Adsorption of copper (II) on mesoporous silica: the effect of nano-scale confinement

Nano-scale spatial confinement can alter chemistry at mineral–water interfaces. These nano-scale confinement effects can lead to anomalous fate and transport behavior of aqueous metal species. When a fluid resides in a nanoporous environments (pore size under 100 nm), the observed density, surface tension, and dielectric constant diverge from those measured in the bulk. To evaluate the impact of nano-scale confinement on the adsorption of copper (Cu²⁺), we performed batch adsorption studies using mesoporous silica. Mesoporous silica with the narrow distribution of pore diameters (SBA-15; 8, 6, and 4 nm pore diameters) was chosen since the silanol functional groups are typical to surface environments. Batch adsorption isotherms were fit with adsorption models (Langmuir, Freundlich, and Dubinin–Radushkevich) and adsorption kinetic data were fit to a pseudo-first-order reaction model. We found that with decreasing pore size, the maximum surface area-normalized uptake of Cu²⁺ increased. The pseudo-first-order kinetic model demonstrates that the adsorption is faster as the pore size decreases from 8 to 4 nm. We attribute these effects to the deviations in fundamental water properties as pore diameter decreases. In particular, these effects are most notable in SBA-15 with a 4-nm pore where the changes in water properties may be responsible for the enhanced Cu mobility, and therefore, faster Cu adsorption kinetics.     

Studies on the recovery of uranium from nuclear industrial effluent using nanoporous silica adsorbent

In this paper, the sorption of uranium onto nanoporous silica adsorbent in the presence of nitrate, sulfate, chloride, fluoride and phosphate was studied. The effect of contact time between the nanoporous sorbent and aqueous solution, pH and initial concentration of uranium was also investigated. Uranium sorption onto nanoporous silica adsorbent is a very fast process as sorption rate increases with pH increment. Optimum pH for uranium sorption was 4?C8. Experimental sorption isotherm is successfully described by Langmuir and Freundlich models. The results obtained by batch experiments showed that the presence of high concentration of nitrate, sulfate, chloride and phosphate anions alone had no interference with uranium recovery. However, the presence of fluoride ions (>250?mg/L) decreases uranium sorption by about 55?%. The results also showed that the presence of phosphate ions (about 300?mg/L) in solution could remove fluoride interference completely. Finally, the efficiency of the nanoporous silica adsorbent for uranium recovery from wastewater of the uranium conversion facility was investigated.     

Adsorption of copper onto goethite in aqueous systems

The adsorption of copper(II) onto goethite was studied as a function of pH, total dissolved copper concentration, surface area of goethite, and ionic strength. The adsorption of copper was similar to that of other hydrolyzable metals. A tenfold increase in goethite surface area had a significant effect on the adsorption edge, but a tenfold increase in the ionic strength of the medium did not effect the adsorption edge. The distribution coefficients increase sharply with increase in pH and ranged from 10 to 60,000 ml/g over a range of two and half pH units, depending on the goethite surface area and copper concentration. A tenfold decrease in ionic strength as well as a tenfold increase in surface area of goethite did not have any effect on the magnitude of distribution coefficients. Distribution coefficients were used to calculate the number of protons released per mole of copper adsorbed during the adsorption process. The average number of protons released per mole of copper adsorbed was estimated to be 1.40 ± 0.10.Managed by Martin Marietta Energy System, Inc., for the U.S. Department of Energy under contract no. DE-AC05-840R21400.     

Adsorption of copper and zinc by oil shale

 Oil shale is able to remove appreciable amounts of copper and zinc ions from aqueous solutions. It was noted that an increase in the adsorbent concentration with constant copper or zinc concentration resulted in greater metal removal from solution. An increase in the copper or zinc concentration with a constant sorbent concentration resulted in higher metal loading per unit weight of sorbent. For both metals, copper and zinc, equilibrium was attained after 24-h contact time. Increase in the initial pH or temperature of the metal solution resulted in an increase in the metal uptake per unit weight of the sorbent. Freundlich isotherm model was found to be applicable for the experimental data of Cu²⁺ and Zn²⁺. The results showed that oil shale could be used for the adsorption of the Cu²⁺ and Zn²⁺ with higher affinity toward Zn²⁺ ions. Addition of sodium salt to the metal solution influenced copper removal positively, but inhibited zinc removal. Received: 3 January 2000 · Accepted: 27 June 2000     

Complexation of copper with polymeric silica in aqueous solution

A series of experiments was conducted to study the uptake of Cu by colloidal SiO₂ in aqueous solution. Solutions consisting of 2400 mg l⁻¹ monomeric SiO₂ were allowed to polymerize for 24 h at pH values from 4 to 9, producing coexisting populations of monomer and polymer in each solution. These solutions were combined with aqueous CuCl₂ solutions in final Cu concentrations of 5–30 mg l⁻¹. After the solutions had equilibrated for 24 h, they were filtered through 0.1 μm Millipore filters and analyzed by ICP-AES and gel filtration chromatography (GFC).Experiments conducted at pH 7 with varying Cu concentrations yielded a critical coagulation concentration of 15±1 mg l⁻¹ Cu. GFC analyses of solutions in which coagulation occurred revealed no SiO₂ polymer in the filtrates, suggesting that coagulation is due to the coalescence of SiO₂ polymers by Cu. Experiments conducted with 20 mg l⁻¹ Cu exhibited a gradual increase in Cu uptake from pH 5 to 7, followed by a sharp decrease in Cu uptake from pH 7.25 to 7.50. The gradual increase in Cu uptake up to pH 7 may reflect the increasingly negative surface charge of SiO₂ polymer with increasing pH. The abrupt decrease in the adsorption of Cu to SiO₂ polymer at pH values > 7.25 may be attributed to the decrease in dissociated Cu²⁺ relative to Cu(OH)₂° at higher pH. Although it is traditionally held that the formation of Cu silicates, such as chrysocolla, occurs under acid conditions in supergene Cu deposits, this investigation suggests that Cu silicate formation may be favored in near-neutral solutions in nature.     

泥沙颗粒表面铜离子吸附分布的模拟分析

泥沙颗粒的表面形貌与污染物质的吸附关系较少受到关注。采用场发射枪扫描电子显微镜进行泥沙颗粒表面形貌的研究与探测吸附作用后铜离子在泥沙颗粒表面的分布,模拟分析了铜离子的吸附分布规律。研究结果表明泥沙形貌对铜离子的吸附分布有重要影响,在泥沙颗粒表面的边脊和凹谷处吸附铜离子数量较多,在其它形貌特征处的铜离子吸附数量相对较少。曲率C_u反映了复杂形貌对于铜离子的吸附能力,当C_u=1.1时该区域吸附铜离子最多。     

海纹石的宝玉石矿物学特征

对产于多米尼加的海纹石样品进行了矿物学测试和分析.镜下观察显示,海纹石呈致密的纤维状结构,纤维长约0.01～0.02 mm;X射线衍射表明,海纹石样品主要由针钠钙石组成,并未检测到其它杂质成分,与能谱分析结果一致;不同色调的海纹石样品在红外光谱和紫外-可见光吸收光谱上都没有表现出本质的差别.     

天然黄铁矿对阳离子有机染料RhB吸附特性研究

以黄铁矿作为吸附剂研究罗丹明B(Rhodamine B,RhB)的吸附特性,用X射线衍射仪(XRD)、扫描电子显微镜(SEM)对黄铁矿进行了表征。考察了接触时间、溶液pH值、离子强度、温度等对黄铁矿吸附RhB的影响。结果表明,在吸附平衡时间120 min、pH值4.0时,吸附量达到最大值21.3 mg/g。升高温度,黄铁矿对RhB的吸附量逐渐增大。而离子强度对吸附几乎没有影响。实验数据与Langmuir吸附模型拟合良好,整个吸附动力学模型符合准二级吸附动力学模型。热力学研究证实了该吸附过程是自发进行的。通过对吸附反应结束后的黄铁矿进行煅烧处理,去除表面吸附的RhB,结果表明煅烧一次的黄铁矿仍然可以吸附废水中约50%的RhB,具有重复利用的价值。     

电气石矿物吸附铜离子试验研究

本文研究了电气石的单晶、电气石微粉对Cu2＋的吸附作用,试验表明：电气石单晶体表面存在着以C轴为两极的静电场,该静电场对Cu2＋的吸附作用效果明显。制备的电气石微粒越细,吸附效果越好。电气石的电场效应使得它在治理污水中Cu2＋污染具有广阔的前景。     

Adsorption of copper and cobalt from fresh and marine systems

The adsorption of copper and cobalt from aqueous solution on to illite and other substrates has been studied as a function of pH, solution composition and solid phase concentration. The results are interpreted in terms of a model whereby the trace metals are adsorbed in exchange for surface bound H⁺ ions. Adsorption varies with solution ionic strength and the concentrations of complex forming ligands; both of these parameters tend to reduce the trace metal adsorption. The Cu²⁺ is two orders of magnitude more reactive toward solid surfaces than Co²⁺ , which is consistent with the general reactivities of these two metal ions. It is also found that Mg₂₊ interferes with adsorption, presumably by competing with the trace metals for the surface sites. A quantitative model was developed which describes adsorption of these metals from natural waters ranging from river water to sea water as a function of pH, complexing ligands and magnesium activity.     

黄土对Cr(III)的吸附特性及机理研究

铬是一种重金属痕量元素,人体通过食物链摄入过量的铬会在人体内富集,随之产生中毒反应。研究Cr(III)的浓度、反应时间、反应温度、pH值等因素对Cr(III)在黄土上吸附特性的影响,结果表明黄土对Cr(III)的吸附非常迅速,并且吸附量非常大,等温吸附模型Freundlich和Dubinin-Radushkevich(D-R)模型都能很好地解释Cr(III)在黄土上的吸附过程。热动力学分析表明,吸附是一个自发的过程,升温可促进吸附作用的进行。随着温度的不断升高,Cr(III)的吸附量逐渐增大。溶液的pH值是影响Cr(III)吸附效果的一个重要因素,当pH>6时,Cr(III)几乎完全被去除。利用X光衍射图谱和红外光谱分析,探讨黄土与Cr(III)的结合机制,黄土中的高岭土、石英等黏土矿物以及有机质成分对吸附过程起重要作用。     

Adsorption characteristics of heavy metals in soil zones developed on spilite

Various soil zones such as Bw, C1, and C3 are developed on spilite. Montmorillonite, vermiculite and chlorite is moderately occurred in the C1 and C3 soil zones, in contrast montmorillonite and vermiculite are absent in Bw soils whereas illite and sesquioxide are relatively increased. The high cation exchange capacity (CEC) of montmorillonite and vermiculte and moderate CEC of chlorite and illite resulted in the high adsorption of heavy metals. The adsorption of the heavy metals on spilite soil zones was studied at different concentrations and pH levels. Heavy metals like lead, cadmium, and copper were selected for adsorption studies considering their contribution as toxic metals in the environment. The initial solute concentrations ranged from 7.0 × 10⁻³ to 1.0 × 10² mg/L. The sorption behavior of Cd²⁺, Pb²⁺, and Cu²⁺ on soil zones of spilite was investigated using the batch equilibrium technique at 25°C. The characteristics of the adsorption process were investigated using Scatchard plot analysis (q/C vs. q) by the batch equilibrium technique at 25°C. In the adsorption of heavy metals, deviation from linearity in the plot of q/C versus q was observed, indicating the presence of multi-model interaction and non-Langmuirean behavior. When the Scatchard plot showed a deviation from linearity, greater emphasis was placed on the analysis of the adsorption data in terms of the Freundlich model, in order to construct the adsorption isotherms of the metal(s) at particular concentration(s) in solutions. The adsorption behavior of these metal ions on spilite soil zones is expressed by the Freundlich isotherms. Adsorption constants and correlation coefficients for the Cd, Pb, and Cu on spilite soil zones were calculated from Freundlich plots.     

Adsorption of copper(II) from aqueous solution by Beidellite

Dry lakes, degraded sandy grasslands, abandoned farmland and mobile dunes which are widely distributed throughout the arid areas of northern China have been investigated in this work. Gain-size distribution of the surface sediments of Manas lake in Junggar basin, Juyan lake in the Alxa plateau, Zhuye lake in Minqin basin and most deserts (such as Mu Us desert, Otindag desert, Horqin desert and Hulun Buir desert) in China have been analyzed. The results show clay with particle sized <10 μm on the surface sediments of dry lakebed and sandy grassland developed from dry lakebed, respectively, account for >60% and ∼50% of the total mass. Since the tiny particles on the surface of abandoned farmland are blown away easily and rapidly, the content of clay particles in Minqin basin is <14%. The grain-size distribution of mobile dunes in northern China mainly consists of particles >63 μm and few particles <10 μm. Consequently, although sand/dust storms originate primarily in the western deserts, the gobi areas of the Alxa plateau, the north and east of Hexi Corridor and in central Mongolia, the widely distributed dry lakebeds, sandy grasslands and abandoned farmland adjacent to the deserts also contribute to aeolian dusts. Hence, the material sources for sand dust storm in East Asia include inland deserts, but also dry lakes, sandy grasslands and abandoned farmland, which are widely distributed throughout the arid inlands of northern China.     

Adsorption of chromium and copper in aqueous solutions using tea residue

In this study, adsorption of copper and chromium was investigated by residue of brewed tea (Tea Waste) from aqueous solutions at various values of pH. It was shown that adsorbent dose, copper and chromium ion concentrations in such solutions influence the degree of these heavy metal ions’ obviation. The adsorption level of the prepared solutions was measured by visible spectrophotometer. The tea residue adsorbed copper (II) and chromium (VI) ions at initial solution pH by 25 % and 3 %, respectively. During the experiments the peak adsorption occured in hydrated copper nitrate aqueous solution at pH range of 5–6. Likewise the maximum adsorption appeared in potassium chromate aqueous solution at pH range of 2–3. In addition, tea residue adsorbed about 60 mg/g of copper (II) ion at pH=5, while chromium adsorption was registered at about 19 mg/g at pH=2. The data obtained at the equilibrium state, was compared with Langmuir and Freundlich models. Results showed that regarding the kinetics of adsorption, the uptake of copper (II) and chromium (VI) ions by tea residue was comparatively faster, with the adsorption process exhaustion completed within the first 20 min of the experiments. Furthermore, results revealed that adsorption data concerning the kinetic phase is closely correlated with a pseudo-second order model with R²> 0.99 for copper (II) and chromium (VI) ions     

Adsorption of copper and zinc onto natural clay in single and binary systems

Calcareous and smectitic clay samples from the Coniacian–Lower Campanian system, Tunisia, were used as adsorbents for the removal of copper and zinc from aqueous solutions in single and binary systems. Calcareous clay sample was treated with acetic acid to obtain carbonate-free sample that was also used for metals removal. The adsorption of metal ions onto natural clay was tested in a batch method by mixing 1 g/L of each sample with a metal ion solution of zinc (300 μmol/L) and/or copper 600 μmol/L under the operating pH of 6, and agitation speed of 200 rpm within the equilibrium time of 60 min at 25 °C for single and binary systems. Our results showed that natural clay samples were mainly composed of silica, alumina, iron, and magnesium oxides. Adsorption data showed that the studied clay samples removed substantial amounts of heavy metals in single and mixed systems. Initial solution pH and carbonates contents enhanced the removal capacities of the studied clay samples, confirming their strong influencing effects. Thermodynamic parameters indicated an endothermic adsorption for metals removal by calcareous clay, but exothermic process for the smectitic sample. These results suggest that the Late Cretaceous clays, Tunisia, can be effectively used as natural adsorbents for the removal of toxic heavy metals in aqueous systems.     

颗粒煤超临界态甲烷吸附相密度特征研究

查明颗粒煤超临界态甲烷吸附相密度特征是研究温度、压力影响煤样吸附甲烷量的基础。选用安阳–鹤壁煤田鹤壁六矿与龙山矿颗粒煤样,借助磁悬浮天平等温吸附仪测量温度为308、313和318 K,压力为1~24 MPa下的等温吸附线。利用截距法、Langmuir三元模型拟合法与液相密度法分别计算超临界甲烷吸附饱和时的吸附相密度,分析其影响因素,并通过定吸附相体积的方法,一方面计算未吸附饱和时的吸附相密度,对峰值型拐点与过剩吸附量出现负值的实验现象进行解释,另一方面校正出较为理想的绝对吸附量。吸附相密度的计算结果表明,甲烷吸附相密度受温度、压力和煤变质程度的影响:随温度升高而降低,随压力升高先快速增加,后逐渐变缓,测量范围内吸附饱和时,无烟煤吸附相密度为121.60~136.17 kg/m3,贫瘦煤为73.29~76.96 kg/m3;绝对吸附量的计算结果表明,采用液相密度法校正出的绝对吸附量会出现负值,明显与实际不符,用截距法和Langmuir三元模型法校正的绝对吸附量会因实验条件的变化而改变,结合吸附常数b值的变化规律,发现用Langmuir三元模型法描述超临界甲烷的吸附行为最为恰当。      

纳米比亚西南部斑岩型铜矿地质特征

纳米比亚西南部奥兰治河海伯地区是纳米比亚重要的铜矿产地之一,区内的海伯铜矿和罗雷铜矿具有明显的斑岩型成矿特征。控制铜矿的斑岩体为古元古代威尔斯锥夫岩基的岩枝、岩株状分支,矿体的围岩为古元古界奥兰治河群海伯亚群。威尔斯锥夫岩基与奥兰治河群均为钙碱性火成岩和火山-沉积岩组合,形成于大陆边缘俯冲带的构造背景环境,结合海伯铜矿和罗雷铜矿地质及同位素特征,文章认为该区斑岩型铜矿可能为板块构造成矿。     

Don Javier斑岩型铜钼矿床地质特征

Don Javier矿床是在秘鲁南部新发现的大型斑岩铜钼矿床,位于秘鲁古近纪斑岩型铜钼成矿带内。该矿区主要出露Yarabamba花岗闪长岩体,NW走向的矿体赋存于英安斑岩及其围岩中。主要的矿石矿物有黄铜矿、辉钼矿、辉铜矿等。矿化蚀变由内向外依次为钾化、石英-绢云母化、泥化、青磐岩化,具有典型斑岩型铜矿床的蚀变分带特征。矿体呈筒状,主要分布于石英-绢云母化蚀变带中。矿区内的英安斑岩有4期,其中的前2期与矿化有关,后2期为成矿后侵位。NW向断裂是区内主要的控矿构造,对成岩成矿具有控制作用。与同一成矿带内相邻的Cerro Verde超大型斑岩型铜矿床相比较,两者具有类似的成矿特征。找矿实践表明,强烈的蚀变带、低阻高极化激电异常是找矿的有效标志。     

青海省绿梁山铜矿床地质特征研究

青海省绿梁山铜矿床位于南祁连地块与柴达木地块拼接部位北缘,是我国西部重要的多金属矿床之一.通过对矿床的地质特征进行详细研究和系统总结认为:该矿床矿体主要赋存于滩间山群变质火山岩中,其围岩蚀变有硅化、黄铁矿化、黄铜矿化、磁铁矿化、绿帘石化及绿泥石化等;矿石类型主要为含石英细脉、网脉蚀变岩型铜矿石;矿床类型属破碎带蚀变岩型铜矿床.结合以上特征,总结了绿梁山铜矿床找矿标志,指出了下一步找矿方向,为该区相同类型矿床的勘查工作提供了思路和理论依据.