氮除磷效果,再生次数以2次为宜;用复合改性海泡石处理污水处理站的二级生化出水,最终出水的pH、N和P含量均达到《城镇污水处理厂污染物排放标准》的要求。     

工业废渣基除磷材料的静态吸附研究

研究了高效除磷材料（EPRC）对磷素的吸附特性,考察了投加量、初始浓度、初始pH值、粒径等对EPRC吸附性能的影响,分析了不同条件下EPRC的吸附过程。结果表明,最佳投加量为3.5 g/250 mL时,去除率达91.07%,出水TP浓度为0.45 mg/L。随着粒径减小,EPRC对磷素的吸附量增大,吸附平衡时间缩短。溶液初始pH值在碱性条件下,吸附容量变大。     

镁盐改性活性炭对普拉红B的吸附性能研究

运用化学沉淀-原位复合法制得氢氧化镁/活性炭复合材料(Mg(OH)2/AC),对其比表面积和XRD谱进行了表征,考察了该复合材料对普拉红B的脱色性能.结果表明,在293～313 K下,Langmuir模型和Freundlich模型都能很好地描述Mg(OH)2/AC对普拉红B的等温吸附过程,而Langmuir模型更为合适...