凹凸棒石与Zn^2＋的长期作用研究

以凹凸棒石与Zn2＋为例研究粘土矿物与重金属离子长期作用过程,并运用高分辨透射电镜和X射线衍射分析粘土矿物与重金属离子长期作用的次生物相。结果表明：Zn2＋与凹凸棒石的长期作用是一个二阶段的过程,初始阶段为快速吸附作用,其后表现为慢速沉淀反应。高分辨透射电镜和X射线衍射分析表明,凹凸棒石与Zn2＋的长期作用过程中,具有纳米矿物特性的凹凸棒石表面快速水化,提高了悬浮液的pH值,诱导Zn2＋水解沉淀。而后,凹凸棒石缓慢溶解释放Al3＋和SiO44-与Zn（OH）2沉淀反应,形成Zn-A1双氢氧化物和异极矿。这一结果对认识土壤环境中重金属与粘土矿物的作用及重金属的归宿具有重要意义。     

针铁矿/水界面反应性的实验研究

选择针铁矿对Pb2+、Cu2+、Cd2+等3种重金属离子的吸附实验,开展矿物/水界面反应性研究.金属离子(M2+)在矿物-水溶液间分配有多种表面反应机制,这些表面反应发生作用的条件主要取决于吸附质水化学性质和矿物表面荷电性,因此,溶液pH值是影响矿物/水界面反应性的关键因素.在不同pH值条件下, 表面羟基可通过发生质子化或去质子化反应而使得矿物表面产生荷电性并发生改变,而金属离子的水解则可显著加快金属羟基配合物的形成,从而进一步增强了矿物/水界面反应.本实验条件下针铁矿表面对重金属离子的吸着量随pH值升高而升高,在一个较窄的pH值范围内吸附率急剧升高,呈S形分布.针铁矿对3种不同的重金属离子的吸附能力的强弱顺序是Cu2+＞Pb2+＞Cd2+.无论是Langmuir方程还是Freundlich方程,都能较好拟合针铁矿对重金属离子的等温吸附过程.Freundlich方程的n值均在0.1～0.5之间,说明重金属离子在针铁矿表面的吸附并不能简单地归结为单配位或双配位模式,可能存在着多种吸附结合形态.表观吸附常数KM值的变化规律,说明重金属离子与针铁矿表面反应模式及其表面吸附形态发生了变化,具体的吸附形态还有待谱学研究进一步证实.     

水悬浮体系中凹凸棒石与Cu2+作用机理

研究矿物吸附重金属性能和机理,对正确认识矿物吸附性质、环境矿物材料应用研究以及重金属环境化学行为具有重要理论和实际意义。凹凸棒石是重要粘土矿物之一,也是重要的环境矿物材料,其吸附净化功能潜在应用受到广泛关注。在制备凹凸棒石纯样基础上,进行了凹凸棒石吸附Cu^2 单因素实验,吸附前后溶液pH值变化观测和吸附Cu^2 后凹凸棒石表面结构高分辨透射电镜调查。结果表明,从表面来看,凹凸棒石对Cu^2 的吸附性能主要受振荡速度、吸附时间、初始溶液pH值、吸附剂用量等因素影响,但实际上,凹凸棒石对Cu^2 的吸附作用主要是凹凸棒石诱导的Cu^2 水解沉淀作用以及凹凸棒石(带负电荷)与氢氧化铜(带正电荷)正负电荷胶体颗粒的互相作用,这有别于严格意义的矿物界面吸附作用。产生这种作用的机制在于凹凸棒石属于天然纳米矿物材料,具有较高的表面化学活性,凹凸棒石一水悬浮体系中凹凸棒石表面水解呈现出碱性,结果导致吸附平衡水溶液pH值较初始水溶液有较大程度的升高,达到Cu^2 水解基本完全的pH条件.     

即时合成Cu/Mg/Al层状双氢氧化物处理含Cu2+废水实验研究

在模拟含Cu2+废水中加入Mg2+和Al3+,以NaOH为沉淀剂,研究金属盐水解即时合成层状双氢氧化物去除Cu2+的可行性,同时考察了体系终点pH值、配料中Mg/Cu摩尔比值及反应温度和时间对Cu2+去除率的影响,探讨了Cu2+去除机理及层状双氢氧化物形成过程。结果表明,实验条件下体系终点pH值显著影响Cu2+去除率,在pH值8.0~11.0范围内去除效果较好,达99%以上。通过X射线衍射分析结合即时合成法特点,废水中Cu2+主要是在晶核生成阶段以Cu/Mg/Al三元层状双氢氧化物形式被去除;三元层状双氢氧化物的形成由反应体系中Al3+、Cu2+、Mg2+分步水解导致,最适pH值约为9.0。     

电气石微粉吸附水体中金属离子及其机理分析

研究了电气石微粉吸附水中Cu2＋、Pb2＋、Zn2＋的过程,讨论了吸附时间、粒度、用量和pH值等因素对吸附效果的影响,分析了电气石对含Cu2＋、Pb2＋、Zn2＋废水的吸附机理。电气石加工成超细粉体时,表面产生大量的不饱和键,在溶液中与水配位,使水发生解离生成羟基化表面,将重金属离子吸附到晶体负极,使局部金属离子浓度增高与电气石表面羟基离解而产生的氢氧根离子发生反应,形成各种沉淀或碱式盐析出,直到溶液中各种离子浓度达到平衡时为止。提出了凡是氢氧化物难溶于水的金属离子,理论上都可以使用电气石微粉进行吸附净化处理的观点。研究结果表明,电气石微粉对Cu2＋、Pb2＋、Zn2＋有较好的吸附效果。     

蒙脱石的电动电位调控及其对重金属离子吸附性能的影响

为了提高蒙脱石对水体中的Cr3+、Ni2+、Cu2+等重金属离子的净化效率,用各种金属离子、聚合羟基铝离子、十六烷基三甲基溴化铵及邻菲罗啉的螯合物等插层蒙脱石,调控其电动电位,研究了改性蒙脱石的电动电位与吸附金属离子性能的关系,探索了pH值及金属离子浓度对吸附性能的影响。结果表明:蒙脱石经不同物质改性后,电动电位发生了不同程度的变化,其中聚合羟基铝离子,十六烷基三甲基溴化铵及邻菲罗啉螯合物的插层,使蒙脱石的电性从负值变为正值,不利于对带正电的金属离子的吸附。利用重金属离子的配位性,先在含有重金属离子的溶液中加入邻菲罗啉,使其生成螯合物,再用蒙脱石进行吸附,能显著改善吸附性能,这一方法不仅提高了对低浓度的金属离子的吸附性能,而且由于氢键和范德华力起主要作用,使得吸附性基本不受溶液pH值的影响。     

国内矿物治理重金属废水研究进展与展望

综述了我国利用天然矿物治理重金属废水方面的研究新成果。天然铁的硫化物、天然铁锰的氧化物、方解石与磷灰石等具有良好的表面吸附与氧化还原化学活性;不同介质中它们能不同程度地表现出对Cr^6 、Pb^2 、Hg^2 、Cd^2 等重金属离子的吸附作用,可广泛用于重金属废水处理。矿物吸附重金属离子机理的研究表明,矿物对重金属的吸附是矿物表面与无机重金属离子之间的表面作用过程,包括矿物表面功能基与重金属离子的配位反应、矿物表面氧化还原反应和沉淀转化作用,以及矿物表面离子交换吸附作用等。     

粘土质白云岩去除水中铜离子的效果及其机制

利用静态吸附实验研究了溶液pH值、反应时间、初始Cu2+浓度等因素对凹凸棒石粘土矿中粘土质白云岩去除Cu2+效 果的影响,将准一级、准二级、Elovich动力学方程与反应动力学进行拟合,再利用Langmuir、Freundlich等温方程对实验数 据进行等温式拟合,并与普通白云岩和凹凸棒石粘土进行了对比研究。结果表明,粘土质白云岩相对于其他两种材料受pH 影响较小,且在pH3~5范围内对Cu2+去除率均大于85%,最佳pH为5;对Cu2+的去除符合准二级动力学模型,粘土质白云 岩对铜的去除速率和去除率均最高;等温数据符合Freundlich模型,对Cu2+的最大去除量（pH=5,30℃）为186.2×10-3。粘 土质白云岩去除水中Cu2+的主要机制为矿物水化与溶解引起的表面沉淀及凹凸棒石与新生碱式碳酸铜[Cu2CO3(OH)2]胶体的静 电吸附。粘土质白云岩中纳米凹凸棒石与亚微米多孔白云石共生,具有较高的化学反应活性,除Cu2+效果明显优于普通白 云岩和凹凸棒石粘土,在处理含Cu2+废水方面具有潜在应用价值。     

凹凸棒石吸附性能应用的制约因素

凹凸棒石是链层状硅酸盐， 具有３－８?×６－３?孔道、较大的比表面积和吸附能力。但是由于凹凸棒石孔道直径小于大多数分子及水合离子的直径， 除少数简单分子和离子外， 多数分子和离子都不能进入凹凸棒石孔道， 而且凹凸棒石选择性吸附水分子， 因而在多数情况下， 凹凸棒石对吸附质的吸附不是内表面吸附， 而是外表面吸附。并且外表面吸附是胶体和离子交换吸附。本文阐述了凹凸棒石的孔道直径、吸附选择性、体系ｐＨ 值及凹凸棒石和蒙脱石胶体颗粒的互相作用对凹凸棒石吸附性能应用的制约。     

铜(Ⅱ)在高岭石表面的吸附

在天然水体系中,铜、铅、镉等重金属元素的形态分布、迁移、归宿和生物有效性强烈取决于重金属元素在水体颗粒物表面的分配趋势.本文对铜(Ⅱ)在常见的重要粘土矿物--高岭石表面的吸附进行了实验和模式研究,结果表明,在同时考虑自由水合离子CU2+和羟基金属离子CuOH+与高岭石表面络合的情况下,单一表面基团、无静电表面络合模式能很好地描述铜(Ⅱ)的吸附行为.拟合得到的CuoH+的络合常数比Cu2+的大得多. 铜(Ⅱ)在高岭石表面的吸附量随pH值的升高而增加.吸附铜的两种表面化合态,>SOCu+和>SOCuOH的浓度在实验的pH范围内,也随pH值升高而增加,并且以>SOCu+为主.     

On the cathodic reaction coupled with the oxidation of xanthates at the pyrite/aqueous solution interface

The adsorption of ethyl, propyl and butyl xanthates on pyrite has been studied through electrokinetics, batch adsorption tests, and quantification of Fe²⁺ ions in solution. Adsorption isotherms for the three alkyl xanthates indicate that their adsorption to dixanthogen produces Fe²⁺ ions in solution and decreases the pyrite zeta potential negatively. It seems that the oxidation reaction of xanthates to dixanthogen on pyrite is coupled with the reduction reaction of surface-ferric hydroxide to ferrous ions, leading to the dissolution of hydrophilic ferric hydroxide and growth of hydrophobic dixanthogen on the surface of pyrite. Flotation of pyrite is presented as a function of pH using various ethyl xanthate concentrations. The floatability results are explained in terms of the surface coverage relationship between ferric hydroxide and dixanthogen, which is pH dependent.     

The adsorption of aqueous heavy metals on inorganic minerals

Two models have been used to explain the in-situ control of heavy metals: (1) solubility controls, where precipitation of a solid phase occurs under varying metal and ligand concentrations, and (2) surface chemical controls, where adsorption or exchange occurs at the solid/solution interface. Based on experiments presented in this paper, surface chemical controls can account for the removal of heavy metals, particularly Zn(II), from metal solutions which are undersaturated with respect to the hydroxide, oxide, or other controlling solid phases. Adsorption isotherms are presented for varying solution pHs, total metal ion concentrations, ionic strengths, and mineral substrates. The minerals chosen for illustration are SiO₂, TiO₂, FeOOH, Al₂O₃, MnO_x and HgS which range widely in surface acidity, electrical double layer properties, specific surface areas, and surface functional groups.     

Potassium Chloride Treatment to Control Alkali Induced Heave in Black Cotton Soil

The results presented in this paper shows that high concentrations of sodium hydroxide causes abnormal changes on the volume change behaviour of illite–smectite (interstratified mineral) soil due to mineralogical changes. The higher swell that occurs is shown in the form of a new second stage of swelling. Increase in negative charges on soil particles and mineralogical changes after interaction with soil, respectively, are responsible for the swelling in these two stages. However, potassium hydroxide does not induce such high swelling in soils. This is mainly due to the fixation of potassium ions. Hence an attempt has been made to control the swelling induced by sodium hydroxide by making used of potassium chloride as an additive. Potassium fixation which is not substantial at neutral pH is favoured at higher pH Addition of potassium chloride salt solution (as 2 and 5% solution) can reduce only the first stage of swelling by linking the unit layers of mineral by reducing development diffuse double layer near clay surface. Potassium chloride is unable to prevent the formation of mineralogical alteration due to soil alkali interaction and hence the swelling associated with mineralogical changes. X-ray diffraction studies have revealed that mineralogical changes leading to formation of zeolite by soil alkali interaction is not inhibited by potassium ions. Morphological changes studied by scanning electron microscope corroborate these observations. Also the compressibility of soil which is increased in alkali solution is reduced in the presence of potassium salts. This reduction is due to reduction in the first stage of swelling.     

溶液介质条件对重金属离子与石英表面反应的影响

实验研究表明,随着溶液ＰＨ值的升高石芟夺Ｃｕ＾２＋、Ｐｂ＾２＿、Ｃｄ＾２＋等重金属离子的吸附量和表面吸附覆盖率逐渐增大,而表面反应产物的结合开矿相应地出现由单核化合物、多核化合物〖ＳＯＣｕ４（ＯＨ）３＾４＋〗,直至表面沉淀（ＳＯＨ…Ｃｕ（ＯＨ）２（ｓ）〗。随着温度升高,石英对Ｃｕ＾２＋、Ｐｂ＾２＋、Ｃｄ＾２＋等重金属离子的吸附量逐渐减是随着溶液离子强度的增大,石英对Ｃｕ＾２＋离子的吸附量和表面离了     

ZH型重金属螯合纤维对水溶液中Sr2+的吸附行为

研究了ZH型重金属螯合纤维对水溶液中Sr~(2+)的吸附行为,考察了pH值、纤维加入量、Sr~(2+)初始浓度、作用时间等对吸附行为的影响,并采用SEM、EDS和FTIR等现代分析测试手段探讨了ZH型重金属螯合纤维对Sr~(2+)的吸附机制。结果表明,在pH值为7.0、纤维加入量为2.0 g/L、Sr~(2+)初始质量浓度为50 mg/L的条件下,纤维对Sr~(2+)的吸附在4 h左右基本达到平衡。实验条件下ZH型重金属螯合纤维对Sr~(2+)的最大吸附量可达26.22 mg/g。等温吸附拟合结果表明,ZH型重金属螯合纤维对Sr~(2+)的吸附可能是以单分子层为主的单分子层和多分子层吸附共同作用的结果。纤维对Sr~(2+)的动力学吸附过程符合准二级动力学模型。红外光谱分析表明Sr~(2+)与纤维上—NH_2和—COOH等基团进行配位络合从而吸附在纤维表面,—CH_2—和C=CH_2等基团参与此吸附过程。能谱分析表明Sr~(2+)与纤维上Na~+和Ca~(2+)还存在着离子交换作用。     

The impacts of common ions on the adsorption of heavy metal

Researches on the impact of common ions onto sediments are of great importance for the study of the heavy metal adsorption mechanisms. Considering the surface sediments from the relatively clean reach in the Baotou section of the Yellow River as the adsorbent, this work presents the impacts of common ions (Na⁺, Mg²⁺, K⁺, Ca²⁺, Cl⁻, SO₄ ²⁻, and NH₄ ⁺) on heavy metals (Cu²⁺, Zn²⁺, Cd²⁺, and Pb²⁺) adsorption. The experimental results reveal that the adsorptive capacities of the heavy metals are controlled by different adsorption mechanisms in different ion concentration ranges. With the increase of the ionic strength, the adsorption of the heavy metals increases for the compression of the electric double layer, whereas decreases for the decreasing of the ionic activities of the heavy metals. The competitive adsorption and complexations between the heavy metals and common ions are also important factors controlling the heavy metal adsorption. According to the experimental results and the real concentration of common ions in the Baotou section of the Yellow River, the increase of the concentrations of Na⁺, Mg²⁺, K⁺, and Ca²⁺ would cause the increase of Zn²⁺ adsorption and reduce the Zn pollution. The NH₄ ⁺ from the industrial discharge of the tributaries has a strong impact on the heavy metal adsorption.