稀散金属硒的综合回收现状及技术进展

本文介绍了硒的资源分布及其应用情况,回顾了从铜阳极泥、含硒酸泥、含硒废料中回收硒的传统工艺,概述了目前硒的综合回收新技术,包括H2O2氧化法、循序提取法、萃取法等。     

火法炼汞过程中硒的行为及其综合回收

本文根据我国某汞矿中硒含量情况,通过理论分析和实践数据证明,在火法(高炉)炼汞过程中,矿石中的硒先经氧化升华,进入汞冷凝系统转变成SeO_2(H_2SeO_3),然后被炉气中的SO_2还原,呈元素硒混入汞炱。汞炱经予分离活汞后的渣中,含汞仍为30—50%,而含硒一般较原矿提高100倍以上。处理这样的汞炱渣,可用蒸馏法或加熔剂蒸馏法,将99%以上的汞加以回收并与硒分离。从含硒蒸馏渣中回收硒,可用硫酸化升华法、氯酸钾-盐酸浸出法或水浸法、碘还原法以及加压氢还原法提取。     

从含硒废料中回收制备高纯硒

介绍从含硒废料回收制备高纯硒的工艺过程,首先采用氧气燃烧法将废料氧化为各自的氧化物,然后于溶剂中分离、升华提纯、再还原处理纯净含硒溶液,制备出的硒粉,采用ICP-AES法对其中杂质元素进行测定,硒粉纯度达到5N(99.999%)。     

从含碲溶液中分离富集碲的研究进展

在提取碲的过程中,常将含碲矿物或原料浸出于溶液再进行分离。从含碲溶液中分离提取碲成为广大冶金学者关注的焦点。本文综述了国内外对含碲溶液分离富集碲的工艺方法,着重介绍了液膜分离法、溶剂萃取法、置换法、SO_2或Na_2SO_3还原法、沉淀分离法、微生物法、吸附法、电解法等。     

铜阳极泥加压浸出液中硒碲分离的研究

先通过脱除铜阳极泥加压浸出液中大部分的铜离子,再进行分步还原分离硒、碲,进而达到高效分离硒、碲的目的,硒、碲分离率＞98%。该方法解决了铜阳极泥加压浸出液在沉硒过程中硒不能完全沉淀、影响硒的直收率指标、后续沉碲尾料中硒含量偏高不利于碲精炼提取的问题。     

铜阳极泥加压浸出液中硒碲分离研究

先通过脱除铜阳极泥加压浸出液中大部分的铜离子,再进行分步还原分离硒、碲,进而达到高效分离硒、碲的目的,硒、碲分离率98%。该方法解决了铜阳极泥加压浸出液在沉硒过程中硒不能完全沉淀、影响硒的直收率指标、后续沉碲尾料中硒含量偏高不利于碲精炼提取的问题。     

铜阳极泥中硒铜银分离提取的基础条件研究

随着光导材料以及功能玻璃技术的不断发展,硒作为光学材料硫系玻璃合成的基础元素,其回收利用已成为研究热点。铜阳极泥中富含硒、铜、银元素,是重要的二次资源。采用H2SO4—MnO2浸出体系从铜阳极泥中浸出硒、铜、银的工艺,可实现硒、铜、银元素的选择性分步提取。研究了H2SO4浓度、浸出时间、浸出温度、MnO2添加量等对硒、铜、银浸出率的影响。同时,针对浸出液中硒、铜、银的选择性分离,还研究了NaCl添加量、Na2SO3添加量和浸出液pH值对于硒、铜、银沉淀率的影响。研究结果表明,在H2SO4浓度为1mol/L,浸出时间为1h,浸出温度为80℃,MnO2添加量为铜阳极泥质量的50%的基础条件下,硒、铜、银的浸出率分别达到95.34%、98.28%和99.32%,优于传统火法冶炼工艺,为含硒物料的绿色、高效分离提取提供了理论依据和数据支撑。     

硒碲的湿法分离

本文开辟了完全采用湿法使硒碲有效分离的一条新途径。运用该方法处理高硒碲渣,可使半成品粗碲含硒达0.05%;同时可使硒得到富集,以便回收。     

从难处理贵金属酸泥中分离回收硒和碲

提出从贵金属酸泥中分离硒和碲的工艺。采用碱浸出时碲的浸出率能够达到77.7%,硒的浸出率为38.78%;中和过程中中和渣含碲72.88%,碲的沉淀率达到98%,硒的浸出率仅为4.3%,还原过程中还原效率达到99%以上,产出粗硒含硒81.55%。     

一种锑冶炼火法精炼除砷除硒方法

本发明公开了一种锑冶炼火法精炼除砷除硒方法，其特征在于，将含砷、硒的粗锑投入精炼炉加热熔化，并升温至650～1000℃，一次性加入除砷、硒所需碱金属氢氧化物，再通入压缩空气搅拌15～150min，完成造渣除砷、硒反应，生成砷酸盐和亚硒酸盐浮渣，渣锑分离后，得合格产品。本方法操作简单，反应速度快，能一次性除去砷、硒，精炼时间短。渣含锑低，渣中砷、硒富集度高，便于砷的二次回收利用，同时产品质量得到了提高。     

Pathology of experimentally induced chronic selenosis (alkali disease) in yearling cattle

Prolonged oral exposure of cattle to elevated dietary selenium (Se) in forage and seleniferous plants in seleniferous areas of the western United States is associated historically with 2 clinical syndromes: alkali disease and "blind staggers." The potential for Se-induced disease in cattle and other species is considerable in areas with seleniferous shales, Se-accumulating plants, arid climates, and alkaline soils. These 2 Se-associated conditions were defined in the 1930s and 1940s, and the nosology of blind staggers is questionable. Seventeen yearling steers fed 0.15, 0.28, and 0.8 mg Se/kg body weight as selenomethionine or selenite for 120 days were euthanized and examined postmortem. Significant lesions were confined to 4 steers in the medium- and high-dose selenomethionine group and to 1 steer in the high-dose selenite group. Grossly, dystrophic hoof lesions developed in 2 steers, 1 of which had extensive separation of horn from lamellar and coronary epidermis and also lost hair from the tail switch. Histologically, tubules in the stratum medium of hooves from these 5 steers were replaced by islands of parakeratotic cellular debris, separated by more normal hoof matrix. Two of the 5 steers also had hyperplasia, acanthosis, parakeratosis, and disorganized germinal epithelium of varying severity in hoof epithelium, particularly at the tips of epidermal lamellae. These changes may distinguish the hoof lesions of chronic selenosis from those of chronic laminitis in cattle, in which dermal (chorial) changes predominate. In skin from the distal part of the tail of the animal that lost its switch, most follicles were atrophic and devoid of hairshafts and displayed dyskeratosis and mild superficial follicular keratosis. No significant lesions developed in tissues other than integument. Autometallographic staining for catalytic Se bonds in various tissues, including skin, liver, and kidney, revealed no positive staining of hair shafts; the correlation between stain intensity and dose group was poor. These findings indicate that dietary exposure for 4 months to 0.28 and 0.8 mg Se/kg in the form of selenomethionine and to 0.8 mg Se/kg in the form of sodium selenite reproduces in some cattle mild (subclinical) to severe (clinical) forms of alkali disease. No significant neurological, renal, or hepatic lesions developed, supporting the contention that blind staggers is caused by factors other than excessive dietary selenium.     

铜阳极泥硒回收率的提高与生产实践

重点叙述了卡尔多炉贵金属工艺中硒的回收及其分布,介绍了提高硒回收率所采取的措施及效果,通过文丘里泥强化洗涤、烟灰水浸脱硒,浸出系统直接生产粗硒,不再产出二次沉硒物,提高粗硒产品一次合格率 5 项措施后硒回收率由 88% 提高至 93.4%。     

The separation of selenium from tellurium in hydrochloric acid media by solvent extraction with tri-butyl phosphate

The separation of selenium from tellurium in hydrochloric acid media by solvent extraction with tri-butyl phosphate has been studied. Extensive laboratory experiments have been carried out at bench scale and pilot scale with different extraction apparatus. Results indicate that under the experimental conditions a high degree of separation between selenium and tellurium can be achieved by using 30 vol% TBP diluted with kerosene as the organic extractant. A process for the separation of selenium from tellurium by selective extraction has been proposed.     

响应面法优化从电解锰阳极液中回收硒工艺

采用响应面设计优化铁炭微电解法回收电解锰阳极液中硒的工艺条件,研究搅拌速率、铁炭比和反应时间对硒回收率的影响。结果表明,各因素对硒回收率的影响大小顺序为:搅拌速率>铁炭比>反应时间,三者之间两两的交互作用均较弱。最优工艺条件为:搅拌速率199r/min、铁炭比1.94g/g、反应时间192min。在此条件下,硒的回收率可达到96.34%,与模型预测值96.52%无显著差异。     

4-甲基-2-戊酮萃取分离-电感耦合等离子体质谱法测定高纯硒中17种杂质元素

利用电感耦合等离子体质谱法(ICP-MS)测定5N~6N(纯度为99.999%~99.999 9%)高纯硒中痕量杂质元素时,硒的基体效应明显,影响结果的准确性。采用硝酸溶解高纯硒,经4-甲基-2-戊酮选择性萃取硒后,对水相进行测定,建立了电感耦合等离子体质谱法测定高纯硒中的Li、Be、B、Sc、Ti、V、Cr、Mn、Co、Ni、Cu、Zn、As、Sr、Cd、Ba、Pb共17种痕量杂质元素的方法。实验表明,萃取时当盐酸浓度为7mol/L、MIBK体积为20mL和萃取时间为2min时,水相中硒的质量浓度低于5mg/L,此时硒基体对测定的影响可忽略。方法中各元素校准曲线的线性关系均大于0.999 5,各待测元素的方法检出限为0.2~7.0ng/g。按照实验方法对高纯硒样品中这17种杂质元素进行测定,测定结果的相对标准偏差(RSD,n=6)在5.0%~11.2%之间,加标回收率在91%~103%之间。     

硒提取工艺的研究现状及应用

介绍了提取硒的主要原料,详细阐述了当前国内外硒提取工艺的研究和应用现状。分析了火法提硒和湿法提硒的特点,指出这两种提硒方法相比,湿法提硒具有能耗低、清洁环保、生产成本低等优点,将逐渐替代火法提硒工艺而成为硒提取的主导工艺。     

亚硫酸钠在稀贵金属冶金中的应用

系统总结了亚硫酸钠在稀贵金属冶金中的应用。主要阐述了从铜镍合金氯化渣中脱硫富集贵金属,从铜阳极泥分金渣中分银,从高硒、碲的铜阳极泥中分离回收金、钯、铂,硒、碲的分离提纯,在盐酸介质中还原精炼金,从负载有机相中反萃金,从弱酸性介质中还原银,制备金的电镀配合物等,以期为从事相关领域的科技人员提供参考。     

废旧不锈钢衬底CIGS太阳能电池中回收钼的研究

废旧铜铟镓硒（CIGS）薄膜太阳能电池芯片中的钼具有很高的回收价值，提出了“氧化酸浸—亚硫酸钠除硒—萃取”的方法回收不锈钢衬底CIGS太阳能电池芯片中的钼。结果表明，采用“双氧水+硫酸”能够浸出镀层中的金属元素，并对不锈钢衬底无伤害；考察了液固比和硫酸添加量对浸出的影响，在最优工艺条件下，废芯片中主要金属元素的浸出率达到95%以上；采用“N235+异辛醇+煤油”萃取酸浸液中的钼时，硒会被同时萃取，采用“亚硫酸钠+双氧水”沉硒后，钼萃取率能够达到98%以上，同时其他金属几乎不被萃取。为不锈钢衬底铜铟镓硒薄膜太阳能电池废芯片的处理提供了一种有效的方法。     

萃取法从铜阳极泥制备的碲化铜中回收碲

进行了从铜阳极泥中以碲化铜形式富集碲,采用萃取法分离碲硒并回收碲的试验研究。结果表明:以20%TOA+20%仲辛醇+60%磺化煤油(体积分数)为萃取剂、浓度均为2mol/L的H2SO4+HCl为洗涤剂、200g/L的NH4Cl溶液为反萃剂,可实现碲与硒、铜的良好分离;反萃液经SO2或水合肼还原,可得到高纯度的金属碲粉。