Pressurized CO2/zero valent iron system for nitrate removal

A fluidized zero valent iron (ZVI) reactor pressurized by CO(2) gas for controlling pH was employed for nitrate reduction. The proposed CO(2) pressurized system potentially has advantages of using less CO(2) gas and reaching equilibrium pH faster than CO(2)-bubbled system. However, due to weak acid nature of carbonic acid, system pH gradually increased with increasing oxidation of ZVI and reduction of nitrate. As pH increased with progress of reaction, nitrate removal rate decreased continuously. The results indicate that nitrate removal efficiency increases with increasing initial ZVI dosage but reaches plateau at ZVI doses of higher than 8.25gl(-1), and initial nitrate concentration up to 100mg l(-1) as N has minimal impact on the removal efficiency. Unlike the fluidized system with pH control by strong acid reported in our pervious study, near 100% of nitrogen recovery was observed in the current process, indicating that nitrate reduction by ZVI with different pH controlled mechanisms will have different reaction routes.     

Mechanisms of NOx removal from flue gas by zero valent iron

Chemical reaction between nitric oxide (NO) andzero valent iron (ZVI) was studied in a packed-bed column process with high temperatures based on ZVI strong reducing abilities. For six controlled temperatures of 523-773 K and 400 ppm of NO (typical flue gas temperature and concentration), under short empty bed contacttime ([EBCT] 0.0226-0.0679 sec), NO was completely removed for temperature of 573-773 K but not for 523 K. Break-through curves were conducted for the five working temperatures, and the results indicated that NO reductions by ZVI were varied from 2 to 26.7 mg NO/g ZVI. Higher temperature and longer EBCT achieved better NO removal efficiency. X-ray diffraction (XRD) and electron spectroscopy for chemical analysis (ESCA) were conducted to analyze the crystal structure and oxidation state of the reacted ZVI. Three layers of iron species were detected by XRD: ZVI, Fe3O4, and Fe2O3. ZVI was the most prevalent species, and Fe3O4 and Fe2O3 were less from the XRD analysis. By ESCA, the oxidation state on the reacted ZVI surface was determined, and the species was identifled as Fe2O3, which is the most oxidizing species for iron. Therefore, three layers from the ZVI core to the ZVI surface can be identified: ZVI, Fe3O4, and Fe2O3. Combining the results from XRD and ESCA, the mechanisms for ZVI and NO can be proposed as two consecutive reactions from lower oxidation state (ZVI) in the core to higher oxidation state on the iron surface (Fe2O3): 3Fe + 4NO<--(high temperature)-->Fe3O4 + 2N2 (A1), 4Fe3O4 + 2NO<--(high temperature)-->6Fe2O3 + N2* (A2) Because there was only <5% ZVI used to remove NO comparing to theoretical ZVI used based on the proposed stoichiometry, it can be concluded that the heterogeneous reaction only occurred on the ZVI surface instead of on bulk of the ZVI.     

零价铝对高氯酸盐污染物的去除

为了考察零价铝对高氯酸盐的去除影响因素和机制,对比了普通铝粉和酸洗铝粉对高氯酸盐的去除效果,并设计正交实验,分析温度、pH值、酸洗零价铝投加量和高氯酸根初始浓度4个因素对高氯酸盐的去除影响规律,另外,检测分析零价铝去除高氯酸盐过程中反应液ClO4-、Cl-随时间的浓度变化。结果表明,酸洗预处理得到较高纯度的零价单质铝,并且对高氯酸盐具有较高的去除效率;正交实验极差分析结果表明,反应的最优水平：温度25℃、pH为4.5、投加量为35 g·L-1、高氯酸根初始浓度为2 mg·L-1,高氯酸根去除效率各影响因素的主次关系为pH >投加量 >温度 >初始浓度;初步表明,零价铝去除高氯酸根的主要机制并非零价铝的还原作用,而是老化铝粉固体表面吸附过程。     

纳米零价铁和零价铁对餐厨垃圾暗发酵制氢过程铁离子和酶活性的影响

通过投加不同浓度的纳米零价铁(NZVI)和零价铁(ZVI),考察了暗发酵制氢过程中铁离子组成和浓度变化、氢化酶和脱氢酶活性,研究了2种添加剂强化餐厨垃圾高温((55±1) ℃)暗发酵制氢的作用机制。结果表明：投加NZVI和ZVI均可提高餐厨垃圾暗发酵制氢性能;当投加100 mg·L⁻¹ ZVI时,产氢效果最佳,最大产氢潜力和最大产氢速率分别为425.72 mL和66.32 mL·h⁻¹,是投加NZVI实验组的1.64倍和1.34倍,代谢途径是以乙醇型发酵为主的混合型发酵;在投加NZVI和ZVI后,暗发酵制氢末端产物的Fe²⁺和Fe³⁺浓度升高,投加300 mg·L⁻¹ NZVI和100 mg·L⁻¹ ZVI实验组Fe²⁺浓度最大,是未投加实验组的2倍和1.87倍;与反应前相比,Fe²⁺显著升高,Fe³⁺由于微生物利用与转化浓度降低,同时可有效提高氢化酶活性。投加100 mg·L⁻¹ ZVI不仅可提高氢化酶活性,还可提高脱氢酶活性。以上结果可为提高餐厨垃圾等复杂有机废物的高效能源化提供参考。     

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.     

A sequential zero valent iron and aerobic biodegradation treatment system for nitrobenzene

The remediation of nitroaromatic contaminated groundwater is sometimes difficult because nitroaromatic compounds are resistant to biodegradation and, when they do transform, the degradation of the products may also be incomplete. A simple nitroaromatic compound, nitrobenzene, was chosen to assess the feasibility of an in situ multi-zone treatment system at the laboratory scale. The proposed treatment system consists of a zero valent granular iron zone to reduce nitrobenzene to aniline, followed by a passive oxygen release zone for the aerobic biodegradation of the aniline daughter product using pristine aquifer material from Canadian Forces Base (CFB) Borden, Ontario, as an initial microbial source. In laboratory batch experiments, nitrobenzene was found to reduce quickly in the presence of granular iron forming aniline, which was not further degraded but remained partially sorbed onto the granular iron surface. Aniline was found to be readily biodegraded with little metabolic lag under aerobic conditions using the pristine aquifer material. A sequential column experiment, containing a granular iron reducing zone and an aerobic biodegradation zone, successively degraded nitrobenzene and then aniline to below detection limits (0.5 microM) without any noticeable reduction in hydraulic conductivity from biofouling, or through the formation of precipitates.     

Removal of thiobencarb in aqueous solution by zero valent iron

A cost-effective method with zero valent iron (ZVI) powder was developed for the purification of thiobencarb (TB)-contaminated water. The removal treatment was performed in the batch system. A sample solution of 10 ml containing 10 microg ml(-1) of TB could be almost completely treated by 100mg of ZVI at 25 degrees C for 12h of treatment time. Since the formation of chloride ion in the aqueous solution during the treatment of TB was observed, the removal of TB with ZVI may contain two processes: reduction (degradation) and adsorption. Because the present treatment for TB is simple, easy handling and cheap, the developed technology with ZVI can contribute to the treatment of agricultural wastewaters.     

Reducing As availability in calcareous soils using nanoscale zero valent iron

Environmental Science and Pollution Research - Different methods, including the use of nanoscale zero-valent iron (NZVI), have been used to treat arsenic (As)-contaminated environments, with much...     

硝酸根对零价铁去除地下水中六价铬的影响

通过批实验和连续通流的柱模拟实验对比研究了存在NO3-和不存在NO3-条件下零价铁（Fe0）去除Cr（Ⅵ）的反应特征,并对比分析了NO3-对零价铁（Fe0）去除Cr（Ⅵ）的影响。批实验结果表明,在不同初始pH条件下,NO3-的加入均使得零价铁（Fe0）去除Cr（Ⅵ）的速率升高;当初始pH=7时,NO3-的促进作用最强,反应速率是无NO3-条件下的2.1倍。柱实验结果表明,NO3-的加入使得Fe0去除Cr（Ⅵ）的反应分成了3个不同的阶段：高效期（1025 PV）。在高效期,反应中的NO3-表现为对Fe0反应位点的竞争,抑制了Cr（Ⅵ）还原。在后期的2个阶段中,反应中NO3-则呈现明显的促进作用。NO3-的存在使得零价铁（Fe0）柱趋于整体性同步钝化,延长了Fe0柱的运行寿命,并且增加了零价铁（Fe0）柱对Cr（Ⅵ）的去除效率。NO3-对Fe0去除Cr（Ⅵ）反应的促进作用原因是由于NO3-与Fe0反应产生Fe3O4,Fe3O4可以还原Cr（Ⅵ）,并且具有阻滞反应的产物在Fe0表面堆积和促进电子传导作用。     

Application of nanoscale zero valent iron (NZVI) for groundwater remediation in Europe

Purpose  

Nanoscale zero valent iron (NZVI) is emerging as a new option for the treatment of contaminated soil and groundwater targeting mainly chlorinated organic contaminants (e.g., solvents, pesticides) and inorganic anions or metals. The purpose of this article is to give a short overview of the practical experience with NZVI applications in Europe and to present a comparison to the situation in the USA. Furthermore, the reasons for the difference in technology use are discussed.     

Sorption and reduction of tetrachloroethylene with zero valent iron and amphiphilic molecules

Effects of surfactants and natural organic matter (NOM) on the sorption and reduction of tetrachloroethylene (PCE) with zero valent iron (ZVI) were examined in this study. PCE reduction by ZVI depended on the ionic type of the surfactants. The removal of PCE and production of TCE with non-ionic Triton X-100 and cationic hexadecyltrimethyl-ammonium (HDTMA) at one-half and two times the critical micelle concentration (CMC) were 1.2-1.8 times higher than without surfactants because of the enhanced PCE partitioning and surface concentration by the sorbed surfactants. When anionic sodium dodecyl benzene sulfonate (SDDBS) at one-half and two times CMC and NOM at 20 mg l(-1) and 50 mg l(-1) concentrations were used, the removal of PCE doubled and TCE production decreased. In the presence of SDDBS, TCE production by ZVI was lower than with HDTMA and Triton X-100 while PCE removal was higher than with the other surfactants.     

改性凹凸棒土负载纳米铁的制备及性能

以200目的天然凹凸棒土为原料,先对原土进行酸活化与微波改性,再以改性凹凸棒土为载体,采用液相还原法由FeCl3·6H2O和NaBH4制备改性凹凸棒土负载纳米铁。通过正交实验、扫描电镜（SEM）、能谱仪（EDS）及红外光谱（IR）对负载前后的凹凸棒土进行表征分析确定其最佳条件。并通过稳定性实验和去除实验对改性凹凸棒土负载纳米铁的性能分析。结果表明：改性凹凸棒土负载纳米铁的最佳条件是铁土比为2.5：1,酸浓度为3 mol·L-1,微波时间为6 min,微波功率为600 W,改性时间为24 h。改性凹凸棒土负载纳米铁在常规水处理环境中能稳定存在。对水中的Cr（Ⅵ）有良好的去除效果,去除率可达97.67%。     

超声波和零价铁联用对氯代苯酚脱氯降解作用的研究

采用超声波和零价铁联用对氯代有机物3氯苯酚(CP)、2,4-二氯苯酚(DCP)和2,4,6-三氯苯酚(TCP)模拟废水进行了脱氯处理研究。以单因素法, 考察了铁粉初始投加量、溶液的初始浓度、超声波功率和溶液的pH值等因素对氯代酚降解的影响,并探讨了降解反应动力学。结果表明,超声波和零价铁联用对氯酚具有显著的降解效果,当水样初始浓度为25 mg/L,溶液pH呈弱酸性,超声波功率为200 W时,氯代酚的脱氯效率达到最大值。降解反应符合准一级反应,CP、DCP和TCP的反应速率常数分别0.0613 h^-1、0.374 h^-1和0.197 h^-1。     

零价铁复合有机膨润土处理染料废水的研究

针对目前印染废水处理现状及膨润土在水处理中回收困难等问题,提出将零价铁复合到有机膨润土中制成零价铁复合有机膨润土(ZVI-OB),以达到高效吸附并降解污染物的目的。以染料废水(Orange II) 作为研究对象,考察了废水中染料的初始浓度、pH以及吸附时间对ZVI-OB去除染料效率的影响,并研究了吸附后降解过程中时间和pH对污染物降解的影响以及降解前后膨润土层结构的变化。研究结果表明,ZVI-OB相对于CTMAB改性的有机膨润土而言,其吸附量有所降低,但ZVI-OB在吸附污染物之后能有效降解有机物。ZVI-OB在饱和吸附Orange II后经催化氧化,总有机碳含量降低为原来的19%,可以重复利用。     

零价铁修复受三氯乙烯污染地下水的实验研究

通过批实验和柱实验研究了三氯乙烯（TCE）初始浓度、四氯乙烯(PCE)等对零价铁去除三氯乙烯的影响,并建立了三氯乙烯降解的反应动力学方程。结果表明：（1）零价铁对TCE具有较好的降解效果,反应符合准一级反应动力学方程,表观反应速率常数随TCE浓度的增加而减小;（2）在铁粉充足的条件下,TCE初始浓度对降解效果影响不显著,且TCE去除率皆可达到90%以上;（3）PCE的存在抑制了TCE的脱氯反应。PCE和TCE共存时,TCE的最大去除率仅为64.2%;TCE脱氯反应的表观反应速率明显降低,反应半衰期由TCE单独存在时的6.8～9.7 h增大到66 h～346.5 h。     

零价铁耦合芬顿氧化法处理TNT红水

采用零价铁耦合芬顿氧化法处理TNT红水,研究了初始pH、零价铁投加量、过氧化氢（H2O2）投加量及温度对红水中总有机碳（TOC）去除效果的影响,同时进行了TOC去除过程中反应动力学的探讨。结果表明,零价铁耦合芬顿氧化体系可有效降解TNT红水中的2,4-二硝基甲苯-3-磺酸钠和2,4-二硝基甲苯-5-磺酸钠。在初始pH为2,温度为20 ℃的条件下,加入1.5 g·L-1零价铁反应1 h后,再加入100 mL·L-1H2O2反应4 h,红水中二硝基甲苯磺酸盐浓度从500 mg·L-1降至0 mg·L-1,去除率为100%,TOC浓度从150 mg·L-1降至30 mg·L-1,去除率达到80%。反应中TOC的降解过程遵循拟二级反应动力学方程。零价铁耦合芬顿氧化法可以作为TNT红水的有效处理途径。     

Modelling of sequential groundwater treatment with zero valent iron and granular activated carbon

Multiple contaminant mixtures in groundwater may not efficiently be treated by a single technology if contaminants possess rather different properties with respect to sorptivity, solubility, and degradation potential. An obvious choice is to use sequenced units of the generally accepted treatment materials zero valent iron (ZVI) and granular activated carbon (GAC). However, as the results of this modelling study suggest, the required dimensions of both reactor units may strongly differ from those expected on the grounds of a contaminant-specific design. This is revealed by performing an analysis for a broad spectrum of design alternatives through numerical experiments for selected patterns of contaminant mixtures consisting of monochlorobenzene, tetrachloroethylene, trichloroethylene (TCE), cis-1,2-dichloroethylene (cis-DCE), and vinyl chloride (VC). It is shown that efficient treatment can be achieved only if competitive sorption effects in the GAC unit as well as the formation of intermediate products in the ZVI unit are carefully taken into account. Cost-optimal designs turned out to vary extremely depending on the prevailing conditions concerning contaminant concentrations, branching ratios, and unit costs of both reactor materials. Where VC is the critical contaminant, due to high initial concentration or extensive production as an intermediate, two options are cost-effective: an oversized ZVI unit with an oversized GAC unit or a pure GAC reactor.     

Chromate transport through columns packed with surfactant-modified zeolite/zero valent iron pellets

Chromate transport through columns packed with zeolite/zero valent iron (Z/ZVI) pellets, either untreated or treated with the cationic surfactant hexadecyltrimethylammonium (HDTMA), was studied at different flow rates. In the presence of sorbed HDTMA, the chromate retardation factor increased by a factor of five and the pseudo first-order rate constant for chromate reduction increased by 1.5-5 times. The increase in rate constant from the column studies was comparable to a six-fold increase in the rate constant determined in a batch study. At a fast flow rate, the apparent delay in chromate breakthrough from the HDTMA modified Z/ZVI columns was primarily caused by the increase in chromate reduction rate constant. In contrast, at a slower flow rate, the retardation in chromate transport from the HDTMA modified Z/ZVI columns mainly originated from chromate sorption onto the HDTMA modified Z/ZVI pellets. Due to dual porosity, the presence of immobile water was responsible for the earlier breakthrough of chromate in columns packed with zeolite and Z/ZVI pellets. The results from this study further confirm the role of HDTMA in enhancing sorption and reduction efficiency of contaminants in groundwater remediation.     

硫/沸石固定床去除硝酸盐工艺研究

采用硫/沸石固定床反应器去除水中硝酸盐。实验结果表明,在硫/沸石固定床反应器内通过自养反硝化作用能使水体中硝酸盐得到有效的去除。在硫与沸石的体积比为1∶2,水力停留时间为2 h,进水COD为50 mg/L时,出水硝酸盐去除率可达到95%以上;不外加碳源,总氮的去除率仍可达80%以上;在不投加CaCO₃的情况下,出水pH可始终保持7.0;温度对该反应器硝酸盐的去除率影响不大,进水水温为12℃时总氮（TN）去除率仍可达91.1%。     

结晶造粒流化床同步去除水中铁、锰及硬度的中试实验

为了实现水中的铁、锰及硬度的同步去除,利用结晶造粒流化床,在中试规模条件下,考察了药剂投加量、晶种填充高度、水力负荷、连续运行时间等因素对出水效果的影响。结果表明,在进水硬度、铁和锰平均浓度分别为300、0.90和1.90 mg·L?1条件下,当水力负荷为13 m·h?1,晶种填充高度为50 cm,NaOH投加量为100 mg·L?1时,出水水质达标,大部分污染物在流化床底部被去除,出水效果随着运行时间的推移有所增强,硬度、铁及锰的去除率分别为59%、70.6%和96.7%,出水pH为9.6;此外,水中硬度的含量较高时,流化床对锰的去除难度加大。通过对长期运行后晶种的结构变化进行SEM﹑EDS和XPS表征,发现流化床运行过程中,结晶颗粒逐渐长大,表面形成致密的结晶产物,其主要成分为CaCO3、FeOOH、Fe3O4、Mn3O4和MnO2等构成的复合物。研究结果为水中铁﹑锰及硬度的同步去除提供可借鉴的理论参考,具有一定的实践指导意义。