复杂金精矿火法冶炼高锑烟尘处理工艺

针对某复杂难处理金精矿火法熔炼造锍产生的高锑烟尘,进行了湿法综合处理工艺研究。采用XRD、SEM对高锑烟尘进行了物相组成分析和微观形貌表征。以盐酸为浸出剂分离烟尘中的砷、锑、铅、锌等元素,得到含杂较低的高品位金精矿,并对所得金精矿通过静态富氧焙烧-酸浸除杂-氰化浸出工艺回收金银等贵金属。结果表明:高锑烟尘主要由Sb_2O_3和As_2O_3物相组成,锑、砷含量分别为31.18%和9.95%;该烟尘由粒度较细、大小较均匀颗粒物所组成;在盐酸浓度为4 mol/L、浸出液固质量比为5.0、温度为85℃条件下搅拌浸出2 h,浸出渣率为13.65%,浸出渣中砷、锑、铅和锌的品位分别为0.52%、0.60%、0.06%和0.49%;所得金精矿静态富氧焙烧脱硫率为98.81%,焙砂酸浸渣中金品位达到116.9 g/t,金的氰化浸出率达到98%。通过该工艺处理复杂难处理金精矿火法冶炼所得高锑烟尘,实现了烟尘中杂质元素的高效分离,有价元素得到有效回收。     

碳热氯化法回收重选尾矿中的稀土

采用摇床重选实验方法使尾矿中的稀土元素得到预富集,获得稀土氧化物（REO）品位为18.02%,粒径小于74μm稀土精矿和稀土氧化物品位为9.19%,粒径大于74μm稀土精矿,稀土总回收率为37.26%。采用碳热氯化法分解,粒径小于74μm的稀土精矿,得到氯化稀土。以SiCl4为脱氟剂,C为还原剂,Cl2为氯化剂,750℃时氯化反应2 h,氯化率高达91.0%。750℃氯化产物的酸不溶物的X射线衍射结果表明酸不溶物的主要物相为SiO2及少量没有完全反应的独居石。     

难处理含金硫精矿的焙烧氧化-硫代硫酸盐浸出

为了提高难处理含金硫精矿中金的浸出率,采用同步热分析仪研究在马弗炉中焙烧氧化难处理含金硫精矿的最佳条件,通过优化实验确定硫代硫酸盐浸出的最佳工艺参数。结果表明:在马弗炉中焙烧氧化难处理含金硫精矿最佳条件为在700℃温度下焙烧2 h,难处理含金硫精矿硫的去除率可达94.7%。焙烧后,金的浸出率大幅度提高。使用组成为0.03 mol/L CuSO4、1.0 mol/L NH3·H2O、0.3 mol/L Na2S2O3、0.1 mol/L(NH4)2SO4和0.3 mol/L Na2SO3的硫代硫酸盐溶液作为浸出剂,最佳浸出工艺参数如下:浸出时间18 h、液固比2:1、振荡速度250 r/min、浸出温度50℃。在此浸出工艺参数下,金浸出率达71.2%。     

铈锆复合氧化物制备及甲烷燃烧催化活性表征

采用共沉淀水热联合法制备了大比表面铈锆复合氧化物材料,在较低焙烧温度400℃下形成了稳定的晶相结构,500℃焙烧新鲜比表面达135.44 m2/g,900℃、6 h老化后比表面仍维持44.07 m2/g。采用沉淀陈化工艺,并掺杂改性,得到的铈锆复合氧化物,稳定性更高,经950℃、2 h老化后,最高比表面可达59.62 m2/g。活性氧化铝与铈锆复合氧化物有协同作用,二者复合得到了更高性能的氧化物材料,新鲜比表面为188.92 m2/g,经950℃、4 h老化后,比表面为71.64 m2/g,经1 050℃、4 h老化后,比表面为58.10 m2/g。对所得铈锆材料进行了X射线衍射、吸脱附表征,并负载钯贵金属制得催化材料,以甲烷完全催化燃烧为探针反应,研究了铈锆复合氧化物材料的甲烷燃烧催化性质。结果表明,铈锆复合氧化物材料是很好的燃烧催化剂二载材料,负载钯催化剂具有较高催化活性,起燃温度降低至352℃。     

复杂金精矿铁锍酸溶渣控电位氯化浸出富集贵金属金

以复杂难处理金精矿火法造锍捕金所得铁锍合金的硫酸浸出渣为原料,采用控电位氯化浸出工艺分离酸溶渣中的Cu、As、Sb等主要杂质元素,贵金属Au单向富集得到高品位金泥,Au泥经过硫酸化焙烧脱硫进一步富集贵金属金。结果表明:双电极体系控电位氯化浸出优化条件为[H⁺]5mol/L、浸出电位380m V、液固质量比5:1、温度85℃和搅拌浸出2 h,所得渣率为28.2%,浸出渣中Cu、As、Sb含量分别降到0.18%、0.095%、0.084%,浸出率分别达到99.6%、99.8%、99.8%,浸出渣主要成分Si和S的含量分别为29.39%和22.72%,Au品位富集到2.609%;浸出渣硫酸化焙烧脱硫的烧成率为66.5%,S含量降至0.87%,脱硫率为96.2%,焙砂的主要物相为SiO₂和单质金,Au品位富集到3.937%。复杂金精矿铁锍合金酸溶渣通过控电位氯化浸出除杂—焙烧脱硫可将贵金属金有效富集。     

低品位钼精矿石灰焙烧-酸浸提取钼

采用XRD和TG-DSC分析研究低品位钼精矿石灰氧化焙烧过程的反应机理,确定石灰法焙烧-酸浸提钼工艺的优化参数。热重分析表明:石灰法焙烧主要发生Ca(OH)2的分解、MoS2的氧化、MoO2的再氧化及钼酸盐的生成等反应,焙烧过程主要产生MoO2、MoO3、CaMoO4、CaSO4等物相。XRD分析表明:当温度高于600℃、反应时间大于90 min时,焙砂中低价态钼的衍射峰完全消失,此时焙砂主要物相为CaMoO4和CaSO4,辉钼矿被充分氧化;石灰焙烧适宜的条件为Ca(OH)2与钼精矿质量比1:1、焙烧温度650℃、焙烧时间90 min,焙烧过程硫的保留率可达91.49%。钼焙砂酸浸适宜的浸出温度为90℃、浸出时间为2 h、H2SO4浓度为70 g/L、液固比为5:1,此时钼浸出率可达99.12%,CaMoO4被完全溶出。     

含氟金绿宝石型铍精矿热分解机理及溶出工艺研究

针对含氟金绿宝石型铍精矿中铍提取分离目的,以含氟金绿宝石型铍精矿为研究对象,采用不同温度焙烧方法对金绿宝石分解机理及铍分离工艺进行研究,并采用TG-DSC、XRD对样品进行表征,采用单因素实验方法对热解产品铍浸出效果进行实验。研究表明:金绿宝石在氟化物作用下在800℃以上开始热分解,但在温度低于1000℃下难以保证金绿宝石分解完全,无法保证铍有效提取分离,应将焙烧温度控制在1067℃以上,以保证杂质"死烧"和金绿宝石快速完全分解;单因素条件下最优焙烧温度1150℃、焙烧时间0.5h;这一焙烧条件下,铍精矿灼减率为18.67%,铍烧损率约9.09%,酸浸浸出率93.13%。     

氟碳铈矿精矿在SiCl4存在时的碳热氯化过程

研究了氟碳铈矿精矿的碳热氯化反应,发现在活性脱氟剂SiCl4存在下,在500℃至900℃之间,稀土氯化率由无脱氟剂时的43%～86%增至51%～96%。当氯化反应温度低于900℃时,氯化产物的酸不溶物量随着温度的升高而降低;而当温度高于900℃时,酸不溶物量明显增加。X射线衍射结果表明:450～500℃时酸不溶物为稀土氟化物、氟氧化物和精矿中没有反应的硫酸钡;550～800℃为稀土氟化物;1000～1100℃为稀土氟氧化物和氟化物。     

铜镍氧硫混合矿焙烧-浸出过程铜、镍、铁的转化

随着硫化镍矿资源的日趋枯竭,铜镍氧硫混合矿的利用将会愈发受到关注。通过对原矿进行差热-热重、XRD以及热力学分析,揭示焙烧过程矿石矿相的转变历程,研究铜镍氧硫混合矿焙烧过程中矿物粒度、焙烧温度和焙烧时间对铜、镍、铁转化的影响,探索浸出过程中溶剂、液固比、浸出温度及浸出时间对铜、镍、铁浸出的影响。结果表明:矿物粒度为74~80μm、焙烧温度为600℃、焙烧时间为2 h、选择水作为浸出溶剂、浸出温度为60℃、液固比为6:1、浸出时间2 h时,镍和铜的浸出率达到最高分别为46.25%和96.27%,铁的浸出率低于1%。     

氟碳铈矿精矿在SiC14存在时的碳热氯化过程

研究了氟碳铈矿精矿的碳热氯化反应，发现在活性脱氟剂SiC14存在下，在500℃至900℃之间，稀土氯化率由无脱氟剂时的43％-86％增至51％-96％。当氯化反应湿度低于900℃时，氯化产物的酸不溶物量随着湿度的升高而降低；而当湿度高于900℃时，酸不溶物量明显增加。X射线衍射结果表明：450—500℃时酸不溶物为稀土氟化物、氟氧化物和精矿中没有反应的硫酸钡；550—800℃为稀土氟化物；1000-1100℃为稀土氟氧化物和氟化物。     

The Influence of the Rare Earth Element Ce on the High-Temperature Oxidation Kinetics of Low-Cr Steels

The oxidation behavior of steels containing low-Cr concentrations (0.5-2.25 wt.%) has been studied in laboratory air in the temperature range of 400-550 °C. The oxidation rate of the steels was lower than that of pure iron, but higher than that of pure iron when a small amount of rare earth element cerium (0.03 wt.%) is added to the 2.25Cr1Mo steel. The mass change follows a nearly parabolic law for the case of pure iron and the steel without Ce addition, while linear behavior describes the oxygen uptake for the case of the 2.25Cr1Mo+0.03Ce steel. SEM cross-section observations and thermodynamic calculations confirm that there is no wustite (FeO) formation during oxidation of pure iron and low-Cr steels at 550 °C, whereas FeO might be formed in the oxide scale of 2.25Cr1Mo+0.03Ce at the same oxidation conditions (temperature, atmosphere, and exposure time). By investigating the temperature for FeO stability, this study reveals that the temperature for FeO formation on pure iron is 568 °C, for the 2.25Cr1Mo steel 589 °C, and 471 °C for the 2.25Cr1Mo+0.03Ce. This low value for the FeO stability temperature found for the steel 2.25Cr1Mo+0.03Ce steel explains why this steel oxidizes very fast at 550 °C.     

Recovery of waste rare earth fluorescent powders by two steps acid leaching

The effects of the acid leaching and alkali fusion on the leaching efficiency of Y,Eu,Ce,and Tb from the waste rare earth fluorescent powders were investigated in this paper.The results show that hydrochloric acid is better than sulfuric acid in the first acid leaching,and NaOH is better than Na2CO3in the alkali fusion.In the first acid leaching,the Wloss is 20.94%when the waste rare earth fluorescent powders are acid leached in H?concentration 3 mol L-1and S/L ratio 1:3 for 4 h due to red powders dissolved.The better results of the alkali fusion can be got at 800℃ for 2 h when the NaOH is used.The blue powders and the green powders can be dissolved into NaAlO2and oxides such as rare earth oxide(REO).The REO can be dissolved in H?concentration 5 mol L-1,S/L1:10 for 3 h in the second acid leaching.The leaching rates of the Y,Eu,Ce,and Tb are 99.06%,97.38%,98.22%,and 98.15%,respectively.The leaching rate of the total rare earth is 98.60%.     

Process optimization and kinetics for leaching of cerium,lanthanum and neodymium elements from iron ore waste's apatite by nitric acid

The leaching of rare earth elements (REEs) including cerium, lanthanum and neodymium from apatite concentrate obtained from iron ore wastes by nitric acid was studied. The effects of nitric acid concentration, solid to liquid ratio and leaching time on the recoveries of Ce, La and Nd were investigated using response surface methodology. The results showed that the acid concentration and solid to liquid ratio have significant effect on the leaching recoveries while the time has a little effect. The maximum REE leaching recoveries of 66.1%, 56.8% and 51.7% for Ce, La and Nd, respectively were achieved at the optimum leaching condition with 18% nitric acid concentration, 0.06 solid to liquid ratio and 38 min leaching time. The kinetics of cerium leaching was investigated using shrinking core model. It was observed that the leaching is composed of two stages. In the first stage a sharp increase in cerium leaching recovery was observed and at the longer time the leaching became slower. It was found that in the first stage the diffusion of reactants from ash layer is the rate controlling mechanism with an apparent activation energy of 6.54 kJ/mol, while in the second stage the mass transfer in the solution is the controlling mechanism.     

Oxidation Properties of a Beta-Stabilized TiAl Alloy Modified by Rare Earth Elements

This paper explores the effects of adding rare earth elements (lanthanum or erbium) on the oxidation properties of Ti–43.5Al–4Nb–1Mo–0.1B (TNM) alloy. Isothermal oxidation tests were performed under air atmosphere at 900 and 1000 °C. Mass gain was measured in several steps during the oxidation test, and the oxidized specimens were characterized by XRD and FE-SEM. The results showed that while adding 0.1 at.% rare earth elements (REEs) reduced oxidation rate of the TNM alloy, 0.2 at.% REEs addition increased the mass gain of the alloys. The oxidation curves were fitted by a power-law equation; the results showed that the oxidation kinetic curves of all alloys obeyed parabolic growth kinetics (n = 2). Meanwhile, the activation energy of oxidation was in the range of 40–50 kCal/mol, thereby suggesting that the scale growth was controlled by mass transport in the TiO₂ layer. Also, the results of the scale characterization showed that addition of REEs at low level (e.g., 0.1 at.%) could reduce diffusion rate in the scale. However, addition of the higher amounts of La or Er (e.g., 0.2 at.%) due to the lower valency (+ 3) of these elements, as compared with Ti (+ 4), could lead to the increased anion diffusion, the formation of hillocks in the scale and a rise of the oxidation rate.     

Effect of temperature-induced phase transitions on bioleaching of chalcopyrite

The phase transformation of chalcopyrite and the effect of its phase status on bacterial leaching were studied. Under the protection of high-purity argon, different temperatures (203, 382 and 552 °C) were applied to natural chalcopyrite to complete the phase change. In addition, the chalcopyrite was bioleached before and after the phase change. The results show that the chalcopyrite heated at 203 and 382 °C remained in the α phase, whereas the chalcopyrite changed from α to β phase at 552 °C. The leaching rates of chalcopyrite after the phase transitions at 203, 382 and 552 °C were 32.9%, 40.5% and 60.95%, respectively. Further, the crystal lattice parameters of chalcopyrite increased and lattice energy decreased, which were the fundamental reasons for the significant increase in leaching rate. Electrochemical experiments demonstrated that with increasing annealing temperature, the polarization resistance decreased and corrosion current density increased. The higher the oxidation rate was, the higher the leaching rate was.     

Effect of Thermal Pretreatment and Acid Leaching on the Removal of Boron from Metallurgical Grade Silicon

The present work aims at investigating the impact of thermal pretreatment and acid leaching (HCl–HF) on the boron removal efficiency of metallurgical grade silicon (MG-Si). The impact of various parameters, involving oxidation temperature (700–1200 °C), oxidation time (1–5 h) and acid leaching (4 mol L^?1 HCl–3 mol L^?1 HF), on the removal of boron from MG-Si was thoroughly explored. It was found that thermal oxidation resulted in an enhanced removal efficiency of boron from MG-Si. By employing MG-Si particles in the range of 75–106 μm in conjunction with acid leaching at 65 °C for 6 h, the boron content was decreased from 19.60 to 14.10 ppmw, offering a removal efficiency of ca. 28%. When the MG-Si powder was subjected to thermal oxidation at 1100 °C for 5 h before leaching, the boron concentration in the purified Si was reduced from 19.60 to 8.90 ppmw, giving an extraction efficiency of 54.59%. An extended characterization study, regarding the microstructure, morphology and chemical composition of both un-treated and treated samples, was conducted to gain insight into the underlying mechanism of boron removal under different conditions.

     

Novel Rare Earth-Bearing Ultra-High-Temperature Ceramics Tested in a Solar Furnace Above 2,200 °C in Air

A novel method for testing ultra-high-temperature ceramics (UHTC) at very high temperature (above to 2,200 °C) in air with an exposure time of several minutes is used. The well-known ZrB₂ + SiC material shows a limited temperature of use in an oxidizing environment due to the low stability above 2,000 °C of any silica that is formed. A few new systems without silicon are proposed, starting with the Hf or Zr, C, B and rare earth elements. The choice of rare earths is motivated by the formation of oxides with melting points higher than 2,000 °C. The complex oxide scales formed during oxidation are accurately described, in terms of presence of porosity and gradients of composition. Similarities with the mechanism of oxidation described for ZrB₂ + SiC materials are shown. A significantly higher thermal stability of rare-earth oxide containing ceramics compared to silica is highlighted. As a consequence, the protective capacity of the oxide scale is improved.     

稀土元素Y对Ti-600合金热稳定性的影响

研究了添加与未添加稀土元素Y的合金固溶时效(STA)处理后以及高温长时暴露(600℃/100 h)后毛坯热暴露的室温拉伸性能,结合显微组织等的分析,探讨了Y对合金热稳定性能的影响。结果表明:稀土元素Y的添加可使合金室温塑性提高,STA时室温延伸率提高25%,600℃热暴露100 h后则提高51.9%。热暴露后,添加稀土合金的塑性损失率明显低于不加稀土合金。合金中,稀土元素Y主要以稀土氧化物Y2O3的形式弥散析出。通过细化组织、降低铝当量、改变合金中的位错组态,改善合金的室温塑性,提高合金的热稳定性。