聚环氧琥珀酸对锰渣中砷的萃取

以锰渣为材料,用聚环氧琥珀酸(PESA)作为萃取剂,研究PESA在不同pH、萃取剂浓度、土液比下对砷(As)的萃取效果。实验结果表明,与丙烯酸/马来酸酐共聚物(MA/AA)相比较,PESA对锰渣中As有优良的萃取效果。在萃取体系条件为pH=1、萃取剂浓度50 mg/mL、土液比1∶200、搅拌60 min并浸泡过夜时,PESA对砷的萃取率可达78.3%。实验还发现,PESA对三价砷和五价砷均有螯合萃取作用,对砷的萃取无价态的选择性。     

复合淋洗剂柱淋洗法修复工业废弃地铬污染土壤

为了更好地修复铬污染土壤,以盐酸、柠檬酸为初始淋洗剂,配合去离子水、石灰水、氯化钙、碳酸钠和磷酸钠,制定了20种复合淋洗剂的淋洗方案对某工业废弃地铬污染土壤进行柱淋洗实验,研究复合淋洗剂对土壤pH、总铬和Cr(Ⅵ)去除效果及对各形态铬变化的影响。结果表明:(1)各淋洗方案对土壤总铬和Cr(Ⅵ)的去除量分别为197.4~1 671.6、113.2~316.8mg/kg,其中初始淋洗剂盐酸、柠檬酸结合使用对总铬有较好的去除效果。(2)石灰水和磷酸钠可以将淋洗后的土壤pH调至接近中性并固定尚未淋洗出的Cr(Ⅵ)。(3)当0.2mol/L柠檬酸、0.1mol/L盐酸、0.2mol/L盐酸、1%(质量分数)石灰水用量分别为2、2、1、2mL/g进行淋洗时,土壤pH为7.37,总铬和Cr(Ⅵ)去除量分别为1 659.8、316.8mg/kg,去除率分别为34.6%、72.7%,水溶态铬、可交换态铬和碳酸盐态铬已被大量淋出,有机态铬与残渣态铬占比较其他淋洗方案低,为最佳淋洗方案。     

羧基化杯[6]芳烃磷氧衍生物(HHPHC)对Cu~(2+)、Ni~(2+)的萃取性能

合成了萃取剂羧基化杯[6]芳烃磷氧衍生物,即5,11,17,23,29,35-六羧基-37,38,39,40,41,42-六氧磷酸二乙酯杯[6]芳烃(HHPHC),并对其进行了红外表征,考察了溶液初始pH值、萃取时间、重金属离子初始浓度、萃取温度对HHPHC萃取重金属离子(Cu~(2+)、Ni~(2+))的影响。结果表明,HHPHC萃取Cu~(2+)和Ni~(2+)的最佳温度均为30℃,最佳pH值均为5.0,且15 min基本达到萃取平衡,适宜处理低浓度重金属废水。准二级动力学模型(R20.94)和Freundlich等温模型(R20.999)均可拟合其萃取过程,Gibbs自由能(ΔG0)和焓变(ΔH0)值均小于0,表明萃取反应是一个自发的放热反应。     

还原剂添加的矿物聚合物对Cr(Ⅵ)的解毒/固化

在对现有Cr(Ⅵ)污染控制方法分析的基础上,提出用还原剂添加的矿物聚合物对Cr(Ⅵ)进行解毒/固化的研究思路。以煤矸石为原料,以水玻璃和Na OH为碱性激发剂,合成矿物聚合物;以Fe Cl2·4H2O为还原剂,用还原剂添加的矿物聚合物对Cr(Ⅵ)进行解毒/固化实验,并采用XRD、TEM/EDS、XPS对固化体进行检测。当添加的Fe(Ⅱ)与Cr(Ⅵ)的摩尔比≥3∶1时,矿物聚合物中总铬的浸出浓度小于1 mg/L,铬固化率大于99%。还原剂添加的矿物聚合物对Cr(Ⅵ)最大固化量为0.8%。在合成过程中,Fe(Ⅱ)和Cr(Ⅵ)添加的矿物聚合物发生了氧化还原反应,Fe(Ⅱ)被氧化成了Fe(Ⅲ),Cr(Ⅵ)被还原成了Cr(Ⅲ),随后Fe(Ⅲ)和Cr(Ⅲ)同时被矿物聚合物中的—OAl(-)(OH)3吸引,并固化在非晶质结构中。     

不同营养条件对薏苡人工湿地去除Cr(Ⅵ)的影响

为研究不同营养水平下薏苡人工湿地对Cr(Ⅵ)的净化与形态转变化的影响,以生活污水(W)、1/2(体积比)Hoagland营养液(Y)、1/2Hoagland营养液+生活污水(Y+W)为灌溉水源,构建微型模拟垂直流薏苡人工湿地,采取间歇进水方式,进水分别以0、10、30mg/L左右Cr(Ⅵ)(以K2Cr2O7形式加入)进行处理。结果表明:(1)根、茎、叶中总铬均随处理时间的延长和Cr(Ⅵ)浓度的提高而提高;不同器官之间相比较,总铬依次为根叶茎。(2)在不同营养条件下,基质中可交换态、铁锰氧化物结合态、有机物结合态、残渣态铬含量均随着Cr(Ⅵ)浓度的增加而提高,而碳酸盐结合态铬则先升高后降低。(3)Y处理出水Cr(Ⅵ)较高,W、(Y+W)处理均能提高人工湿地对含铬污水的处理效果。     

淀粉基黄原酸盐处理重金属废水的条件优化研究

采用淀粉基黄原酸盐处理含重金属的电镀废水 ,对淀粉基黄原酸盐的用量、pH值和反应时间等条件进行了研究。结果发现 ,1L含氰电镀废水 (含Cr3+15mg/L、Cu2 +3mg/L、Ni2 +9.2mg/L和Zn2 +6mg/L) ,加入 1g淀粉基黄原酸盐 ,调节 pH为 8,搅拌 1h ,过滤 ,处理后的废水中Cr3+、Cu2 +、Zn2 +和Ni2 +残余浓度分别为 0 .0 8mg/L、0 .0 1mg/L、0 .1mg/L和 0 .0 8mg/L。含有重金属盐的残渣 ,可用硝酸处理 ,以回收重金属     

5,11,17,23,29,35-六羧基-37,38,39,40,41,42-六羟肟酸甲氧基杯[6]芳烃对铀(Ⅵ)的萃取

以上沿羧基化的杯[6]芳烃羟肟衍生物-5,11,17,23,29,35-六羧基-37,38,39,40,41,42-六羟肟酸甲氧基杯[6]芳烃(HHMHC)为萃取剂,利用HHMHC萃取U(Ⅵ),探讨U(Ⅵ)溶液初始p H值、萃取剂浓度、温度、萃取时间、初始U(Ⅵ)浓度等因素对HHMHC萃取U(Ⅵ)的影响。实验结果表明,在萃取剂浓度为2×10-4mol/L,U(Ⅵ)初始浓度为2.1×10-5mol/L,温度为25℃时,HHMHC萃取U(Ⅵ)的最佳p H值为6.0,萃取平衡时间为30 min,且最佳萃取分配比大于10。用准二级动力学模型(R20.99)和Freundlich等温模型(R20.999)均可较好地拟合其萃取过程,通过计算萃取过程的热力学参数焓变(ΔH0)小于0,表明此萃取反应是一个放热反应。以0.1 mol/L的HCl溶液作为反萃取液,初次反萃取率达96%,证明HHMHC具有一定的重复利用价值。     

利用CPS还原稳定化修复Cr(Ⅵ)污染土壤

通过研究多硫化钙(CPS)与水溶液中六价铬(Cr(Ⅵ))中的反应,得出CPS与Cr(Ⅵ)的化学计量关系及主要反应产物;以CPS为修复剂,开展还原稳定化法对Cr(Ⅵ)污染土壤的修复实验,并用Fe SO_4作对比,比较两者的稳定化效果。结果表明:CPS与水溶液中Cr(Ⅵ)反应的化学反应计量比为3∶2,对反应产物进行XRD表征,发现其主要成分为Cr(OH)3和单质S;CPS能够在短时间内大幅度降低砂土中总铬和Cr(Ⅵ)的浸出浓度以及土壤的Cr(Ⅵ)含量;经CPS处理之后的Cr(Ⅵ)污染土壤,pH值从原来的8.9下降至8.2,而经Fe2+处理的土壤明显酸化,其pH值降至7.5;土壤氧化还原电位(ORP)先显著下降,后期随着CPS的逐步消耗稍有上升;经CPS稳定化处理后,土壤可交换态铬和碳酸盐结合态铬均明显减少,铬的稳定性增强,环境风险显著减小。     

螯合沉淀联合微滤法脱除电镀废水中的低浓度络合金属

针对电镀废水中络合金属采用常规硫化钠沉淀法难以脱除问题,选用螯合沉淀-微滤法对实际电镀废水中低浓度络合Fe、Cu、Zn和Cr进行深度脱除。重点考察了pH值,重金属捕集剂EDTC投加量,EDTC反应时间,絮凝剂PAC投加量及其共存金属等因素对Fe、Cu、Zn和Cr去除效果的影响,并对EDTC去除各金属的反应机制进行了对比研究。结果表明,在pH为7,EDTC为60 mg·L~(-1),反应时间为1 min,PAC为20 mg·L~(-1),反应时间为2 min,PAM为2.5 mg·L~(-1),反应时间为2 min条件下,经微滤作用后,出水Cu 0.020 mg·L~(-1)(0.3 mg·L~(-1)),Fe 0.43 mg·L~(-1)(2.0 mg·L~(-1)),Zn 0.37mg·L~(-1)(1.0 mg·L~(-1)),Cr 0.45 mg·L~(-1)(0.5 mg·L~(-1)),均低于《电镀污染物排放标准(GB21900-2008)》中的特别限值。Fe、Cu、Zn和Cr之间存在抢夺EDTC的竞争关系,而Fe、Zn对Cr的去除又具有一定促进作用。红外光谱图表明,EDTC脱除金属Fe、Cu、Zn和Cr的反应机制是一致的,EDTC与金属发生螯合反应,EDTC巯基中硫原子捕捉金属阳离子,生成难溶的螯合产物,从而有效地去除废水中金属。     

萃取技术分离工业废水中的苯胺

研究以硝基苯为萃取剂,25℃下通过盐析萃取法回收工业废水中苯胺。以静态分批实验考察了废水酸度、初始苯胺浓度、萃取剂与废水比(油水比)、萃取级数、无机盐种类(NaCl,KCl,Na2SO4,CaCl2,K2SO4)和浓度对苯胺萃取率的影响,获得了最佳操作工艺条件。实验结果表明,硝基苯盐析萃取技术可以有效回收废水中苯胺,且高pH和溶剂比有利于苯胺萃取,随着无机盐浓度的增加苯胺回收率增加。在适宜的条件下,通过盐析作用,经过五级萃取苯胺萃取率接近100%。     

Comparative study of chromium biosorption by red, green and brown seaweed biomass

Dried biomass of the macroalgae Fucus vesiculosus and Fucus spiralis (brown), Ulva spp. (comprising Ulva linza, Ulva compressa and Ulva intestinalis) and Ulva lactuca (green), Palmaria palmata and Polysiphonia lanosa (red) were studied in terms of their chromium biosorption performance. Metal sorption was highly pH dependent with maximum Cr(III) and Cr(VI) sorption occurring at pH 4.5 and pH 2, respectively. Extended equilibrium times were required for Cr(VI) binding over Cr(III) binding (180 and 120min, respectively) thus indicating possible disparities in binding mechanism between chromium oxidation states. The red seaweed P. palmata revealed the highest removal efficiency for both Cr(III) and Cr(VI) at low initial concentrations. However, at high initial metal concentrations F. vesiculosus had the greatest removal efficiency for Cr(III) and performed almost identically to P. lanosa in terms of Cr(VI) removal. The Langmuir Isotherm mathematically described chromium binding to the seaweeds where F. vesiculosus had the largest q(max) for Cr(III) sorption (1.21mmol g(-1)) and P. lanosa had the largest Cr(VI) uptake (0.88mmol g(-1)). P. palmata had the highest affinity for both Cr(III) and Cr(VI) binding with b values of 4.94mM(-1) and 8.64mM(-1), respectively. Fourier transform infrared analysis revealed interactions of amino, carboxyl, sulphonate and hydroxyl groups in chromium binding to Ulva spp. The remaining seaweeds showed involvement of these groups to varying degrees as well as ether group participation in the brown seaweeds and for Cr(VI) binding to the red seaweeds.     

利用钢渣对聚驱采油废水进行深度处理

利用钢渣对模拟聚驱采油废水进行深度处理，依靠吸附作用去除水中的HPAM。考察了钢渣粒径、搅拌速度、pH以及吸附时间对HPAM去除率的影响，进行了吸附等温线和吸附热力学分析，并对钢渣进行了吸附再生实验。当搅拌速度为250r／min，pH为2～10，吸附时间为90rain，钢渣粒径为10-16目、投加量为100g／100mL时，HPAM的去除率可达到84％以上。钢渣对HPAM的吸附符合Langmuir等温式，吸附自由能变和吸附焓的结果都表明，该吸附属于物理吸附。吸附之后的钢渣可以通过600℃焚烧得到再生，再生后仍可保持良好的吸附性能。     

Remediation of Cr(VI) from chromium slag by biocementation

Here we demonstrate a calcifying ureolytic bacterium Bacillus sp. CS8 for the bioremediation of chromate (Cr(VI)) from chromium slag based on microbially induced calcite precipitation (MICP). A consolidated structure like bricks was prepared from chromium slags using bacterial cells, and five stage Cr(VI) sequential extraction was carried out to know their distribution pattern. Cr(VI) mobility was found to significantly be decreased in the exchangeable fraction of Cr slag and subsequently, the Cr(VI) concentration was markedly increased in carbonated fraction after bioremediation. It was found that such Cr slag bricks developed high compressive strength with low permeability. Further, leaching behavior of Cr(VI) in the Cr slag was studied by column tests and remarkable decrease in Cr(VI) concentration was noticed after bioremediation. Cr slags from columns were characterized by SEM–EDS confirming MICP process in bioremediation. The incorporation of Cr(VI) into the calcite surface forms a strong complex that leads to obstruction in Cr(VI) release into the environment. As China is facing chromium slag accidents at the regular time intervals, the technology discussed in the present study promises to provide effective and economical treatment of such sites across the country, however, it can be used globally.     

Waste Fe(III)/Cr(III) hydroxide as adsorbent for the removal of Cr(VI) from aqueous solution and chromium plating industry wastewater

Fe(III)/Cr(III) hydroxide, a waste material from the fertilizer industry, has been used for the adsorption of Cr(VI) from aqueous solution, over a range of initial metal ion concentrations (5-30 mg litre(-1)), agitation times (1-180 min), adsorbent dosages (100-1200 mg per 50 ml), temperatures (24, 29 and 38 degrees C) and pH values (4.5-10). The adsorption of Cr(VI) increased with the initial concentration of Cr(VI) and with temperature. The process of uptake follows both the Langmuir and the Freundlich isotherm models. The applicability of Lagergren and empirical kinetic models has also been investigated. Almost quantitative removal of Cr(VI) at 10 mg litre(-1) in a 50-ml solution by 500 mg of adsorbent was found at an equilibrium pH of 5.6. The efficiency of chromium removal was also tested using wastewater from the chromium plating industry.     

Chromium transport, oxidation, and adsorption in manganese-coated sand

We examine how the processes of advection, dispersion, oxidation-reduction, and adsorption combine to affect the transport of chromium through columns packed with pyrolusite (beta-MnO2)-coated sand. We find that beta-MnO2 effectively oxidizes Cr(III) to Cr(VI) and that the extent of oxidation is sensitive to changes in pH, pore water velocity, and influent concentrations of Cr(III). Cr(III) oxidation rates, although initially high, decline well before the supply of beta-MnO2 is depleted, suggesting that a reaction product inhibits the conversion of Cr(III) to Cr(VI). Rate-limited reactions govern the weak adsorption of each chromium species, with Cr(III) adsorption varying directly with pH and Cr(VI) adsorption varying inversely with pH. The breakthrough data on chromium transport can be matched closely by calculations of a simple model that accounts for (1) advective-dispersive transport of Cr(III), Cr(VI), and dissolved oxygen, (2) first-order kinetics adsorption of the reduced and oxidized chromium species, and (3) nonlinear rate-limited oxidation of Cr(III) to Cr(VI). Our work supplements the limited database on the transport of redox-sensitive metals in porous media and provides a means for quantifying the coupled processes that contribute to this transport.     

钢渣预处理含铬废水及其废渣与铬渣的固化

用钢渣对含铬废水进行预处理,探讨了钢渣粒度、用量、废水pH值和添加硫酸亚铁还原剂的影响.结果表明,经硫酸亚铁还原处理后再用钢渣处理比单纯用钢渣处理的效果明显提高,采用钢渣/总铬质量比为40的100目钢渣处理经硫酸亚铁还原后的含铬废水,总铬和Cr6 去除率分别达79%和84%,采用钢渣柱进行的两级淋滤实验进一步表明该方法可作为工业上含铬废水处理的预处理段.处理后的废钢渣同工业铬渣一起进行水泥固化,标准养护20 d后固化体表面Cr6 浸出率、破碎至5 mm粒径以下和酸雨淋溶下的浸出液Cr6 浓度均符合安全标准,可作为普通建材或进行填埋处置.     

Effect of operational parameters on heavy metal removal by electrocoagulation

In the present paper, the performance of electrocoagulation (EC) for the treatability of mixed metals (chromium (Cr), copper (Cu), lead (Pb), nickel (Ni), and zinc (Zn)) from metal plating industrial wastewater (EPW) has been investigated. The study mainly focused on the affecting parameters of EC process, such as electrode material, initial pH, distance between electrodes, electrode size, and applied voltage. The pH 8 is observed to be the best for metal removal. Fe–Fe electrode pair with 1-cm inter-electrode distance and electrode surface area of 40 cm² at an applied voltage of 8 V is observed to more efficient in the metal removal. Experiments have shown that the maximum removal percentage of the metals like Cr, Ni, Zn, Cu, and Pb are reported to be 96.2, 96.4, 99.9, 98, and 99.5 %, respectively, at a reaction time of 30 min. Under optimum conditions, the energy consumption is observed to be 51.40 kWh/m³. The method is observed to be very effective in the removal of metals from electroplating effluent.     

The effect of hydrological factors on trace metal contamination in the river Tawe, South Wales

The concentrations of nickel, copper, iron, chromium, lead, cadmium, manganese and zinc have been studied in a small river in South Wales. The river drains the contaminated industrial wasteland of the Lower Swansea Valley which is currently undergoing redevelopment and landscaping activity. The high trace metal levels found in the river waters result from weathering and erosion of this waste material, as well as from two industrial point sources of nickel, and iron and chromium. Hydrological factors found to be of importance in determining current spatial and temporal patterns of contamination included: (1) the river's available dilution at any one time, (2) antecedent river flow conditions, (3) river water pH and (4) the prevailing runoff processes in operation at any one time. The metals are present mostly in their dissolved state (i.e. > 70%), with the exception of iron and chromium which are present mostly as particulates (i.e > 80%).     

微波法处理含铬废渣的可行性分析

微波辐照解毒铬渣是一项新技术,为考察该技术应用的可行性,本文对铬渣解毒前后性状的变化进行了讨论。结果表明,该技术能较完全地使高价铬转化为低价铬,解毒渣中铬主要以三价形态存在,铬渣毒性得到消除;解毒渣浸出液中Cr6+浓度远低于国家危险废物鉴别标准,解毒渣已不属于危险固体废弃物,其在环境条件下可安全存放。说明该技术具有应用前景。     

The solid-solution partitioning of heavy metals (Cu,Zn, Cd,Pb) in upland soils of England and Wales

Ninety-eight surface soils were sampled from the uplands of England and Wales, and analysed for loss-on-ignition (LOI), and total and dissolved base cations, Al, Fe, and trace heavy metals (Cu, Zn, Cd, Pb). The samples covered wide ranges of pH (3.4-8.3) and LOI (9-98%). Soil metal contents measured by extraction with 0.43 mol l-1 HNO3 and 0.1 mol l-1 EDTA were very similar, and generally lower than values obtained by extraction with a mixture of concentrated nitric and perchloric acids. Total heavy metal concentrations in soil solution depend positively upon soil metal content and [DOC], and negatively upon pH and LOI, values of r2 ranging from 0.39 (Cu) to 0.81 (Pb). Stronger correlations (r2=0.76-0.95) were obtained by multiple regression analysis involving free metal ion (Cu2+, Zn2+, Cd2+, Pb2+) concentrations calculated with the equilibrium speciation model WHAM/Model VI. The free metal ion concentrations depend positively upon MHNO3 and negatively upon pH and LOI. The data were also analysed by using WHAM/Model VI to describe solid-solution interactions as well as solution speciation; this involved calibrating each soil sample by adjusting the content of "active" humic matter to match the observed soil pH. The calibrated model provided fair predictions of total heavy metal concentrations in soil solution, and predicted free metal ion concentrations were in reasonable agreement with the values obtained from solution-only speciation calculations.