常压富氧浸出含锗氧化锌烟尘EI北大核心CSCD

为提高含锗氧化锌烟尘中锗的浸出率,提出采用富氧常压浸出−中和工艺处理含锗氧化锌烟尘,通过调节合适的酸度控制烟尘中硅的浸出及氧的溶解,避免形成铁硅锗胶体造成锗的损失的同时控制溶液中Fe^(3+)浓度便于烟尘中硫化物的溶出。结果表明:常压富氧条件下,在温度为90℃、液固比为7 mL/g、控制终点pH为0.3~0.7的条件下浸出4 h,锗浸出率为83%,较传统工艺条件下的锗浸出率提高13%。浸出渣的物相主要为硫酸铅和硫化锌以及二氧化硅,表面出现多孔、蓬松状结构。锗主要以硅酸盐态赋存,84.94%以该状态赋存的锗被浸出,占总锗的59.24%。浸出液中Fe^(3+)浓度约为0.4 g/L,硅含量约为64.5 mg/L,实现了对Fe^(3+)及Si的控制。采用含锗氧化锌烟尘对溶液进行中和还原,表明控制溶液温度为90℃,pH为3.0,反应1.5 h,可将溶液中Fe^(3+)浓度控制在0.025 g/L内,满足后续的沉锗要求。     

从锌置换渣中分段浸出锌、铅、镓和锗

采用分段浸出方法从锌置换渣中选择性提取锌、铅、镓和锗.首段浸出过程通过控制合适的硫酸浓度与液固比条件,锌和镓的浸出率达到90％和99％以上,超过92％的锗留在硫酸浸出渣中;二段采用盐酸作为浸出剂选择性提取铅,铅的浸出率为99％,锗损失率小于2％;三段采用1 mol/L氢氧化钠作为浸出剂,通过破坏硅锗固溶体的结构,实现锗...     

锌粉置换镓锗渣草酸浸出过程

考察锌粉置换镓锗渣草酸浸出过程中,草酸浓度、浸出时间、液固比、浸出温度、双氧水浓度对镓、锗、锌、铁、铜、硅浸出率及浸出料浆过滤性能的影响,揭示在草酸浸出体系下添加双氧水促进镓、锗浸出的作用机理。结果表明,采用草酸和双氧水为浸出剂,不仅可实现镓、锗的选择性浸出,还可显著改善浸出料浆的过滤性能。双氧水促进镓、锗浸出的机理为其作为氧化剂使镓、锗单质及其硫化物氧化为可溶的氧化物;草酸与镓、锗可生成稳定络合物,而与硅的作用较弱,从而促进镓、锗的浸出,同时使浸出渣的过滤性能得以改善。在草酸浓度为110 g/L、双氧水浓度为0.12 mol/L、液固比(L/S)为8、搅拌速度为300 r/min、浸出温度为40℃、浸出时间为30 min的条件下,镓和锗浸出率分别为99.32%、98.86%,而铜、锌、硅的浸出率分别在0.82%、0.84%、0.43%,且浸出料浆的过滤速度由常压硫酸浸出体系下的0.48 mL/min提高到100 mL/min。     

采用HBL121从锌置换渣高浓度硫酸浸出液中萃取回收镓

针对现行的湿法炼锌渣中萃取镓工艺存在调酸复杂、添加络合剂成本高、有机相损失严重等弊端,采用新型萃取剂HBL121从锌置换渣的高浓度硫酸浸出液中直接萃取镓,考察料液酸度、萃取剂浓度、萃取温度、萃取时间和相比对萃取的影响以及H2SO4浓度、反萃温度、反萃时间和反萃相比对反萃的影响,分别绘制萃取平衡等温线和反萃平衡等温线,并对萃取剂转型条件进行研究。结果表明:以有机相组成为40%HBL121(质量分数)+20%癸醇(体积分数)+磺化煤油作为萃取剂,料液酸度为108.67 g/L H2SO4,其最佳萃取条件为萃取温度25℃、萃取时间10 min、相比O/A=1:1,经过4级逆流萃取,镓萃取率达到98.14%。负载有机相用200 g/L的H2SO4溶液可选择性反萃镓,得到高纯度硫酸镓溶液,其最佳反萃条件为反萃温度25℃、反萃时间8 min、相比O/A=4:1。经过5级逆流反萃,反萃率可达到99.18%。反萃镓后负载有机相再用7 mol/L盐酸溶液反萃共萃的铁并转型,控制反萃温度25℃、反萃时间2 min、O/A=1.5:1,经过3级逆流反萃,铁反萃率可达到99.23%并完成转型,萃取剂循环使用。     

锌粉置换镓锗渣硫酸浸出过程

考察锌粉置换镓锗渣硫酸浸出中,硫酸浓度、温度、液固比、浸出时间和添加剂对Ga、Ge浸出率及浸出渣过滤性能的影响,揭示添加硝酸钠和十二烷基磺酸钠促进浸出过程的作用机理。结果表明:浸出液中添加适量硝酸钠或十二烷基磺酸钠,均可促进Ga、Ge浸出;此外,十二烷基磺酸钠还可改善浸出渣的过滤性能。添加剂的作用机理为硝酸根能使Ga、Ge单质及其硫化物氧化,从而促进Ga、Ge浸出;十二烷基磺酸钠则通过促进溶液中硅胶的絮凝,减少其对Ga、Ge的吸附,同时,使浸出渣的过滤性能得以改善。在温度为90℃、液固比为10 m L/g、搅拌速度为300 r/min、浸出时间为4 h、硫酸浓度为156 g/L、硝酸钠浓度为52.29 g/L、十二烷基磺酸钠浓度为20.5 g/L的条件下,Ga和Ge的浸出率可分别达到97.01%和90.45%,浸出料浆过滤速度由未添加十二烷基磺酸钠时的0.48 m L/min提高到30.65 m L/min。     

锌粉置换镓锗渣高压酸浸的浸出机理

研究锌粉置换镓锗渣的高压酸浸过程,考察硫酸浓度、液固比、浸出时间、浸出温度、助浸剂种类和添加量对Ga、Ge浸出率以及浸出渣过滤性能的影响。结果表明:增加硫酸浓度有利于Ga、Ge的浸出,但硫酸浓度超过156 g/L后,反而不利于Ge的浸出。浸出时间和温度对Ga、Ge浸出率影响较小,但增加浸出时间或提高反应温度均有利于改善浸出渣的过滤性能。添加硝酸钠或硝酸钙均可促进Ga、Ge的浸出,且硝酸钙的添加还可改善浸出渣的过滤性能。在硫酸浓度156 g/L、助浸剂硝酸钙60 g/L、液固比8、浸出温度150℃下浸出3 h,Ga、Ge浸出率可分别达到98%和94%以上,且浸出料浆过滤速度较常压酸浸时的提高近20倍。     

银锗合金的元素分析

为准确测定银锗合金中银和锗的含量,选择了滴定法和ICP - AES光谱法.得出以下结论:①采用常规的伏尔哈特法和电位滴定法测定银含量,锗元素不会产生干扰.2种方法均可用于日常检测,电位滴定法更适宜用于仲裁检验和监督抽查;②ICP - AES光谱法测定银合金中银含量的常规方法是先将样品用稀硝酸溶解后加盐酸沉淀银,再分析滤液中的其它金属杂质元素.使用含C1-试剂溶解银锗合金时,当温度≥86℃会引起GeCl4的挥发,对分析锗含量的影响较大,采用此法须严格控制温度;③尝试了用滴定后的溶液过滤定容后再测定锗含量.实际样品测试结果与其他元素含量分析结果的元素总合量趋于100％,由此表明测试滴定的滤液所得检测结果准确,选用该方法操作简单,结果更为理想.     

沉铂钯后液中碲铋的分离与回收工艺

以铜阳极泥处理中的沉铂钯后液为原料,经过氢氧化钠沉淀、酸浸沉淀渣、SO_2还原后,得到碲粉和还原碲后液,在还原碲后液中加入氢氧化钠沉淀后过滤得到氯氧铋,在氯氧铋中加入氢氧化钠溶液脱氯制得氧化铋。结果表明:加入氢氧化钠调节沉铂钯后液pH为6、反应温度20~25℃、反应时间为1 h时,沉铂钯后液中碲和铋沉淀率分别达到99.91%和99.96%;沉铂钯后液得到的沉淀渣混酸浸出适宜条件是3 mol/L盐酸和1.5 mol/L硫酸体积比为2:1,H~+浓度为3 mol/L,反应温度为50℃,反应时间为2 h,铋和碲的浸出率分别为99.93%和98.21%;在富集碲铋的浸出液中通入SO_2还原,当SO_2流量为0.25 L/min、反应温度为70℃、反应时间为50 min时,碲的还原率为96.59%,还原碲粉中碲含量达到79.45%,砷和铋含量仅为0.003%和0.067%(质量分数);在SO_2还原碲后液中加入氢氧化钠调节溶液pH值为2,过滤后得到氯氧铋;在氯氧铋中加入6 mol/L氢氧化钠溶液,当液固比为3:1、反应温度为80℃、反应时间为2 h时,所得氧化铋产物中氧化铋含量达到93.80%。     

混合酸溶液浸出刚玉烟尘灰中的镓（英文）

为了从高硅含量的刚玉冶炼烟尘中提取镓,提出一种硫酸与氢氟酸混合酸溶液浸出的方法,并对浸出过程的各项实验参数进行优化。结果显示,当单独使用硫酸作为浸出剂时,刚玉烟尘中镓的浸出率仅为38%。从刚玉烟尘灰的微区成分分析结果中可知,烟尘中的富硅相镓含量较高;这部分镓无法溶入硫酸溶液。氢氟酸的加入对二氧化硅产生侵蚀,从而显著提高了刚玉烟尘灰中镓的浸出率。研究反应时间、温度、氢氟酸浓度和硫酸浓度对镓浸出率的影响。结果表明,在最佳浸出条件下,烟尘中镓的浸出率可达到91%。最佳的浸出参数如下:反应时间4 h、反应温度80°C、混合酸溶液中硫酸浓度1.5 mol/L、氢氟酸浓度6.4 mol/L和液固比5:1 (mL/g)。     

含锗真空炉渣在HCl-CaCl2-H2O体系中浸出锗的动力学研究

为提高真空炉渣中锗的浸出率提供理论依据,对含锗真空炉渣在HCl-CaCl2-H2O体系中锗的浸出动力学进行了研究。结果表明,浸出过程属于生成固体产物层的"未反应核收缩模型",其宏观动力学方程为:1–2/3x–(1–x)2/3=4.66×10-3CHCl1.027CCaCl21.046d-0.862exp(–21068/RT)t,表观活化能为21.068kJ/mol,浸出过程受灰分层扩散控制;提高盐酸的浓度、氯化钙浓度、浸出温度、液固比及减小矿物粒度均可加快锗的浸出速度,提高锗的浸出率。     

Recovering germanium from coal ash by chlorination with ammonium chloride

A new process of enriching germanium from coal ash was developed.The process involves in mixing the coal ash and ammonium chloride and then roasting the mixture to produce germanium chloride that is then absorbed by dilute hydrochloric acid and hydrolyzed to germanium oxide.The germanium recovery reached to 80.2% at the optimum condition:mass ratio of NH4Cl/coal ash is 0.15,roasting temperature 400℃ and roasting time 90min.     

Leaching process of germanium oxide dust

A thermodynamic analysis on the acid leaching process of germanium oxide dust and discussion on the behaviors of main substances of the dust in the leaching process were carried out. The effects of temperature, acid concentration, leaching time and stirring speed on the leaching rate of germanium were investigated. Based on the characteristic of the dust, the kinetics and reactive mechanism of acid leaching were stud- ied. The results show that the leaching of the dust by acid belonged to "the unreacted core shrinking model" of producing solid outgrowth layer. The chemical reaction was controlled by inner diffusion process. The apparent activation energy of leaching process was 12.60 kJ/mol. The leaching reaction of germanium was determined to be mainly second order reaction. The optimum conditions were the reaction tem- perature of 363 K, the leaching time of 2.5 h, the stirring speed of 120 r/min, the solid-to-liquid ratio of 1/8 and the acid concentration of 120 g/L. Under these conditions, the leaching rate of germanium can come up to more than 87%.     

二氧化锗离心过滤工艺研究

采用离心分离工艺对Ge Cl4水解生成的二氧化锗进行过滤实验,分析了各工艺参数对Ge O2直收率、Ge O2滤饼含水量与含氯量的影响规律。通过研究得到最优工艺参数组合:离心机滤布孔径为2.6μm,脱水转速为1200 r/min,滤饼厚度为80~100 mm,单次洗涤洗液量为20 L,洗涤循环次数为3~5次。结果表明:Ge O2直收率可达到99.62%,制备的Ge O2滤饼含水量小于8%,含氯量小于0.05%,此样品再经过干燥则可以达到国标规定的Ge O2-06产品要求。     

Recovering in,Ge and Ga from zinc residues

A novel solvent extraction process has been developed to selectively recover indium, germanium and gallium from the cement residue sulfuric acid leach solutions in a hydrometallurgical zinc plant. The key work was to determine a special organic molecule for gallium and germanium extraction. Continuous countercurrent tests on the mini-pilot plant level were performed successfully with 90.7%, 94.2% and 92.9% yield from cement residue to metals, for indium, gallium and germanium, respectively.     

Recovery of gallium from phosphorus industry flue

The flue dust generated during electric furnace production of elemental phosphorus was investigated for the recovery of gallium. Then the flue dust was slurried with water and blended with concentrated sulfuric acid, followed by ageing. The gallium in the dust was thereby converted to soluble sulfate. The factors affecting the dust curing were investigated to understand the process chemistry of the pretreatment. The optimal curing conditions are determined as follows: the mass ratio of dust to water and acid is 1 : 1 : 1, ageing temperature and time are 200℃ and 2h, respectively. Almost all the gallium available to acid dissolution in the dust, about 90% gallium, can be extracted by leaching the cured dust at 80℃ for 1h.     

Acid Leaching Extraction of Ga and Ge

The U.S. Bureau of Mines recently investigated sulfuric acid leaching to extract gallium and germanium from a zinc processing residue containing 0.32% Ga and 0.46% Ge. These metals can be extracted by leaching with sulfuric acid alone or by leaching with sulfuric acid and sulfur dioxide. A low temperature roasting treatment also aids in extracting 20% more germanium. A high percentage of the residue’s remaining zinc and cadmium is extracted using either technique.     

Recovery of germanium from lignite by microorganism

The recovery of Ge from lignite by microorganism includes tow stages:(1) the breaking-down of Ge complex of humus in lignite into simple compunds assisted by microorganism;(2) the desorption of Ge compounds from the lignite.The recovery rate of Ge has been enhanced by 14% since the discovery of adsorption and desorption of Ge from coal.The effects of pH,leaching agents,and coal size on the recovery of Ge were experimentally investigated,and the optimized process parameters were obtained.The reaction heat of Ge adsorption and desorption in lignite was determined.It is about 23-53kJ/mol,which reveals that the adsorption belongs to physical process,The recovery rate of Ge from lignite with direct microorganism leaching can reach about 85%,Which is higher than that of 60% reported elsewhere.A potential process for leaching Ge in lignite was suggested.     

铅锌矿伴生金、银、铟、锗和镓综合回收利用综述

综述了我国铅锌矿中伴生贵金属金、银和稀散金属铟、锗和镓的资源概况,对相关回收技术进行了阐述。铅锌矿中的伴生金、银主要赋存于铅矿物中,低碱性条件有利于伴生金、银的浮选回收。稀散元素铟、锗和镓主要赋存于锌矿物中,回收率随锌矿物回收率的增加而增加;抑制锌的ZnSO4对稀散元素也有很强的抑制作用,CuSO4活化剂可显著提高稀散元素的品位及回收率。     

黄磷电炉电尘浆提取镓的预处理

根据在电炉还原炼磷过程中,磷灰石中的镓在电尘浆中高度富集,成为可供利用的镓资源,提出了一种提取镓的预处理技术:用浓硫酸熟化电尘,将其中的镓先转化成水溶性化合物,再从预处理物料中浸出镓.考察了预处理过程中电尘的化学和矿物学变化以及影响镓提取率的因素,并给出了适宜的预处理条件;在最佳质量比电尘:水:硫酸=1:1:1,200℃下熟化2 h.实验结果表明,在优化条件下将预处理的电尘在80℃浸出1 h,镓的浸出率可达90%以上.     

Leaching of gallium from corundum flue dust using mixed acid solution

In order to extract gallium from a high-silica-content flue dust generated in corundum production, a mixed acid solution of H₂SO₄ and HF was used for leaching, and test parameters of the leaching process were optimized. Experimental results show that the leaching rate of gallium was only 38% when H₂SO₄ was used as leaching agent. Composition analysis results of micro areas in this corundum flue dust indicate that the content of gallium in silica-enriched phases was high; this portion of gallium was insoluble in H₂SO₄ solution. The leaching rate of gallium increased significantly with addition of HF due to corrosion of silica. Effects of reaction time, temperature, and concentrations of HF and H₂SO₄ on leaching rates of gallium were investigated. The leaching rate of gallium reached 91% when this corundum flue dust was leached in a mixed acid solution of H₂SO₄ and HF for 4 h, at a temperature of 80 °C, with a liquid-to-solid ratio of 5:1 (mL/g). The optimal concentrations of H₂SO₄ and HF in the mixed acid solution were 1.5 and 6.4 mol/L, respectively.