零价铁对2,4-二氯酚的还原脱氯研究

氯酚是环境中常见的难降解污染物,氯酚中氯原子的脱除可以提高其生化性。在恒温条件下,利用零价铁(Fe0)还原2,4-二氯酚(2,4-DCP)的模拟废水,研究得出在不同条件下溶液的脱氯率,表明在初始溶液pH=4.2时有利于脱氯反应的进行,Fe/C和Fe/Cu体系形成原电池,脱氯能力大大提高,Fe/Cu体系的脱氯率达到了60%,Fe/C体系的脱氯率达到了44%。溶解氧对2,4-DCP的脱氯反应有明显的抑制作用,厌氧条件下过6个小时脱氯率能够达到50%,而在好氧条件下的脱氯率为40%左右。通过XRD检测,分析了使零价铁钝化的原因。     

Ni-Fe双金属对氯代苯酚催化还原脱氯的试验

分别采用Ni-Fe双金属体系和单一零价铁对氯代有机物2,4-二氯苯酚、2-氯苯酚和4-氯苯酚进行了催化还原脱氯的研究。结果表明:单一零价铁能够对氯代苯酚还原脱氯,但效率不高,通常在10%～25%。在镍的催化作用下,零价铁对氯代苯酚的还原脱氯效率大大提高。当零价铁加入量为60 g/L,硫酸镍为0.6 g/L,初始氯代苯酚的质量浓度在25 mg/L左右,反应初始pH值控制在偏酸性的条件下,还原脱氯效率可达到70%以上。氯代苯酚降解的准一级速率常数和降解率满足以下规律:4-氯苯酚大于2-氯苯酚大于2,4-二氯苯酚。     

醇水体系制备纳米Pd/Fe颗粒去除水中2,4-DCP

为了提高纳米铁的活性和分散性,在醇水体系下制备出纳米钯铁(Pd/Fe)双金属颗粒并表征,将制得的纳米Pd/Fe颗粒应用于水中2,4-二氯苯酚(2,4-DCP)的去除,考察了材料投加量、反应温度、初始pH值、2,4-二氯苯酚初始浓度等因素对2,4-DCP去除的影响,分析了2,4-DCP的去除机理并进行动力学拟合。结果表明,在醇水体系中制备纳米铁有利于纳米颗粒的稳定分散;钯的加入将脱氯途径转变为催化加氢,极大改善了2,4-DCP的去除效果;当2,4-DCP初始浓度为20 mg/L、反应温度30℃、纳米Pd/Fe颗粒投加量为2 g/L时,2,4-DCP可在5 h内去除99.9%;反应过程符合修正的一级反应动力学方程。     

Pd/Fe双金属对1,2,4-三氯苯的催化脱氯

采用Pd/Fe双金属体系对1,2,4-三氯苯（1,2,4-TCB）进行了快速催化还原脱氯的研究.结果表明,在钯的催化作用下,零价铁对1,2,4-TCB有较好的还原脱氯效率.当Pd/Fe双金属的钯化氯为0.06%时,催化剂用量为1g/40mL,反应1h后TCB的脱氯率可达99%.反应速率随钯化氯的提高而增加.反应在Pd/Fe表面进行,符合准一级反应,反应速率常数为0.0837min-1.TCB在催化脱氯的过程中先脱氯成为DCB,再依次脱氯为氯苯和苯.     

6种二氯酚电催化还原脱氯:表观动力学过程比较

采用自制的钯/聚吡咯(十二烷基苯磺酸钠)/钛(Pd/PPy(SDBS)/Ti)电极对二氯酚(DCP)的6种同分异构体进行了电化学还原脱氯研究。探讨了脱氯电流、溶液初始pH和污染物初始浓度对2,5-DCP脱氯过程的影响。在脱氯电流5 mA、溶液初始pH 2.5、温度25℃、污染物初始浓度100 mg·L^-1的条件下对2,3-DCP、2,4-DCP、2,5-DCP、2,6-DCP、3,4-DCP和3,5-DCP的脱氯过程进行了比较。6种DCP的脱氯产物均以苯酚为主,有少量的单氯酚产生,脱氯反应速率常数依次为4.735×10^-2、4.609×10^-2、4.845×10^-2、4.317×10^-2、3.973×10^-2、3.770×10^-2 min^-1。推测DCP的降解速率受pK_a、质子化效应和溶液pH等因素的影响,降解难度由小到大依次为2,4-DCP< 2,3-DCP< 2,5-DCP< 2,6-DCP< 3,4-DCP< 3,5-DCP。     

超声波/零价铁协同降解2,4-二氯苯酚和五氯苯酚的研究

以2,4-二氯苯酚和五氯苯酚为目标污染物,分别在单一超声波体系、单一零价铁还原体系和超声波/零价铁协同体系下进行间歇性试验,结果表明:超声波/零价铁协同体系对2,4二氯苯酚和五氯苯酚的降解率明显高于单一超声波体系或单一零价铁体系下的降解率,也高于两单一体系下的降解率之和,表现出显著的协同作用,各反应体系下的降解规律符合一级反应动力学方程;同时考察了初始pH、初始浓度、零价铁投加量以及超声波声功率等控制参数对协同体系下降解率的影响。     

超声波／零价铁联合降解2，4-二氯酚的特性研究

研究了2,4-二氯酚（2,4-DCP）在超声波／零价铁联合体系中（US／Fe^0）的降解,考察了零价铁（Fe^0）投加量、初始pH、初始2,4-DCP浓度（C0）等控制参数对2,4-DCP降解效率的影响。结果表明,其降解效率分别在Fe^0投加量1．2g／L～1．6g／L,及初始pH2～3时达最大值,随目标污染物初始浓度的提高,其降解效率降低,超声波和零价铁联合体系适合降解较低浓度的2,4-DCP溶液。     

Cu@nZVI制备及降解2,4-DCP研究

众所周知,在液相体系中纳米铁(n ZVI)对有机氯化物具有良好的脱氯能力。本文采用一部液相还原法制备Cu@n ZVI和n ZVI纳米颗粒,并将其应用于2,4-DCP降解的对比研究。对Cu/Fe质量比、2,4-DCP初始浓度及p H的影响进行了探讨。得出最佳降解条件为Cu/Fe质量比=1∶1,2,4-DCP初始浓度=100 mg/L,p H=3.5。同时证明Cu@n ZVI体系的氧化还原效果明显好于n ZVI体系。     

零价铁对土壤中六氯乙烷还原脱氯研究

本文研究了常温常压下Fe^0及其负载贵金属的多组分体系及其他反应条件对土壤中六氯乙烷还原脱氯效率的影响。实验证明：Fe^0及其负载Pd、Pt、Rh多组分金属体系对六氯乙烷都有还原脱氯作用,Pd、Pt、Rh之间不存在协同催化还原脱氯效应;反应初始pH呈酸性时有利于脱氯反应进行;加入甲醇能够提高六氯乙烷在土壤溶液中的溶解度,但不能有效提高其在土壤中的还原脱氯率;甲酸铵是Fe^0体系对六氯乙烷还原脱氯的良好助剂,当甲酸铵加入量为400mg时,用Fe^0还原六氯乙烷脱氯率可以提高59％左右;相同实验条件下,用Pd／Fe还原六氯乙烷的脱氯率可以提高77％左右。文中对零价铁还原脱氯反应机理和助剂甲酸铵的作用机理作了初步探讨。     

改性纳米铁镍去除水中2,4-DCP的研究

采用Pluronic F-127改性纳米零价铁后负载镍,形成改性纳米铁镍(F-NZVI/Ni)。探讨了Ni的负载量、F-NZVI/Ni的投加量、2,4-DCP初始浓度、pH及反应温度对2,4-DCP去除率的影响。同时探究了F-NZVI/Ni去除2,4-DCP的最佳条件下F-NZVI/Ni去除2,4-DCP的反应过程。结果表明,F-NZVI/Ni去除2,4-DCP的能力优于NZVI,当F-NZVI/Ni投加量为3 g/L,镍负载率为5%,2,4-DCP初始浓度为20 mg/L,反应温度为35℃,初始pH值为7时,2,4-DCP的去除率为97%。F-NZVI/Ni去除2,4-DCP主要是先吸附,然后在镍催化剂作用下将2,4-DCP降解为苯酚。     

Hydrodechlorination of 2,4,6-trichlorophenol for a permeable reactive barrier using zero-valent iron and catalyzed iron

Dehalogenation of toxic organic compounds has been intensively studied during the last decade by using zero-valent iron (ZVI). However, the reactivity of iron is compound specific and very low reactivities were reported for aromatic compounds including chlorophenols. In this study, hydrodechlorination of 2,4,6-trichlorophenol (2,4,6-TCP) was conducted in a batch system by using ZVI and catalyzed iron. No degradation was observed with ZVI over the 40 days experiments. Catalyzed ZVIs removed 2,4,6-TCP and palladium-coated iron (Pd/Fe) and nickel-coated iron (Ni/Fe) showed relatively enhanced reactivity while copper-coated iron (Cu/Fe) and platinum-coated iron (Pt/Fe) showed lower reactivities. The surface area normalized kinetic constants (k _SA ) of Pd/Fe, Ni/Fe, Cu/Fe, Pt/Fe are 2.54×10⁻⁴, 1.01 × 10⁻⁴, 2.24×10⁻⁵, 2.56×10⁻⁵ L m⁻² h⁻¹, respectively. The identification of less chlorinated phenols and phenol confirmed that the removal is dechlorination. Pd/Fe system exerts relatively low pH compared with the ZVI system, and the low pH is favorable for the dechlorination. The reactivity enhancement of catalyzed iron was discussed in terms of catalytic effects and the corrosion potential by the bimetal coupling. Variable Pd content on the Pd/Fe was tested, and the degradation rate of 2,4,6-TCP increased in proportion to the increase of Pd content.     

Reductive transformation and dechlorination of chloronitrobenzenes in UASB reactor enhanced with zero‐valent iron addition

BACKGROUND: Zero‐valent iron (ZVI) is increasingly being applied in biological wastewater treatment to enhance the conversion of various contaminants. The objective of this present study was to investigate the effect of ZVI on the anaerobic biotransformation and dechlorination of chloronitrobenzenes (3,4‐DClNB and 4‐ClNB). Experiments were conducted in two upflow anaerobic sludge blanket (UASB) reactors, one (R2) with 30 g L^?1 ZVI added, and the other (R1), serving as control reactor. RESULTS: ZVI‐based anaerobic granular sludge (ZVI‐AGS) composed of bacteria associated with precipitated FeCO₃ and FeS was successfully developed within 5 months in reactor R2. ZVI addition obviously enhanced 3,4‐DClNB transformation and dechlorination efficiencies under high 3,4‐DClNB loads, and further promoted dechlorination of 4‐chloroaniline (4‐ClAn) to aniline. Compared with the AGS formed in R1 reactor, iron and its corrosion products were observed and colonized with anaerobes such as methanothrix in ZVI‐AGS, and the specific transformation rates of 3,4‐DClNB and 4‐ClNB using ZVI‐AGS were improved by 34.0% and 64.4%, respectively. Furthermore, ZVI‐AGS provided higher 3,4‐dichloronailine and 4‐ClAn dechlorination efficiency than AGS. Abiotic transformation of ClNBs by ZVI, appropriate concentration of iron corrosion products, lower redox potential and greater hydrogen production were the main factors providing enhanced transformation and dechlorination of ClNBs in the UASB reactor. CONCLUSION: Addition of ZVI to a UASB reactor enhanced the reductive transformation and dechlorination of ClNBs. It provides a feasible proposal for the design and optimization of a high‐rate anaerobic wastewater treatment technique for industrial wastewater. Copyright © 2010 Society of Chemical Industry     

ZVI/Fe2+/H2O2类Fenton法深度处理烟草薄片废水

采用零价铁(ZVI)/Fe2+/H2O2类Fenton法深度处理造纸法烟草薄片废水(二级生化出水),探讨了反应时间、初始pH、Fe2+浓度、H2O2浓度和ZVI质量浓度对COD和色度去除效果的影响。结果表明,当反应时间为60 min、初始pH为5.0、Fe2+浓度为1.0 mmol/L、ZVI质量浓度为2.0 g/L、H2O2浓度10 mmol/L时,处理后色度为84 C.U.、脱色率为95.5%;COD为73 mg/L,COD去除率为80.4%。与传统Fenton法对比发现,ZVI/Fe2+/H2O2类Fenton法具有可在弱酸性条件下(pH=5.0)使用、总铁需求量少(减少26%)和产泥量少(减少2/3左右)的优点。     

氯代有机物结构性质对还原脱氯速率的影响

研究了氯代甲烷系列和氯代乙烷系列的多种氯代烷烃在铁、铜二相金属体系中的还原脱氯反应,分析了氯代有机物结构性质对还原脱氯反应的影响和规律性。结果表明氯代有机物的结构性质对还原脱氯速率有着明显影响,有机物氯化程度越高,脱氯速率越快,四氯化碳经过1h后脱氯率可达50.7%,而二氯甲烷脱氯则很慢,在氯代乙烷系列中脱氯速率最快的是1,1,1-三氯乙烷。电子直接转移是氯代烷烃还原脱氯的主要途径。     

Effect of reduction temperature on the preparation of zero-valent iron aerogels for trichloroethylene dechlorination

Zero-valent iron (ZVI) aerogels have been synthesized by sol-gel method and supercritical CO₂ drying, followed by H₂ reduction in the temperature range of 350–500 °C. When applied to trichloroethylene (TCE) dechlorination, the ZVI aerogel reduced at 370 °C showed the highest performance in the conditions employed in this study. Thus, the effect of reduction temperature in preparing ZVI aerogels has been investigated by several characterizations such as BET, XRD, TPR, and TEM analyses. As the reduction temperature decreased from 500 to 350 °C, the BET surface area of the resulting aerogels increased from 6 to 30 m²/g, whereas their Fe⁰ content decreased up to 64%. It was also found that H₂ reduction at low temperatures such as 350 and 370 °C leads to the formation of ZVI aerogel particles consisting of both Fe⁰ and FeO _x in the particle cores with a different amount ratio, where FeO _x is a mixture of maghemite and magnetite. It is, therefore, suggested that reduction at 370 °C for ZVI aerogel preparation yielded particles homogeneously composed of Fe⁰ and FeO _x in the amount ratio of 87/13, resulting in high TCE dechlorination rate. On the other hand, when Pd- and Ni-ZVI aerogels were prepared via cogellation and then applied for TCE dechlorination, we also observed a similar effect of reduction temperature. However, the reduction at 350 or 370 °C produced Pd- or Ni-ZVI aerogel particles in which Fe⁰ and Fe₃O₄ co-exist homogeneously. Since both Fe⁰ and Fe₃O₄ are advantageous in TCE dechlorination, the activities of Pd- and Ni-ZVI aerogels reduced at 350 °C were comparable to those of both aerogels reduced at 370 °C, although the former aerogels have less Fe⁰ content.     

The improvement of boron-doped diamond anode system in electrochemical degradation of p-nitrophenol by zero-valent iron

Boron-doped diamond (BDD) electrodes are promising anode materials in electrochemical treatment of wastewaters containing bio-refractory organic compounds due to their strong oxidation capability and remarkable corrosion stability. In order to further improve the performance of BDD anode system, electrochemical degradation of p-nitrophenol were initially investigated at the BDD anode in the presence of zero-valent iron (ZVI). The results showed that under acidic condition, the performance of BDD anode system containing zero-valent iron (BDD-ZVI system) could be improved with the joint actions of electrochemical oxidation at the BDD anode (39.1%), Fenton's reaction (28.5%), oxidation–reduction at zero-valent iron (17.8%) and coagulation of iron hydroxides (14.6%). Moreover, it was found that under alkaline condition the performance of BDD-ZVI system was significantly enhanced, mainly due to the accelerated release of Fe(II) ions from ZVI and the enhanced oxidation of Fe(II) ions. The dissolved oxygen concentration was significantly reduced by reduction at the cathode, and consequently zero-valent iron corroded to Fe(II) ions in anaerobic highly alkaline environments. Furthermore, the oxidation of released Fe(II) ions to Fe(III) ions and high-valent iron species (e.g., FeO²⁺, FeO₄²⁻) was enhanced by direct electrochemical oxidation at BDD anode.     

Influence of mixed-surfactant on reductive dechlorination of trichloroethylene by zero-valent iron

Mixed nonionic and cationic surfactants were used to enhance the reductive dechlorination rate of trichloroethylene (TCE) with zero valent iron (ZVI). Among tested combinations of four cationic and three nonionic surfactants, a mixed surfactant system of hexadecyl-trimethyl ammonium (CTAB) and Brij30 at a mixing ratio of 1: 1 with 0.5 critical micelle concentration (CMC) exhibited the highest reaction rate constant, 0.0269 h⁻¹; the dechlorination rate constant of TCE with ZVI in the absence of surfactant was 0.0206 h⁻¹. The effect of this mixed surfactant on the reductive dechlorination of TCE was investigated using ZVI in a column to simulate field conditions. Unlike batch tests, column tests of the mixed surfactant system exhibited higher and lower TCE removal as compared to a nonionic and a cationic surfactant system, respectively. Consequently, if surfactants are applied for surfactant-enhanced aquifer remediation (SEAR), the performance of a permeable reactive barrier (PRB) system using ZVI to remove the residual TCE in groundwater might be affected by surfactant types; thus, the application should be carefully considered.     

腐殖质/铁氧化物协同促进2,4-D微生物厌氧降解

构建"铁/腐殖质还原菌(Comamonas koreensis,CY01)、腐殖质模式物、铁氧化物、2,4-D"厌氧反应体系,研究2,4-D转化效率与转化途径,探讨2,4-D转化促进机制。结果表明,CY01对2,4-D的直接脱氯效果微弱,蒽醌-2,6-二磺酸钠(AQDS)与针铁矿(α-FeOOH)的加入可有效促进2,4-D厌氧转化,25 d时降解率提高2倍,达33.3%。CY01/AQDS/α-FeOOH/2,4-D体系中,AQDS、Fe(Ⅲ)及2,4-D微生物还原3种过程同时存在,AQDS和Fe(Ⅲ)充当电子穿梭体,加速胞内电子向胞外2,4-D的转移,协同促进2,4-D还原脱氯。本研究可为难降解有机氯农药污染土壤的修复研究提供借鉴。     

Ni-B非晶态合金催化加氢制备氯代苯胺

采用水合肼和硼氢化钾为共还原剂,适当比例的甲醇、乙醇和水的混合物为溶剂,在333 K下制得负载催化剂P1。XRD、TEM、SAED测定结果表明,该催化剂是一种纳米级非晶态合金。将P1催化剂用于邻氯硝基苯加氢反应,在底物100%转化时,生成邻氯苯胺的选择性达到94.3%。对一系列氯代硝基芳烃化合物在P1催化剂上的催化加氢反应进行了考察,得出脱氯顺序依次为:2-氯-5-硝基甲苯>邻氯硝基苯>间氯硝基苯=对氯硝基苯>2,5-二氯硝基苯,分析了不同氯代硝基苯的结构与脱氯的关系,认为在该催化剂上脱氯的主要原因,是生成的氯代苯胺在催化剂表面的吸附。讨论了金属添加剂(Cr、Mn、Fe、Co、Cu、Mo、Zn、La)对P1催化剂催化加氢制备邻氯苯胺的影响,发现添加Cu、Fe能提高催化剂的选择性,在底物基本转化时,选择性由不加金属添加剂时的94.3%,分别提高到97.2%和97.6%。