Extraction of arsenic from arsenic-containing cobalt and nickel slag and preparation of arsenic-bearing compounds

The arsenic extraction from the arsenic-containing cobalt and nickel slag,which came from the purification process of zinc sulfate solution in a zinc smelting factory,was investigated.The alkaline leaching method was proposed according to the mode of occurrence of arsenic in the slag and its amphoteric characteristic.The leaching experiments were conducted in the alkaline aqueous medium,with bubbling of oxygen into the solution,and the optimal conditions for leaching arsenic were determined.The results showed that the extraction rate of arsenic was maximized at 99.10%under the optimal conditions of temperature 140 ℃,NaOH concentration 150 g/L,oxygen partial pressure 0.5 MPa,and a liquid-to-solid ratio 5：1.Based on the solubilities of As2O5,ZnO and PbO in NaOH solution at 25 ℃,a method for the separation of As in the form of sodium arsenate salt from the arsenic-rich leachate via cooling crystallization was established,and the reaction medium could be fully recycled.The crystallization rate was confirmed to reach 88.9%（calculated on the basis of Na3AsO4） upon a direct cooling of the hot leachate down to room temperature.On the basis of redox potentials,the sodium arsenate solution could be further reduced by sulfur dioxide（SO2） gas to arsenite,at a reduction yield of 92%under the suitable conditions.Arsenic trioxide with regular octahedron shape could be prepared successfully from the reduced solution,and further recycled to the purification process to purify the zinc sulfate solution.Also,sodium arsenite solution obtained after the reduction of arsenate could be directly used to purify the zinc sulfate solution.Therefore,the technical scheme of alkaline leaching with pressured oxygen,cooling crystallization,arsenate reduction by SO2 gas,and arsenic trioxide preparation,provides an attractive approach to realize the resource utilization of arsenic-containing cobalt and nickel slag.

Utilization of nickel slag using selective reduction followed by magnetic separation

In order to utilize slag discarded by nickel plants, the selective recovery of nickel and copper versus iron was investigated by selective reduction, which was achieved by controlling the reduction parameters and magnetic separation process on bench scale. The results show that increasing the basicity （mass ratio of CaO to SIO2） of nickel slag facilitates the enrichment of nickel and copper The process parameters for selective reduction were optimized as follows： basicity of 0.15, reducing at 1200 ~C for 20 min, 5% coal on a dried slag mass base. The grinding-magnetic separation results of reduced briquettes show that concentrate containing 3.25%Ni, 1.20%Cu and 75.26%Fe is obtained and selective enrichment is achieved with a recovery of 82.20%, 80.00% for nickel and copper respectively, while the recovery of iron is only 42.17%. The S and P contents are not reduced obviously and further research may be needed to examine the behaviors of S and P in the process.

Improvement of carbothermic reduction of nickel slag by addition of CaCO3

The effect of CaCO3 addition on the carbothermic reduction of nickel slag was studied,and the mechanism of CaCO3 in improving the reduction was analyzed.The results showed that when the CaCO3 content added to the slag was increased from 0 to 8 wt.%,initiation temperature of the carbothermic reaction decreased from 1100 to 1000℃,the temperature reaching the maximum reduction rate decreased from 1150 to 1100℃,and the reduction degree of the nickel slag increased from 58%to 88%.The iron particles in the reduced nickel slag were coarsened and the X-ray diffraction intensity of metallic iron peaks increased,confirming that the addition of CaCO3 was beneficial to the reduction of nickel slag and recovery of iron.

Application of Modified Nickel Slag Adsorbent on the Removal of Pb^(2＋) and Cu^(2＋) from Aqueous Solution

Al（OH）_3 modified nickel slag adsorbent was prepared by sintering technology. The structure of the sample was characterized by BET, XRD, IR, SEM and EDAX. The sample＇s adsorption performance of Pb^（2＋） and Cu^（2＋） from aqueous solution was studied. Results indicated that the adsorbent is a loose and porous mesoporous material. Its surface had mass aluminosilicate, high-activity γ-Al_2O_3 and its p H ranges from 4 to 12 that all have negative charges. The BET surface of the adsorbent is 23.90 m^2/g. Furthermore, its surface contains rich oxygenic functional groups, which could not only provide abundant adsorption sites for Pb^（2＋） and Cu^（2＋）, but also improve the adsorption performance of Pb^（2＋） and Cu^（2＋） from waste water through the complexation of heavy metal ions. The best p H values selected in the adsorption of Pb^（2＋） and Cu^（2＋） are 6 and 5, respectively. With the increase of the initial concentration of simulated solution, the adsorption capacities of Pb^（2＋） and Cu^（2＋） gradually increased but the removal rates showed a downward trend. The competitive adsorption results of Pb^（2＋） and Cu^（2＋） showed that Pb^（2＋） has better preferential adsorption than Cu^（2＋）.

Adsorption of Pb^2+and Cu^2+with Unburned Desulphurization Slag Modified Nickel Slag

Desulphurization slag modified nickel slag adsorbent was prepared by unburned forming technology. The structure of the sample was characterized by BET,XRD,IR,SEM and EDAX. The adsorption performance of Pb^2＋ and Cu^2＋ onto the resultant adsorbent from aqueous solution was studied. Results indicated that the adsorbent possesses a network pore structure formed by the AFt and C–S–H through cross lapping; the adsorbent contains a large number of Si–OH and Al–OH functional groups. The presence of functional groups not only provides abundant adsorption sites for Pb^2＋ and Cu^2＋,but also improves the adsorption performance of Pb^2＋ and Cu^2＋ from waste water through the complexation of heavy metal ions. The result of specific surface area analysis showed that the adsorbent sample possesses mesoporous structure and the BET specific surface area is 27.15 m^2/g. The solution p H values for the adsorption of Pb^2＋ and Cu^2＋ were optimized to be 6 and 5.5,respectively. The adsorption capacities of Pb^2＋ and Cu^2＋ gradually increase,whereas the removal rates of the two metal ions decrease with increasing the initial concentration of simulated solution. The resultant adsorbent gives a higher adsorption capacity for Cu^2＋ than for Pb^2＋ in the single ion solution. However,it shows preferential adsorption of Pb^2＋ rather than that of Cu^2＋. Meanwhile,results of recyclability indicate the remarkable regeneration capacity,re-adsorption ability and reusability performance of the adsorbent sample.

Effect of mechanical activation on enhancement of carbothermal reduction of nickel slag

The effects of mechanical activation on particle size distribution,crystalline phase,morphology,and mechanical energy storage of nickel slag were studied.Then,the direct reduction experiments of mechanically activated nickel slag mixed with reducing agent graphite powder were performed under conditions of 873-1273 K and reduction for 30-70 min.The results show that after 12 h of activation,90%of the nickel slag has a particle diameter less than 1.05 pm,and the total energy storage is 1790.4 kJ mol^(-1).With the extension of the mechanical activation duration,the intensity of the dift'raction peaks of the main crystalline phases Fe_(2)SiO_(4) and Mg2SiO4 in the nickel slag decreases.Mechanical activation is also an effective means to enhance the reduction of nickel slag.With the extension of the activation time,the reduction effect of the nickel slag and metallization degree increase.After 12 h of mechanical activation,the nickel slag was reduced at 1273 K for 70 min,and the metallization degree of the reduced product could reach 83.12%.

Enhancement of the nickel converter slag-cleaning operation with the addition of spent potlining

The slag cleaning(or matte settling) process was experimentally investigated at 1573 K using a fayalitic nickel converter slag containing spinel and matte/alloy particles.The addition of various amounts of spent potlining(SPL) was studied in terms of its influence on matte settling and the overall metal recoveries.The slags produced were characterized by scanning electron microscopy,energy-dispersive spectroscopy,and wet chemical analysis using inductively coupled plasma optical emission spectrometry.The presence of solid spinel particles in the molten slag hindered coalescence and settling of matte/alloy droplets.Matte settling was effectively promoted with the addition of as little as 2 wt% SPL because of the reduction of spinel by the carbonaceous component of the SPL.The reduced viscosity of the molten slag in the presence of SPL also contributed to the accelerated matte settling.Greater metal recoveries were achieved with larger amounts of added SPL.Fast reduction of the molten slag at 1573 K promoted the formation of highly dispersed metal particles/clusters via accelerated nucleation in the molten slag,which increased the overall slag viscosity.This increase in viscosity,when combined with rapid gas evolution from accelerated reduction reactions,led to slag foaming.

Leaching of magnesium from desiliconization slag of nickel laterite ores by carbonation process

The leaching of magnesium from desiliconization slag of nickel laterite ores by carbonation process was studied.The influence of various parameters was investigated to optimize the conditions and determine the kinetics of the reaction.The results show that with increasing stirring speed,liquid-to-solid ratio and reaction time,and decreasing temperature,the leaching rate of magnesium enhances.The leaching process of the desiliconization slag in the range of 288-298 K is controlled by the surface chemical reaction model.The apparent activation energy is-20.45 kJ/mol,and the kinetics model is obtained.

Viscosities of Fe_nO-MgO-SiO_2 and Fe_nO-MgO-CaO-SiO_2 slags

The viscosities of molten FenO-MgO-SiO2 and FenO-MgO-CaO-SiO2 semi-synthetic slags for nickel flash smelting were mearured in the temperature range of 1 2001 450 ℃ by use of a rotational viscometer. The mass ratio of Fe to SiO2 was fixed at 1.2, calcium oxide and magnesium oxide contents varied in the range of 2%8% and 9%12%（mass fraction）, respectively. The results show that silicate anions become smaller by increasing CaO content, which results in the viscosity decrease of slag. In the case of addition of MgO the viscosity behaviour is complicated. When MgO content is less than 11%, the viscosity increases with the increase of MgO at all temperatures tested . However, when the MgO content is more than 11%, the viscosity decreases slightly for FenO-MgO-CaO-SiO2 system. At higher MgO contents, low-viscosity slags can be obtained by adding CaO. As for a given composition, the viscosity decreased with increasing temperature .The higher the temperature, the more MgO can be added before saturation. The effect of Fe3O4 on the viscosity is quite significant. The viscosity of slag increases to 300 mPa·s at （1 300 ℃） when Fe3O4 content varied from 2.84% to 9.53%. The viscosity values are expressed as the functions of temperature and composition. A comparison between FenO-MgO-SiO2 and FenO-MgO-CaO-SiO2 systems are also given.

Activity coefficients of NiO and CoO in CaO–Al_2O_3–SiO_2 slag and their application to the recycling of Ni–Co–Fe-based end-of-life superalloys via remelting

To design optimal pyrometallurgical processes for nickel and cobalt recycling, and more particularly for the end-of-life process of Ni-Co-Fe-based end-of-life（EoL） superalloys, knowledge of their activity coefficients in slags is essential. In this study, the activity coefficients of NiO and CoO in CaO-Al_2O_3-SiO_2 slag, a candidate slag used for the EoL superalloy remelting process, were measured using gas/slag/metal equilibrium experiments. These activity coefficients were then used to consider the recycling efficiency of nickel and cobalt by remelting EoL superalloys using CaO-Al_2O_3-SiO_2 slag. The activity coefficients of NiO and CoO in CaO-Al_2O_3-SiO_2 slag both show a positive deviation from Raoult＇s law, with values that vary from 1 to 5 depending on the change in basicity. The activity coefficients of NiO and CoO peak in the slag with a composition near B =（%CaO）/（%SiO_2） = 1, where B is the basicity. We observed that controlling the slag composition at approximately B = 1 effectively reduces the cobalt and nickel oxidation losses and promotes the oxidation removal of iron during the remelting process of EoL superalloys.

Study of decomposing carbonyl slag

A new technology was put forward to deal with the carbonyl slag at low acidity and low oxygen pressure in the kettle. With the orthogonal experiments for analyzing the sequence of four factors and some single factor experiments for the best conditions. The best conditions are used for extracting nickel, cobalt and copper and enriching precious metals: the cupric ion concentration is 5 g/L; and pH=6; the sulfur coefficient is 1.4; the oxygen pressure is 0.08 MPa; the time bubbling oxygen is 20 min; the ratio of liquid to solid is 8:1; the leaching time is 2 h; the heating time is 2.5 h. The leaching rates of nickel and cobalt are more than 98% and that of copper is above 97%. Nickel and cobalt can be separated efficiently from copper and precious metals from the carbonyl slag. Moreover, its leaching liquor has less copper. Nickel and cobalt can be reclaimed only once. During the whole process, the leaching rates of Au and Ag are more than 99.9%, while other precious metals are still in the residue without any loss.

响应曲面法优化二次镍渣微晶玻璃热处理制度

镍渣作为有色冶炼过程产生的冶金废渣,以堆存形式处理,环境影响突出,但含铁量高,是一种极具开发前景的二次利用资源。以二次镍渣为原料制备微晶玻璃,采用响应曲面法并结合Box-Behnke原理设计探讨了核化温度、核化时间、晶化温度、晶化时间及其交互作用对微晶玻璃抗折性能的影响,建立了抗折强度与各因子间的模型。通过模拟优化,确定了最佳热处理工艺参数:核化温度和晶化温度分别为845℃和955℃、核化时间和晶化时间均为80 min。采用最优工艺参数试验验证发现,微晶玻璃主晶相为铁硅灰石和钙长石,抗折强度均值达到126.78 MPa,与模型预测值偏差较小,表明该预测模型可靠有效及工艺优化合理可行。

单组分电炉镍渣基地聚物修补材料制备与性能调控

为利用具有潜在活性的固体废弃物电炉镍渣,制备单组分电炉镍渣基地聚物修补砂浆.基于正交实验和极差分析,通过掺入掺合料并改变碱模数和碱当量等关键影响因素,对地聚物砂浆各项修补性能进行调控,获取满足修补性能的最优配合比,确定各因素对修补性能的影响主次.结果表明,最优配比是矿渣掺量为30%,粉煤灰掺量为30%,碱模数为1.2,碱当量为6.5%,其28 d抗压、抗折强度分别为90.29、9.23 MPa,干燥收缩率为0.56×10-3,14 d拉伸粘结强度为3.64 MPa,满足修补砂浆规范要求.经比较,矿渣掺量对修补砂浆性能调控影响最为显著.

基于调渣提铁的镍冶炼渣熔化温度调控

目前,镍渣提铁工艺存在提铁效率低、工艺实施难度大、成本高等问题。本文通过相图分析、单因素和正交实验等方法,研究了炉渣中主要氧化物含量对半球点温度的影响,得到了有利于提铁的炉渣渣型优化方案。结果表明:当CaO含量(质量分数)为25%、MgO含量为9%、铁硅比为0.8时,该渣型的半球点温度最低。考虑到现行工艺,选择MgO含量为13%、CaO含量为20%、铁硅比为1.0为较优方案,所得炉渣的半球点温度明显低于现行顶吹炉渣的半球点温度。调整后的炉渣中含铁物相由以硅酸亚铁为主转化为以钙铁榴石和铁氧化物为主,有利于后续提铁。

镍冶炼渣中铁资源回收研究现状及发展分析

镍渣为有色冶炼过程中产生的冶金废渣,铁品位高达40%,具有较高的回收利用价值。镍渣中的铁主要以硅酸亚铁形式的化合物为主,难以对其进行有效提取。如何合理利用镍渣,对行业可持续、绿色化发展具有重大意义,是目前的研究热点。本文对镍渣中铁资源回收技术进行了综合分析,针对现有镍渣提铁工艺中存在的问题,提出在镍冶炼过程中加钙以调整镍渣渣型和降低冶炼温度,使铁橄榄石向铁酸钙形式转变,降低后续提铁难度,以期实现镍渣的高值资源化综合利用。

镍渣—全尾砂混合骨料配比试验研究

为实现固废循环利用,降低尾砂和镍渣的固废堆存,开展了镍渣—全尾砂混合骨料配比试验。通过扫描电镜和X射线荧光光谱测定(XRF)方法分析了镍渣和全尾砂的粒级分布和化学成分,利用骨料堆积密实度理论确定了镍渣—尾砂的配比优化范围为4∶6、5∶5和6∶4;考虑料浆的流动性、和易性及充填体强度,最终推荐镍渣—全尾砂的最优配合比为5∶5,料浆的质量浓度为77%~79%,水泥添加量为310 kg/m^(3);针对镍渣—全尾砂充填,镍渣利用量最高不超过50%,最大质量浓度为79%,对应的剪切应力为112.634 Pa,黏度为0.938 Pa·s。

还原介质对镍渣直接还原提铁的影响

如何从富铁镍渣中高效提铁是该资源综合再利用的关键。本文采用焦炭和烟煤作为还原剂,对镍渣进行直接还原提铁试验研究,对比两种还原剂在镍渣还原过程中产生有效还原介质的差异,借助热力学软件对不同还原介质的还原能力进行热力学分析,然后通过试验及表征研究两种还原剂对镍渣还原过程金属化率变化及微观结构演变的影响。结果表明:烟煤含有的高挥发分会产生CO-H_(2)混合的还原介质,而焦炭则主要以CO还原介质为主;热力学分析结果表明,CO-H_(2)混合气对铁氧化物的还原能力优于纯CO。镍渣还原焙烧试验结果显示,使用烟煤作为还原剂,1 300℃下还原20 min,镍渣球团的金属化率可达90.20%;而采用焦炭作为还原剂时其金属化率仅达到72.97%,烟煤对镍渣的还原能力优于焦炭。

遵义某钼镍矿矿渣自燃机理及防治方法探讨

为对自燃钼镍矿矿渣开展综合治理,通过遵义某钼镍金属矿矿渣现场调查及样品采集分析,查明了钼镍矿矿渣的矿物成分、元素含量及主要自燃气体成分,初步确定钼镍矿矿渣自燃的引燃物为黄铁矿,提供可持续燃烧的可燃物主要为炭质,当矿渣自身属性满足要求,供氧及聚热条件达到某一平衡时,便会发生自燃;提出了“降温+切断供氧通道”,“注浆+覆盖”综合治理措施以及尚未自燃矿渣的预防建议。工程验证治理取得了良好的效果,研究成果为同类型工程问题提供了一定的解决经验和思路。

富镁镍渣-偏高岭土基地质聚合物的制备及耐火性能研究

在富镁镍渣(HMNS)中掺入偏高岭土(MK)制备了富镁镍渣基地质聚合物,通过高温实验探究了富镁镍渣基地质聚合物的耐高温性能,并采用XRD、FT-IR、SEM和同步热分析(TG-DSC)等表征分析了富镁镍渣基地质聚合物的水化产物、相变和显微结构。结果表明,富镁镍渣基地质聚合物在室温下的抗压强度可达16.0 MPa。暴露于1200℃后,抗压强度提高至38.8 MPa且热膨胀率仅为1.05%,表现出优异的耐高温性能。室温下主要的结晶产物是镁磷石和柏林石。非晶相主要由—Al—O—P—、—Si—O—P—、—Si—O—P—O—Al—和—P—O—Mg—等结构组成。暴露于高温后,相变、物理自由水的蒸发、化学结合水的脱水、去羟基化、胶凝相的收缩以及烧结是影响富镁镍渣基地质聚合物力学性能和微观结构变化的主要因素。

不锈钢冶金废渣制备超细掺合料配比研究

在节能减排和绿色发展的背景下,大量堆放的冶金固废对环境污染的问题亟待解决。针对不锈钢生产过程中排放的工业固废—镍铁渣与不锈钢尾渣,复掺粉煤灰、脱硫石膏,以7d活性和28d活性为性能指标,基于力学性能进行配比优化研究。结果表明:不锈钢尾渣和镍铁渣的掺入比例对于超细掺合料的活性影响最大,其次是粉煤灰的掺入量,脱硫石膏的掺入量对于活性的影响相对较小。比表面积超过600cm^(2)/g以后继续粉磨对活性提升不明显。综合考虑制备超细固废掺合料的配比为镍铁渣:不锈钢尾渣=8∶2,粉煤灰掺量为20%,SO_(3)的含量控制在3.0%,比表面积为600cm^(2)/g,此时超细掺合料的28d活性最高,7d活性80%,28d活性达91%。