叔胺萃取分离钴(Ⅱ)、铁(Ⅱ)

研究了不必预先氧化二价铁,直接用叔胺从氯化物溶液中萃取分离钴(Ⅱ)、铁(Ⅱ)的新方法.考察了不同改性剂对叔胺萃取钴(Ⅱ)、铁(Ⅱ)的影响以及各种因素对钴(Ⅱ)、铁(Ⅱ)萃取、洗涤及反萃的影响.提出了用叔胺萃取分离钴(Ⅱ)、铁(Ⅱ)的最佳工艺参数.     

仲辛基苯氧乙酸萃取Zn(II)的性能

研究了一种新型萃取剂仲辛基苯氧乙酸(CA–12)的皂化以及从盐酸介质中萃取Zn(II)的性能. 考察了萃取温度、平衡水相酸度、萃取剂浓度等因素对萃取的影响. 氨水皂化CA–12的最佳条件是使用含有1.0 mol/L NaCl的稀氨水制皂、皂化率为80%；分配比随平衡水相酸度的增加而减小，且lgD与pH呈线性关系，其斜率约为2；分配比随萃取剂初始浓度的增大而增大；初始酸度pH=6.0~6.5、萃取剂初始浓度CHA>0.10 mol/L时，水相中0.01 mol/L Zn(II)几乎被定量萃取. 计算得到了CA–12从盐酸介质中萃取Zn(II)的过程热效应DH=3.28 kJ/mol.     

球形零价铁生物炭吸附Cd(II)的性能和机制

本研究提供了一种一步热解法制备纳米零价铁生物炭的方法。将海藻酸铁在高温缺氧条件下热解制备了球形零价铁生物炭复合材料（ZVIBC），考察了Cd(II)溶液pH、初始浓度、吸附时间、背景离子、空气中老化时间对ZVIBC吸附Cd(II)性能的影响，通过FTIR、XRD、XPS、EDS等方法对ZVIBC以及ZVIBC-Cd(II)进行了表征，研究了ZVIBC对Cd(II)的吸附机理。结果显示：pH对ZVIBC吸附Cd(II)有显著的影响，4为最佳吸附pH条件。ZVIBC吸附Cd(II)的过程符合Langmuir模型，拟合的饱和吸附量为240 mg/g。主要吸附机理为：活性官能团（O—H、C—O、C=C、C=O、COO）与Cd(II)形成配合物，以及Cd(II)与Fe2+生成Cd(OH)2沉淀。     

电渗析与萃取耦合技术分离Ni(II)与Co(II)

为实现混合溶液中Ni(II)与Co(II)的分离,设计了电渗析与萃取耦合的集成分离技术,借助自行设计的设备,在选P507为萃取剂后,考察了电流密度、酸用量、体积流量、萃取剂皂化率、原料与萃取剂摩尔比、萃取方式等对分离效果的影响.结果表明:在实验范围内,电流密度3.8 mA/cm2,酸用量为理论用量的1.3倍,体积流量60 L/h、皂化率60%,原料与萃取剂摩尔比1:1.7为优取的操作条件;料液循环重复萃取,能显著提高分离效果.由此表明,电渗析与萃取耦合的分离技术,可分离混合体系中的Ni(II)、Co(II),且无需溶剂参与.     

三价铁离子浓度对As(V)-Fe(II)-Fe(III)体系沉淀臭葱石的影响

在常压、95℃、初始pH=1.5的条件下,研究了As(V)–Fe(II)–Fe(III)体系中初始Fe(III)浓度对砷的去除率和臭葱石合成的影响。结果表明,溶液中初始Fe(III)/As(V)摩尔比为0时,沉淀产物为结晶度良好的臭葱石,但砷的去除率仅为24.3%,沉淀浸出砷浓度高于国标规定的浓度限值5 mg/L。溶液中初始Fe(III)/As(V)摩尔比大于0时,在升温过程中生成了无定形砷酸铁,当初始Fe(III)/As(V)摩尔比不超过1.6时,砷酸铁反应8 h后转化为臭葱石;随初始Fe(III)/As(V)摩尔比增大,砷的去除率增大,臭葱石沉淀的结晶度降低、浸出砷浓度降低;其中,初始Fe(III)/As(V)摩尔比为0.8和1.6时,臭葱石沉淀的浸出砷浓度低于5 mg/L,适合安全堆存。当初始Fe(III)/As(V)摩尔比大于1.6时,无定形砷酸铁反应8 h仍不能转化成臭葱石,砷的去除率降低,沉淀浸出砷浓度超标,不适合安全堆存。     

人工神经网络光度法同时测定水中Fe(II)、Fe(III)

应用径向基函数人工神经网络(RBF)和误差反向传播神经网络(BP),采用磺基水杨酸-邻菲罗啉双显色剂光度法同时分析了水中Fe(II)和Fe(III)。实验证明,RBF算法在所需神经元个数、训练时间、预测准确度等方面均明显优于BP网络算法。该技术和光度法结合有望成为多组分分析的有效选择方法之一。     

Nitroso-R光度法检测湿法炼锌净化渣中的Co(Ⅱ)

湿法炼锌净化渣中的钴是重要的二次资源,测定钴含量是钴合理回收的基本条件。在pH=7.5时,亚硝基R盐与Co(II)形成络合物并被氧化形成Co(Ⅲ)的稳定络合物,并以浓硫酸破坏样品中干扰离子的络合物,消除干扰。在波长λ=522 nm检测,检测限为0.027 4μg/mL(n=6),在0~5.0μg/mL范围内符合比尔定律。方法用于检测样品中的钴含量为2.80%,ICP检测结果为2.89%,结果满意。     

水葫芦对水中Pb(Ⅱ)的吸附性能研究

通过静态吸附实验,研究了干体水葫芦对水中的重金属离子Pb(II)的吸附性能,考察了吸附剂投加量、重金属溶液起始浓度、溶液起始pH值及吸附时间对Pb(II)去除效果的影响。研究结果表明,水葫芦对Pb(II)吸附效果明显优于桔子皮、木屑和玉米芯屑,具有吸附时间短、投加量少、适应pH值范围广的特点。     

改性膨润土对废水中Cd(II)的吸附特征及吸附动力学研究

为探讨改性膨润土对Cd(II)的吸附特征及吸附动力学机制,通过吸附实验探讨了pH值、初始浓度和吸附时间对改性膨润土吸附Cd(II)的影响。结果表明,盐酸改性膨润土对Cd(II)的去除率表现为随溶液pH值升高而升高,而氢氧化钠改性膨润土、膨润土与十二烷基磺酸钠改性膨润土的去除率分别在pH=6和7时达到最大值。膨润土及改性膨润土对Cd(II)的去除率随初始浓度的增加而降低,吸附量随平衡浓度增加而增大,并趋向平稳,吸附符合Langmuir方程,吸附为单分子层吸附。膨润土及改性膨润土的吸附反应在240 min内基本达到平衡,吸附动力学分析表明吸附过程更符合准二级动力学模型,吸附过程以化学吸附为主,膨润土及改性膨润土的吸附速率大小依次为K2HCl-B＞K2NaOH-B＞K2B＞K2SDS-B,液膜扩散与颗粒内扩散过程均为控速步骤。该研究可为改性膨润土处理含镉废水和修复镉污染土壤提供参考。     

钴掺杂NaP分子筛合成及其吸附Pb(II)性能

以硅酸钠和偏铝酸钠为原料,通过水热合成法制备钴掺杂NaP分子筛,通过X射线衍射光谱(XRD)、扫描电子显微镜(SEM)、N₂吸附-脱附等表征手段对样品的晶相、形貌和孔结构进行表征分析,并对其Pb(II)吸附性能进行评价。结果表明:与未掺杂钴的NaP分子筛相比,掺杂量为n(Al₂O₃)∶n(Co(NO₃)₂)=8∶1的Co-NaP分子筛的比表面积增大了约5倍(从26.767 m²/g增大到162.490 m²/g);其孔容约增大了约2.5倍(从0.029 cm³/g增大到0.104 cm³/g)。吸附时间为120 min,吸附温度为25 ℃,Pb(II)初始浓度为100 mg/L时,Co-NaP分子筛对Pb(II)的去除率可达98.8%,以乙二胺四乙酸二钠为再生助剂,在30 ℃下再生30 min,可使吸附后时Co-NaP分子筛完全再生,再生后的吸附剂经过3次吸附-再生循环后,Pb(II)去除率仍可达97%。     

THE EXTRACTION OF COBALT(II) FROM A THIOCYANATE MEDIUM BY SOME DIAMINE AND MONOAMINE EXTRACTANTS DISSOLVED IN 5% ISODECANOL - BENZENE

The tertiary amine extractants N,N,N’,N’-tetra-n-octylethylenediamine, N,N-di-n-octyl-2-(aminomethyl)pyridine and Alamine 336 were used to extract cobalt(II) from a thiocyanate medium. The extraction equilibria were identified and the extraction constants for these equilibria are presented.

Thiocyanic and sulphuric acid extraction was investigated. The protonation constants of the tertiary amines with these acids are reported.

The potential of the chelate mode, displayed by tertiary diamine extractants, was evaluated. The extraction properties of tertiary diamine extractants were demonstrated to be superior to a tertiary monoamine extractant, Alamine 336.     

Synergistic extraction and separation of Fe(III) and Zn(II) using TBP and D2EHPA

Waste chloride pickle liquors from hot-dip galvanizing plants, steel plants and flue dust contain reasonable amounts of heavy metals such as Zn, Cr, Ni, etc. Iron is invariably associated with most of these materials and comes into solution during leaching. Thus, the synergistic extraction of zinc(II) and iron(III) from leach solutions in tri-n-butyl phosphate (TBP)–di(2-ethylhexyl) phosphoric acid (D2EHPA) system diluted in kerosene was investigated. The Zn and Fe concentrations in the leach liquor used in the present study were 2 g/L. Experiments were carried out in the pH range of 0.5–4.0, temperature of 25°C, using sole D2EHPA, sole TBP and D2EHPA–TBP mixtures at different ratios. Results showed that the co-extraction of zinc(II) and iron(III) increased with increasing equilibrium pH using D2EHPA. It is demonstrated that the mixtures of TBP and D2EHPA are more efficient and selective than D2EHPA alone. At low pH values, the separation factor is low when pure D2EHPA is used as an extractant; however, using TBP as a synergist, the separation factor increases and results in a better separation of zinc from iron. Increasing TBP to D2EHPA ratios in the organic phase caused a slight shift to the right in the extraction isotherm of iron and a marked shift to the right in the extraction isotherm of zinc, and the maximum separation factor of 13.3 × 10³ was achieved at a TBP to D2EHPA volume ratio of 4:1 (0.58 M TBP: 0.12 M D2EHPA). Furthermore, the effect of equilibrium pH, organic to aqueous phase ratio and Cl^? concentration on the selective extraction was investigated. Using two extraction stages at the O/A ratio of 2:1 and pH_e (equilibrium pH) of 3 and 1 for zinc and iron, respectively, 99% of zinc(II) and 96.25% of iron(III) were extracted.     

Selective Transport of Cu(II) across a Polymer Inclusion Membrane with 1-Alkylimidazole from Nitrate Solutions

The selective transport of copper(II), zinc(II), cobalt(II), and nickel(II) ions from nitrate solutions across polymer inclusion membranes (PIMs), which consist of cellulose triacetate as polymeric support, o-nitrophenyl pentyl ether as plasticizer, and 1-alkylimidazole (alkyl from hexyl- to decyl) as ion carrier was reported. PIM was characterized by using atomic force microscopy (AFM) technique. The results show that Cu(II) can be separated very effectively from other transition metal cations as Zn(II), Co(II), and Ni(II) (at a concentration of 10^?3 mol/dm³ each). Alkyl substituents at position 1 of the imidazole ring have been found to affect the hydrophobic properties and initial flux of the transported metal ions. The efficiency of separation of metal ions by 1-alkylimidazole followed the sequence: Cu(II) > Zn(II) > Co(II) > Ni(II). The highest selectivity coefficient for Cu(II) was found with 1-hexylimidazole and its 1 mol/dm³ solution in PIM. Separation of the ions was more effective for the nitrates(V) than for chlorides.     

Separation and concentration processes of solutions of Co(II), Ni(II), Cr(III), Fe(III) and Mn(II) by extraction with toluene-dissolved rosin

The extraction and stripping of Co(II), Ni(II), Cr(III) and Fe(III) from aqueous solutions by rosin dissolved in toluene has been investigated. Results obtained show that rosin is better extractant than abietic or n-lauric acids under comparable conditions. From these results, and the data of Mn(II) solvent extraction studied previously under the same conditions, a separation and concentration process for these five cations in aqueous solutions has been designed. Saturated solutions of Fe(III), Cr(III), Mn(II) and finally Co(II) and Ni(II) have been obtained successively by extraction and stripping, by addition of ammonium hydroxide to obtain the appropriate pH value, and by modifying adequately the organic phase/aqueous phase volume ratio.     

Solvent-Extraction Behavior of Cobalt(II), Nickel(II), Copper(II), and Palladium(II) with Tri-n-butylphosphate

Abstract

A systematic study of the extraction behavior of cobalt(II), nickel(II), copper(II), and palladium(II) with TBP from thiocyanate system in various ranges of acid concentrations has been performed. The thiocyanate medium leads to enhanced extractions in all these cases compared to those in the previously used chloride medium. For palladium, the chloride and nitrate systems have been critically examined. Sixty-two per cent extraction occurs from 4 M hydrochloric acid using 100% TBP in a single run and the extraction becomes quantitative (>99%) after four successive equilibrations. A simpler method has been proposed for rapid extraction of palladium(II) as the thiocyanate complex. Quantitative extraction occurs in the presence of 1.2% thiocyanate solution from 0.5 to 2 M hydrochloric acid (initial) up to pH 8.0. The extractable species of cobalt(II), nickel(II), copper(II), and palladium(II) from thiocyanate medium are probably similar and of the type [M(CNS)₄]^2? [K·TBP·3H₂O]₂ ⁺ (buffer solution) and [M(CNS)₄]^2? [H·TBP·3H₂O]⁺ ₂ (acid solution). A simple extraction scheme has been worked out for the separation of palladium(II) from iron(III), cobalt(II), nickel, manganese(II), copper(II), and platinum.     

Sorption of Pb(II), Cd(II) and Zn(II) by iminodiacetate chelating resins in non-competitive and competitive conditions

Two chelating resins (CRs) bearing iminodiacetate (IDA) groups derived from acrylonitrile - divinylbenzene (AN-DVB) copolymers having 10 and 15 wt.% nominal cross-linking degrees and a high mobility of the functional groups caused by the presence of a longer spacer between the matrix and the IDA groups were synthesized and tested as sorbents for heavy metal ions like: Pb(II), Cd(II) and Zn(II) from aqueous solutions by batch and column techniques. Experimental data obtained from batch equilibrium tests have been analyzed by two isotherm models: Freundlich and Langmuir. The overall adsorption tendency of CRs toward Pb(II), Cd(II) and Zn(II), under non-competitive conditions, followed the order: Cd(II) > Pb(II) > Zn(II). Selectivity studies were performed in ternary mixture of Pb(II), Cd(II) and Zn(II) to check if the synthesized CRs can be useful for selective separation of heavy metal cations. The results revealed that the CRs with IDA groups exhibited high selectivity toward Pb(II), both in batch and column techniques. Regeneration of the resins was achieved using 0.1 M HCl solution.     

SOLVENT EXTRACTION EQUILIBRIA OF TRIS(BENZOYL- TRIFLUOROACETONATO)COMPLEX OF COBALT(II) AND NICKEL(II) AS ION-PAIRS WITH TETRABUTYLAMMONIUM

Abstract

Solvent extraction of cobalt(Il) and nickel(II) in aqueous 1 mol dm^?3 NaCl solutions with benzoyltrifluoro-acetone(Hbfa) in carbon tetrachloride has been measured in the absence and presence of tetrabutylammonium(tba⁺). In the absence of tba⁺, M(bfa)₂ species is extracted and the extraction of cobalt(II) is better in the higher Hbfa concentration range but in the presence, M(bfa)₃ ^?tba⁺ type ion-pair is extracted and the extraction of nickel-(II) is always better. This is explained in terms that although the bis-nickel(II) complex is more stable, it is much more strongly hydrated than the bis-cobalt(II) complex and consequently its extraction is hindered but in the tris-complexes such a large difference of the hydration may not occur and the more stable nickel(II) complex is extracted better.     

COBALT–NICKEL SEPARATION: THE EXTRACTION OF COBALT(II) AND NICKEL(II) WITH BIS(2-ETHYLHEXYL) PHOSPHINIC ACID (PIA-8) IN TOLUENE

The extraction behaviour of cobalt(II) and nickel(II) from sulfate solutions with bis(2-ethylhexyl) phosphinic acid (PIA-8) in toluene has been studied. Quantitative extraction of Co(II) was observed at pH 5.0–5.9 while that of Ni(II) at pH 6.8–7.0 with 0.03 M PIA-8 in toluene. The difference in pH_0.5 for Co(II) and Ni(II) was 1.9. The stoichiometry of the extracted species were determined by slope analysis method. The extraction reaction proceeds by cation exchange mechanism and the extracted species were Co · R₂(HR)₂ and Ni · R₂ · 2(HR)₂. Temperature dependance of the extraction equilibrium constants were determined to estimate the apparent thermodynamic functions (ΔG, ΔS and ΔH). The method was used for separation of cobalt(II) and nickel(II). Cobalt(II) was separated from nickel even at 1:20 (Co:Ni) ratio. The separation of cobalt(II) from nickel(II) was favoured with the increase in temperature.     

Synergistic Solvent Extraction and Transport of Zn(II) and Cu(II) across Polymer Inclusion Membranes with a Mixture of TOPO and Aliquat 336

Separation of zinc(II) and copper(II) ions from aqueous solutions by synergistic extraction and transport through polymer inclusion membranes (PIMs) has been investigated. A mixture of trioctylphosphine oxide (TOPO) and trioctymethylammonium chloride (Aliquat 336) was used as a selective extractant as well as an ion carrier in polymer membranes. The effects of hydrochloric acid concentration in the aqueous phase and extractants concentration in the organic phase on the separation process of zinc(II) and copper(II) ions have been studied. Zn(II) ions were successfully separated from Cu(II) ions in solvent extraction process using 0.025 M TOPO and 0.06 M Aliquat 336 in kerosene. Polymer inclusion membranes (PIMs) containing a mixture of TOPO and Aliquat 336 as the ion carrier have been prepared and the facilitated transport of Zn(II) and Cu(II) ions has been studied. The influence of membrane composition on the transport kinetic of Zn(II) and Cu(II) has been evaluated. Zn(II) ions were preferably transported from the aqueous solutions containing Cu(II) and above 87% of Zn(II) ions were effectively recovered from the 0.5 M HCl solution as the source phase through PIM into 0.5 M H₂SO₄ as the stripping phase.     

Recent studies in adsorption of Pb(II), Zn(II) and Co(II) using conventional and modified materials:a review

ABSTRACT

Heavy metal contamination and its detrimental effects on human health and environment have been a worldwide concern. Over the years, various technologies have been adapted to tackle this problem. Adsorption is still considered to be one of the most feasible and cost-effective methods for treating wastewater contaminated with heavy metals. Adsorbents such as activated carbon, clay, zeolites and silica have been studied extensively in the past. Modification of these conventional adsorbents and the synthesis of nonconventional adsorbents such as nanocomposites and metal organic frameworks (MOF’s) have been the main focus of study in recent times. This review article attempts to present a detailed account of various adsorbents and their removal efficiencies for the treatment of wastewater contaminated with lead(II), zinc(II) and cobalt(II) in the current decade. Influence of various parameters, adsorption isotherms and kinetics best described for their removal have also been reviewed in detail. It is observed that most of the adsorbents followed pseudo second order kinetics suggestive of a chemisorption process. After conducting a thorough review of more than 120 recently published papers, it can be inferred that nanomaterials and nanocomposites have shown excellent adsorption capacity for removal of these heavy metals.