铜渣基铁系磷酸盐化学键合材料的制备及其固化Pb2+的研究

利用富含铁氧化物的铜渣和磷酸二氢钾反应制备铁系磷酸盐化学键合材料,并将其作为基体材料固化重金属离子Pb~(2+)。研究了原料配比、缓凝剂及硝酸铅掺量对胶凝材料初凝时间和抗压强度的影响。结果表明,当m(P)/m(CS)为1/4及硼砂掺量为2%时,材料性能最好,自然养护28d和常压蒸汽养护24h抗压强度分别可达44.78 MPa和30.48 MPa。随着重金属铅掺量的增加,固化体抗压强度逐渐降低,铝掺量为4.5%时,自然养护28d和蒸汽养护24h固化块抗压强度均大于10 MPa。对固化体的重金属毒性浸出试验表明:铁系磷酸盐化学键合材料对重金属离子Pb~(2+)具有很好的固化效果,固化体毒性浸出质量浓度远低于国家浸出毒性鉴别标准限值(5mg/L)。通过XRD、SEM和FTIR对重金属固化体进行表征分析,发现固化体中形成了PbHPO_4和Pb_3(PO_4)_2等重金属磷酸盐产物,并被铁系磷酸盐胶凝相物质紧密包裹,从而通过化学键合和物理包裹等双重作用实现重金属Pb的稳定固化。     

磷酸盐矿化菌矿化重金属离子Zn2+的研究

选取一种菌株A,利用其在底物诱导下产生的酶化作用,分解产生PO34-,矿化固结重金属离子(以Zn2+为代表),使其沉积为结晶态的磷酸盐;并通过SEM及XRD等手段定性分析出中性条件下的矿化产物;通过对不同pH值环境下的矿化产物的定量分析,结合XRD分析出酸性、中性、碱性条件的矿化产物;通过实验可发现用该菌株矿化重金属离子的矿化率较高,环境友好、工艺简单,以期应用于实际污染修复中。     

大洋多金属结核浸出渣对含Cr6+重金属废水的吸附研究

用新型固体工业废渣——大洋多金属结核浸出渣作为吸附剂,通过改变废水溶液pH值、吸附时间、溶液体积等条件,研究大洋多金属结核浸出渣对重金属离子Cr⁶⁺吸附率的影响,从而确定了浸出渣作为吸附剂处理Cr⁶⁺重金属废水的最佳吸附条件。     

Cu2+磁性壳聚糖印迹粒子的制备及对Cu2+的吸附

采用一步共沉淀法和离子印迹技术,制备了Fe3O4-壳聚糖(Fe3O4-CTS)印迹粒子。通过X射线衍射、傅里叶红外光谱,振动样品磁强计、热重分析、Zeta电位等手段对Fe3O4-CTS印迹粒子及对比粒子进行结构和性能表征。研究了pH、吸附剂的量、Cu2+初始浓度、吸附时间及温度等不同因素对吸附性能的影响。结果表明,对于印迹粒子,pH=6,吸附时间为4 h,为较理想的吸附条件;当溶液中Cu2+的质量浓度为120 mg/g,吸附剂的质量为50 mg时,吸附基本达到了平衡,单位吸附量约为21.304 mg/g。     

纤维素接枝共聚物对Cu2+和Ni2+吸附性能的研究

以己内酯为单体,在绿色溶剂离子液体中对纤维素进行接枝改性。研究了改性纤维素对金属离子Cu2+、Ni 2+的吸附性能,考察了金属溶液初始质量浓度和温度对吸附效果的影响,对比了改性纤维素对Cu2+和Ni 2+的吸附效果,同时对Cu2+的吸附热力学进行了研究。结果表明,在温度为298K,时间为2h时,改性纤维素对Cu2+、Ni 2+的吸附量分别为133mg/g、40.4mg/g;Cu2+初始质量浓度的增加及温度的降低有利于吸附的进行;改性纤维素对Cu2+的静态等温吸附符合Langmuir和Freundlich吸附等温式,吸附过程是放热过程。     

氯氧镁水泥对焚烧飞灰固化作用及影响因素

利用氯氧镁水泥对飞灰进行固化处理,研究了氯氧镁水泥对飞灰重金属离子的固化效果及影响因素。结果表明,氯氧镁水泥对飞灰固化存在一个最佳摩尔比,在最佳摩尔比条件下Pb浸出浓度最低,固化率达94%;随着活性氧化镁含量上升(由28.9%提高到60.56%),Pb浸出浓度显著降低,固化率提高23.9%,当活性氧化镁含量进一步增加时,Pb浸出浓度降低幅度减小;按摩尔比为10∶1,水灰比为0.3配制氯氧镁水泥,在掺量为20%的条件下,固化效果优于掺量为40%的P·O42.5水泥,且满足生活垃圾填埋标准的限值,具有很好的应用前景。     

过渡金属(Mn2+、Ni2+、Fe3+、Cu2+)掺杂ZnO基稀磁半导体的制备及性质

利用溶液腐蚀法制备了Mn2+、Ni2+、Fe3+、Cu2+离子掺杂的ZnO基稀磁半导体。XRD表明掺杂后的ZnO仍然保持单一的纤锌矿结构,没有任何杂质相产生。由紫外-可见光反射谱可知掺杂后吸收边发生了红移。掺杂前ZnO的带隙为3.20eV,对样品分别掺入Mn、Ni、Fe和Cu后的带隙分别为3.19eV、3.15eV、3.08eV和3.17eV。掺杂后样品的室温PL谱除了紫外发射峰外,对于Mn掺杂的样品还在蓝光区域出现了2个分别位于424nm和443nm的发射峰,Fe掺杂的样品出现了一个位于468nm的微弱发射峰,Cu掺杂的样品出现了位于469nm及535nm的很宽的发射峰。室温磁滞回线显示掺杂后样品有明显的铁磁性,掺入Mn、Ni、Fe和Cu样品的剩余磁化强度(Ms)分别为0.3902×10-3emu/cm3、0.454emu/cm3、0.372emu/cm3和0.962×10-3emu/cm3,矫顽力分别为47Oe、115.92Oe、99.33Oe和23Oe。经分析室温铁磁性来源于缺陷调制的Mn2+-Mn2+长程铁磁交换相互作用。     

红色长余辉材料Y2O2S:Eu3+,Si4+,Zn2+的微波合成及性能研究

采用微波法合成了红色长余辉发光材料Y2O2S:Eu3+,Si 4+,Zn2+,研究了微波辐射功率和加热时间对制备Y2O2S:Eu3+,Si 4+,Zn2+的影响。并且对样品进行了XRD、SEM、荧光光谱和热释光谱等表征。XRD测试表明所制备的Y2O2S:Eu3+,Si 4+,Zn2+为单相,六方晶系;荧光光谱测试表明,用λem=626nm作为监控波长,在200～400nm之间有宽的激发光谱,峰值位于325nm。而发射光谱的谱线较窄,来源于Eu3+的5 D0→7F2跃迁的发射峰627.0nm最强。其中以辐射功率为750w,反应时间为25min所制备的样品发光性能最好。     

生态水泥中SiO2掺量对焚烧飞灰中重金属固溶特性的影响

按不同SiO2掺量(质量分数)进行垃圾焚烧飞灰的水泥固化试验,研究了SiO2掺量对熟料试样的重金属分布、浸出毒性的影响。结果表明,SiO2掺量低于16%时,提高掺量有利于增加熟料中Cr、Ni、Cu、As固溶率;但SiO2掺量超过16%后,重金属固溶率与其成反比。Cd、Pb、Zn的挥发率随SiO2掺量增加而减少,掺加SiO2能明显抑制Zn的挥发,但基本不影响Hg的挥发。SiO2掺量增加后熟料结构进一步致密化,重金属浸出量减少。     

壳聚糖/聚氨酯树脂的制备及对Cu2+吸附研究

以壳聚糖和聚氨酯预聚体为原料制备了壳聚糖/聚氨酯树脂(CTS/PU),考察了其对铜离子吸附性能。结果表明,CTS/PU树脂表面较粗糙;随预聚体用量增大,树脂吸附量先增加后降低。CTS/PU比例为1∶1时,树脂对Cu2+吸附量可达到优;pH值为6时,树脂对Cu2+吸附量最大。动力学研究表明,树脂对Cu2+吸附过程符合准二次动力学模型。     

含铬熟料的烧成、水化及其浸出毒性

为探索水泥窑协同处置含铬固体废弃物的可行性,通过测定熟料的f-CaO含量、强度、铬浸出浓度,以及分析熟料的矿物、水化产物和水化放热,研究了CrO3对熟料烧成、水化及浸出毒性的影响规律及机制。结果表明:当CrO3掺量低于2%时,熟料的f-CaO含量和3d、28d、90d强度随掺量的变化不明显;Cr(Ⅵ)/∑Cr浸出浓度随CrO3掺量增加而增大,随养护龄期延长而减小。当CrO3掺量小于0.25%时,熟料Cr(Ⅵ)浸出浓度均低于0.05mg/L,符合Ⅱ类地表水环境质量标准限值;当CrO3掺量较高时,抑制C3S形成,并显著延缓水化;熟料对铬的固化可归因于熟料矿物和水化产物对铬的固溶和包裹。掺加少量CrO3对熟料烧成、水化、性能均无不利影响,产品的环境安全性能够得到保证,水泥窑协同处置含铬废弃物是值得深入研究的技术途径。     

Leaching behaviour of major and trace elements from concrete: Effect of fly ash and GGBS

The leaching of major and trace elements from concrete made with Portland cement, fly ash and GGBS (ground granulated blast-furnace slag) was studied using pH static availability and tank leach tests. The release of substances during the tank leach test occurs by surface dissolution of phases at the concrete surface and diffusion inside the concrete, the amounts depending on the phases controlling solubility and concrete porosity. Alkali release is controlled by diffusion and is thus reduced by lower water/binder ratios and the replacement of Portland cement by fly ash. Ca, Al and S release occurs mainly by surface dissolution of portlandite and AFt/AFm, respectively. The release of V is determined by surface dissolution of V substituted ettringite and/or calcium vanadate. Although fly ash can increase the total V content of concrete, enhancing release, only 2% of the total V content in concrete was available for release.     

Immobilization of Co(Ⅱ) Ions in Cement Pastes and Their Effects on the Hydration Characteristics

The immobilization of Co(Ⅱ) in various cement matrices was investigated by using the solidification/stabilization(S/S) technique.The different cement pastes used in this study were ordinary Portland cement in absence and presence of water reducing-and water repelling-admixtures as well as blended cement with kaolin.Two ratios of Co(Ⅱ) were used(0.5% and 1.0% by weight of the solid binder).The hydration characteristics of the used cement pastes were tested via the determination of the combined water content,phase composition and compressive strength at different time intervals up to 180 d.The degree of immobilization of the added heavy metal ions was evaluated by determining the leached ion concentration after time intervals extended up to 180 d.The leachability experiments were carried out by using two modes:the static and the semi-dynamic leaching processes.It was noticed that the concentration of the leached Co2+ ions in the static mode of leachability was lower than the solubility of its hydroxide in all the investigated cement pastes.     

A comparative study on Pb2+, Zn2+ and Cd2+ sorption onto zirconium phosphate supported by a cation exchanger

In the present study, a novel hybrid sorbent ZrP-001 was prepared by loading zirconium phosphate (ZrP) onto a strongly acidic cation exchanger D-001. Sorption behavior of Pb(2+), Zn(2+), and Cd(2+) onto ZrP-001 was experimentally examined by comparing with the host exchanger D-001. ZrP-001 was characterized by scanning electron micrograph (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), pH-titration and pore size distribution analysis. Sorption of the heavy metals onto ZrP-001 was found to be pH-dependent due to the ion exchange mechanism. Compared to D-001, a smaller pore size of ZrP-001 due to the ZrP dispersion consequently resulted in a lower sorption rate. Competitive effect of Ca(2+) on sorption of heavy metals onto ZrP-001 and D-001 was compared to elucidate sorption preference of the hybrid sorbent towards heavy metals. More favorable sorption of ZrP-001 than D-001 was observed for all the three metals and their sorption preference onto ZrP-001 followed the order Pb(2+)>Zn(2+) approximately Cd(2+). Fixed-bed sorption results and its efficient regeneration property further demonstrated that ZrP-001 is a potential candidate for removing heavy metals from contaminated water.     

Influence of Zn^2＋ or Cu^2＋ on Reduction and Recalcination Behavior of Fe2TiO5

Fe2O3, TiO2, CuO and ZnO powders were mixed according to the formula of （1-x）TiO2 xCuO-Fe2O3 or （1-x）TiO2 xZnO-Fe2O3 （x=0, 0.2 0.4, 0.6, 0.8, 1）, and well ball-milled with H2O for 3 h to ensure homogeneity of the powdered solids, then fired at 1200℃ for 4 h. The fired samples were reduced at 500℃ with hydrogen gas. The reduced samples were subjected to recalcination at 500℃ in CO2 atmosphere. Both of fired, reduced and calcined samples were characterized by X-ray diffraction, vibrating sample magnetometry, reflected light microscopy and scanning electron microscopy. Different phases were formed after firing of Cu^＋2 or Zn^2＋ substituted Fe2TiO5. Magnetization （Bs） of the formed phases after firing are very low corresponding to diluted magnetic semiconductors （DMS） and increases with increasing the substituted cations （Cu^＋2 or Zn^2＋）. The reduction of the fired samples enhanced the Bs values whereas the reducibility increases with increasing the Cu^＋2 or Zn^2＋ content. Samples show different tendency toward CO2 decomposition which is very important for environmental minimization for CO2.     

Use of rice straw as biosorbent for removal of Cu(II), Zn(II), Cd(II) and Hg(II) ions in industrial effluents

Adsorption experiments were carried out using waste rice straw of several kinds as a biosorbent to adsorb Cu(II), Zn(II), Cd(II) and Hg(II) ions from aqueous solutions at room temperature. To achieve the best adsorption conditions the influence of pH and contact time were investigated. The isotherms of adsorption were fitted to the Freundlich equation. Based on the experimental data and Freundlich model, the adsorption order was Cd(II) > Cu(II) > Zn(II) > Hg(II) on the rice straw. This quick adsorption process reached the equilibrium before 1.5 h, with maximum adsorptions at pH 5.0. Thermodynamic aspects of the adsorption process were investigated. The biosorbent material was used in columns for the removal of ions Cu, Zn, Cd and Hg of real samples of industrial effluent and its efficiency was studied.     

Simultaneous sorption and desorption of Cd, Cr, Cu, Ni, Pb, and Zn in acid soils I. Selectivity sequences

The sorption and desorption of six heavy metals by and from the surface or immediately subsurface horizons of eleven acid soils of Galicia (N.W. Spain) were characterized by means of batch experiments in which the initial sorption solution contained identical mass concentrations of each metal. Concentration-dependent coefficients K(d) were calculated for the distribution of the metals between the soil and solution phases, and the values obtained for initial sorption solution concentrations of 100mgL(-1) of each metal (K(d100)) were used, for each soil, to order the metals as regards their sorption and retention. Pb and Cu were sorbed and retained to a greater extent than Cd, Ni or Zn, which had low K(d100) values. Pb was sorbed more than any other metal. Cr was generally sorbed only slightly more than Cd, Ni or Zn, but was strongly retained, with K(d100) (retention) values greater than those of Pb and Cu in soils with very low CEC (<3cmol((+))kg(-1)). The sorption of Pb and Cu correlated with organic matter content, while the retention of these and the other metals considered appeared to depend on clay minerals, especially kaolinite, gibbsite, and vermiculite.     

In-situ stabilization of Pb, Zn, Cu, Cd and Ni in the multi-contaminated sediments with ferrihydrite and apatite composite additives

Three additives were evaluated for their effectiveness in the attenuation of Pb²⁺, Zn²⁺, Cu²⁺, Cd²⁺, Ni²⁺ in contaminated sediments. Apatite, ferrihydrite and their composite were applied to the sediments. For the remediation, BCR, SEM/AVS and TCLP were adopted as the evaluating method and comparison of their results were used for the first time to test in-situ stabilization effect. The results showed that after 5 months composite treatment, more than 70% Pb²⁺, 40% Zn²⁺, 90% Cu²⁺, 50% Cd²⁺ and 80% Ni²⁺ was immobilized in oxidizable and residual phases, respectively. Compared to untreated sediment, Pb²⁺, Zn²⁺, Cu²⁺, Cd²⁺ in residual fraction increased 20%, 10%, 10%, 10% with composite treatment after 5 months, respectively. ΣSEM/AVS ratio declined from 12.6 to 9.3, in addition, composite treatments reduced the leaching of Pb²⁺ and Zn²⁺ from 10.6 mg L⁻¹and 42.5 mg L⁻¹to 5.4 mg L⁻¹ and 24.1 mg L⁻¹ in the sediment by TCLP evaluation. Meanwhile, apatite and ferrihydrite composite additives lowered the bioavailability and toxicity of sediments as well. Ferrihydrite had a positive effect in controlling the bioavailability and toxicity of heavy metals because it effectively retarded the oxidation of AVS in sediment.     

Removal of Zn(II), Cu(II), Ni(II), Ag(I) and Cr(VI) present in aqueous solutions by aluminium electrocoagulation

The performance of an electrocoagulation system with aluminium electrodes for removing heavy metal ions (Zn2+, Cu2+, Ni2+, Ag+, Cr2O7(2-)) on laboratory scale was studied systematically. Several parameters - such as initial metal concentration, numbers of metals present, charge loading and current density - and their influence on the electrocoagulation process were investigated. Initial concentrations from 50 to 5000 mg L(-1) Zn, Cu, Ni and Ag did not influence the removal rates, whereas higher initial concentrations caused higher removal rates of Cr. Increasing the current density accelerated the electrocoagulation process but made it less efficient. Zn, Cu and Ni showed similar removal rates indicating a uniform electrochemical behavior. The study gave indications on the removal mechanisms of the investigated metals. Zn, Cu, Ni and Ag ions are hydrolyzed and co-precipitated as hydroxides. Cr(VI) was proposed to be reduced first to Cr(III) at the cathode before precipitating as hydroxide.