废旧锂离子电池中钴的回收

采用高温煅烧-酸浸-化学沉淀工艺回收废旧锂离子电池中的钴,根据电极材料的热重性质确定煅烧温度,探究不同因素对钴的浸出和沉淀效果的影响,利用响应面技术优化酸浸过程,并对酸浸液进行回收处理。实验结果表明：煅烧温度为500 ℃时可充分去除黏结剂;优化实验得出H2SO4+H2O2体系浸出钴的最佳实验条件为液固比（mL ：g）6.15,浸出温度96.34 ℃,浸出时间44.52 min,H2SO4浓度1.20 mol·L-1,浸出率97.51%;当浸出液pH为1.5,[C2O42-]/[Co2+]比值为1.10,反应温度为70 ℃,沉淀时间为50 min时,钴的沉淀率为95.69%。回收得到的CoC2O4纯度高,晶体结构较好。     

还原焙烧电镀污泥中的金属形态和浸出性

分别以煤粉和稻杆为还原剂对电镀污泥进行还原焙烧,并通过酸浸回收焙烧渣中的金属。研究了焙烧温度、焙烧时间和还原剂投加量对目标金属Cu浸出率的影响以及主要杂质金属的浸出性,并采用BCR逐级提取法分析了焙烧前后污泥中的金属形态分布。结果表明,当在电镀污泥中投加30％的煤粉在600℃下焙烧1h后Cu的浸出率达到97．78％,当投加50％的稻杆时浸出率为89．47％,而氧化焙烧后浸出率仅为37．71％;并且还原焙烧渣中多数杂质金属的浸出率较低,从而可以实现Cu与杂质金属的初步分离。氧化焙烧容易导致金属从易浸出的非残渣态向难浸出的残渣态转化,而还原焙烧则能抑制这种转化过程,金属形态是决定其浸出性的重要因素。     

电子废弃物的预处理技术

主要探讨硝酸-硫酸这一混酸体系溶解电子废弃物的条件。试验表明：在60℃下，1．23mol／L硝酸和3．22mol／L．硫酸组成的混酸体系与电子废弃物在机械搅拌下反应2h，就可使得电子废弃物的溶解率达到93％以上，铜的浸出率达到99％以上。     

中温焙烧/钠化氧化法回收电镀污泥中的铬

采用中温焙烧/钠化氧化法从电镀污泥中回收铬.结果表明,影响铬浸出率的最主要因素为焙烧温度.电镀污泥与碳酸钠质量比、焙烧时间、水浸时间对铬浸出率的影响较接近,在水浸水固比为10.0 ; 1.0(质量比)、室温、焙烧温度为650℃、焙烧时间为2.0h、电镀污泥与碳酸钠质量比为1:1、水浸时间为60 min的最佳浸出条件下,铬浸出率为99.3%;去除氢氧化铝、氢氧化锌的最佳反应温度和pH分别为90～95℃和7.5;去除硫酸钠晶体的最佳pH为4.0,在最佳试验条件下,铬回收率为90.57%.     

砷华生产废渣中硫的回收利用研究

高温下氧化焙烧细磨后的砷华生产废渣，利用软锰矿浆吸收产生的SO2气体，吸收液经净化除杂、浓缩结晶等工序可制备工业产品硫酸锰。适宜的焙烧条件如下：焙烧温度为650℃，焙烧时间为60min，废渣粒度为-97μm。选择合适的吸收工艺，Mn的浸出率可达96．20％，此时SO2脱除率为87．20％。     

失效锂离子电池材料真空热处理及氨性浸出

研究了失效锂离子电池中塑料、电极隔膜等有机物的真空脱除,并以电池级纯钴酸锂(LiCoO2)为原料,与活性炭粉混合,在真空中进行热还原,还原产物用含NH3和NH4HCO3的氨性水溶液浸出。实验结果表明,当加热温度大于450℃,真空压力<400 Pa时,失效锂离子电池中有机挥发物基本被脱除。在400℃真空温度下纯LiCoO2不被炭粉还原;当还原温度达到600℃,LiCoO2转变为CoO、Co和Li2CO3;在800℃时,还原产物主要为六方相、立方相金属钴及少量的CoO。还原产物中的钴易于被氨性水溶液浸出,浸出3 h后,钴基本进入溶液中,锂的浸出率也达到97%以上。     

基于响应曲面法的钠化焙烧-水浸法回收废加氢催化剂中有价金属工艺优化

为提高废加氢催化剂钠化焙烧-水浸分离工艺回收有价金属的效率,采用响应面法优化了废加氢催化剂钠化焙烧-水浸工艺条件,探讨了焙烧温度、焙烧时间、碳酸钠添加量、浸出温度和液固比对Mo、Al浸出率的影响,并确定了最优工艺条件;同时,采用热重-差示扫描量热法 (TG-DSC) 和X射线衍射法 (XRD) 分析了废催化剂预处理与钠化焙烧过程的物相变化。结果表明：适宜的预处理温度为400~500 ℃。随着预处理温度的升高,钼与铝结合生成Al₂(MoO₄)₃;Al₂(MoO₄)₃可参与钠化反应。在钠化焙烧温度为950 ℃、焙烧时间为2 h、碳酸钠与废加氢催化剂质量比为1.1∶1、浸出液固比为6：1、浸出温度为70 ℃的条件下,Mo的浸出率可达98%以上、Al的浸出率可达94%以上。当碳酸钠添加量较少时,未参与钠化反应的Mo和Al会结合生成Al₂(MoO₄)₃,从而造成Mo、Al浸出率降低。Mo、Al发生钠化反应的温度在700~1000 ℃之间;当焙烧温度为700 ℃时,钠化反应未大量发生;随着反应温度的提高,钠化反应大量发生,至950 ℃时钠化反应最充分。本研究结果可为废加氢催化剂钠化焙烧-水浸分离回收有价金属提供参考。     

用钛白废酸和副产锌泥制备活性氧化锌

以次硫酸氢钠甲醛副产锌泥和钛白废酸为原料,经高剪切乳化、酸浸、锌粉置换、除杂、碱锌合成等工艺制得碱式碳酸锌,再经过滤、洗涤、干燥、煅烧制备活性氧化锌。考察了浸取工艺液固比(硫酸与副产锌泥的质量比)和硫酸质量分数对锌浸出率的影响,以及煅烧温度和时间对活性氧化锌质量的影响。实验结果表明,锌泥酸浸工艺的最佳液固比4,硫酸质量分数30%,在此工艺条件下,锌浸出率达95%。活性氧化锌的最佳煅烧温度为600℃,煅烧时间为240 min,在此条件下测定产品质量,氧化锌质量分数大于96%,比表面积大于50 m2/g,堆积密度小于0.35 g/mL。     

钒钛磁铁矿制备絮凝剂用于有机污水处理的研究

以钒钛磁铁矿为原料,利用盐酸浸出工艺制备铁、钛、钒三元絮凝剂,对工艺条件进行优化后用于处理模拟有机污水,并与聚合氯化铁(PFC)的絮凝效果进行对比.结果表明:在浸出时间为4 h、浸出温度为80℃、液固质量比为5、盐酸初始质量分数为20％时,浸出效果最佳,钒、铁、钛的浸出率分别为99.98％、97.77％、10.41％;...     

湿法回收砷碱渣中锑的工艺研究

本研究先以水浸实现砷碱渣中的砷锑分离，再对水浸渣进行盐酸浸出，得到了可作为工业原料氯化锑溶液。研究结果表明，在液固比为6：1，温度40℃，浸出时间40min的条件下，可使水浸过程中锑的浸出率低于3％，砷的浸出率达到99％；盐酸浸出中，控制酸浓度为1：1，液固比10：1，温度60℃，授出时间30min，能使锑的浸出率达到88％以上。经过水浸和盐酸浸出，锑的直接回收率为85．36％。     

Chloroaromatic pollutants in mussels incubated in two finnish watercourses polluted by industry

Concentrations of different chlorinated compounds were measured in mussels incubated in two polluted watercourses, a river (the River Kymijoki) and a lake (Lake Vanaja) for four weeks in summer 1995. The sum concentrations of polychlorinated phenols (PCP) and biphenyls (PCB) were both about 1 μg/g lipid weight (lw) in Lake Vanaja mussels, while in the River Kymijoki mussels PCPs were non-detectable and PCBs were measured 120 ng/g lIw. The concentrations of toxic polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) congeners ranged between <17 and 370 pg/g Iw in Lake Vanaja mussels and between <38 and 11,000 pg/g lw in the River Kymijoki mussels. Polychlorinated diphenyl ethers (PCDE) were detected in the mussels incubated in the River Kymijoki (0.4–1.1 ng/g Iw), but not in those incubated in Lake Vanaja. Polychlorinated phenoxyanisoles (PCPA) were measured 33 ng/g lw and polychlorinated phenoxyphenols (PCPP) 300 ng/g lw in the mussels incubated in the River Kymijoki. PCPAs were also detected in reference samples, which were sediment and pike from the River Kymijoki and Baltic salmon, seal and white-tailed sea eagle.     

Evaluation of trichloroethene recovery processes in heterogeneous aquifer cells flushed with biodegradable surfactants

The ability of two biodegradable surfactants, polyoxyethylene (20) sorbitan monooleate (Tween 80) and sodium dihexyl sulfosuccinate (Aerosol MA), to recover a representative dense non-aqueous-phase liquid (DNAPL), trichloroethene (TCE), from heterogeneous porous media was evaluated through a combination of batch and aquifer cell experiments. An aqueous solution containing 3.3% Aerosol MA, 8% 2-propanol and 6 g/l CaCl(2) yielded a weight solubilization ratio (WSR) of 1.21 g TCE/g surfactant, with a corresponding liquid-liquid interfacial tension (IFT) of 0.19 dyn/cm. Flushing of aquifer cells containing a TCE-DNAPL source zone with approximately two pore volumes of the AMA formulation resulted in substantial (>30%) mobilization of TCE-DNAPL. However, a TCE mass recovery of 81% was achieved when the aqueous-phase flow rate was sufficient to displace the mobile TCE-DNAPL toward the effluent well. Aqueous solutions of Tween 80 exhibited a greater capacity to solubilize TCE (WSR=1.74 g TCE/g surfactant) and exerted markedly less reduction in IFT (10.4 dyn/cm). These data contradict an accepted empirical correlation used to estimate IFT values from solubilization capacity, and indicate a unique capacity of T80 to form concentrated TCE emulsions. Flushing of aquifer cells with less than 2.5 pore volumes of a 4% T80 solution achieved TCE mass recoveries ranging from 66 to 85%, with only slight TCE-DNAPL mobilization (<5%) occurring when the total trapping number exceeded 2 x 10(-5). These findings demonstrate the ability of Tween 80 and Aerosol MA solutions to efficiently recover TCE from a heterogeneous DNAPL source zone, and the utility of the total trapping number as a design parameter for a priori prediction of DNAPL mobilization and bank angle formation when flushing with low-IFT solutions. Given their potential to stimulate microbial reductive dechlorination at low concentrations, these surfactants are well-suited for remedial action plans that couple aggressive mass removal followed by enhanced bioremediation to treat chlorinated solvent source zones.     

Book review

The Pesticide Manual ‐ A World Compendium, 8th Edition, C.R. Worthing, Editor and S.B. Walker, Assistant Editor, British Crop Protection Council, BCPC Publications Sales, Bear Farm, Binfield, Bracknell, Berkshire RG12 5QE, England. 1987, 1100 pp., UK £50; Overseas £56. ISBN 0–948404–01–9.     

Organochlorine compounds in a three-step terrestrial food chain

The concentrations of 15 organochlorine chemicals (PCBs and pesticides) were studied in a Central European oak wood food chain system: Great tit (Parus major), caterpillars (Tortrix viridana, Operophtera brumata, Erannis defoliaria), and oak-leaves (Quercus robur). Juvenile tits receive organochlorines from the mother via egg transfer and, eventually to a greater extent, from the caterpillar food source during nestling period. The concentrations of PCB 153 (2,2′,4,4′,5,5′-hexachlorobiphenyl, the most abundant in this study) was found in leaf material at ca. 1 ng/g, in caterpillars 10 ng/g, and in bird eggs 170 ng/g on an average and on a dry mass basis.     

The chemical stability of formulations of some hydrolyzable insecticides in aqueous mixtures with hydrolysis catalysts

Abstract

The active ingredients in commercial formulations of malathion, oxamyl, carbaryl, diazinon, and chlorpyrifos diluted to “spray tank”; concentrations with buffered distilled or natural water of pH 4–9 were stable for at least 24 hr. Formulations of trichlorfon were not stable at pH 7 or above but disappearance rates were slower than for the pure chemical in homogeneous solution. Cupric ion was observed to be an effective catalyst for the hydrolysis of a variety of pure organophosphorus insecticides but did not catalyze hydrolysis of the active ingredients of the formulations examined. Increasing the dilution of the formulation increased the susceptibility of malathion, oxamyl, and carbaryl to hydrolysis.     

The variation of street air levels of PAH and other mutagenic PAC in relation to regulations of traffic emissions and the impact of atmospheric processes

The occurrence of particle associated PAH and other mutagenic PAC was determined in 1996 in the street air of Copenhagen. In addition, particle extracts were tested for mutagenicity. The measurements were compared with previous measurements in 1992/1993. The levels had decreased in this period. The decrease was caused by an implementation of light diesel fuels for buses and the exchange of older petrol-driven passenger cars with catalystequipped new ones. About 65% of the reduction was caused by the application of the light diesel fuels. Under special conditions, chemical processes in the atmosphere produced many more mutagens than the direct emissions. The concentrations of S-PAC and N-PAC were 10 times lower than those of PAH, while the levels of oxy-PAH were in the same order of magnitude as those of PAH. Benzanthrone, an oxy-PAH, is proposed to be formed in the atmosphere in addition to direct emissions. Benzo(a)pyrene, often applied as an air quality criteria indicator, was photochemically degraded in the atmosphere. A strong increase in the mutagenic activities was observed to coincide with a depletion of benzo(a)pyrene.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.     

Teratological effects of pesticides in vertebrates: a review

Abstract

In the last decades, the use and misuse of pesticides in the agriculture have increased, having a severe impact on ecosystems and their fauna. Although the various effects of pesticides on biodiversity have been already documented in several studies, to our knowledge no consistent overview of the impact of pesticides in vertebrates, both terrestrial and aquatic, is available. In this review, we try to present a concise compilation of the teratogenic effects of pesticides on the different classes of vertebrates – mammals, birds, reptiles, amphibians and fish.     

Radionuclides in pinon pine (Pinus edulis) nuts from los alamos national laboratory lands and the dose from consumption

Abstract

One of the dominant tree species growing within and around the eastern portion of Los Alamos National Laboratory (LANL), Los Alamos, NM, lands is the pinon pine (Pinus edulis). Pinon pine is used for firewood, fence posts, and building materials and is a source of nuts for food—the seeds are consumed by a wide variety of animals and are also gathered by people in the area and eaten raw or roasted. This study investigated the (1) concentration of ³H, ¹³⁷Cs, ⁹⁰Sr, ^totU, ²³⁸Pu, ^{239, 240}Pu, and²⁴¹ Am in soils (0‐ to 12‐in. [31 cm] depth underneath the tree), pinon pine shoots (PPS), and pinon pine nuts (PPN) collected from LANL lands and regional background (BG) locations, (2) committed effective dose equivalent (CEDE) from the ingestion of nuts, and (3) soil to PPS to PPN concentration ratios (CRs). Most radionuclides, with the exception of ³H in soils, were not significantly higher (p < 0.10) in soils, PPS, and PPN collected from LANL as compared to BG locations, and concentrations of most radionuclides in PPN from LANL have decreased over time. The maximum net CEDE (the CEDE plus two sigma minus BG) at the most conservative ingestion rate (10 lb [4.5 kg]) was 0.0018 mrem (0.018 μSv); this is far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem (1000 μSv). Soil‐to‐nut CRs for most radionuclides were within the range of default values in the literature for common fruits and vegetables.     

Degradation and sorption of imidacloprid in dissimilar surface and subsurface soils

Degradation and sorption/desorption are important processes affecting the leaching of pesticides through soil. This research characterized the degradation and sorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) in Drummer (silty clay loam) and Exeter (sandy loam) surface soils and their corresponding subsurface soils using sequential extraction methods over 400 days. By the end of the incubation, approximately 55% of imidacloprid applied at a rate of 1.0 mg kg^?1 degraded in the Exeter sandy loam surface and subsurface soils, compared to 40% of applied imidacloprid within 300 days in Drummer surface and subsurface soils. At the 0.1 mg kg^?1 application rate, dissipation was slower for all four soils. Water-extractable imidacloprid in Exeter surface soil decreased from 98% of applied at day 1 to > 70% of the imidacloprid remaining after 400 d, as compared to 55% in the Drummer surface soil at day 1 and 12% at day 400. These data suggest that imidacloprid was bioavailable to degrading soil microorganisms and sorption/desorption was not the limiting factor for biodegradation. In subsurface soils > 40% of ¹⁴C-benzoic acid was mineralized over 21 days, demonstrating an active microbial community. In contrast, cumulative ¹⁴CO₂ was less than 1.5% of applied ¹⁴C-imidacloprid in all soils over 400 d. Qualitative differences in the microbial communities appear to limit the degradation of imidacloprid in the subsurface soils.