镍沉降渣深度还原过程中的相变特征

通过化学成分、光学显微镜、X射线衍射、扫描电镜能谱分析等测试手段,分析了镍沉降渣矿物成分和嵌布特点和沉降渣深度还原过程中物相的转变特征,结果表明,渣的物相由铁镁橄榄石和玻璃质组成.渣中主要有用成分铜镍铁硫化物嵌布粒度微细,分布无规律,回收困难.经深度还原,沉降渣逐渐转变为镁黄长石、含镍金属铁、辉石、钙霞石、钠闪石、石英等新的矿物成分,加热至1300℃,还原产物物相组成稳定,镁黄长石和含镍金属铁相对含量最高.还原时间也是影响还原效果重要因素,含镍金属铁相对含量随还原时间的增加而增长,120 min时相对含量最高.热力学分析表明,镍沉降渣深度还原过程中主要发生的反应为铁镁橄榄石与氧化钙作用生成镁黄长石和FeO,FeO被C和CO还原为金属铁.金属硫化物与CaO和C通过氧化还原作用,生成的金属铜和镍溶于金属铁中,产生的CaS与硅酸盐一起析出.      

含碳球团熔融渗碳机理

使用CaO-SiO_2-Al_2O_3合成渣与磁铁矿、石墨粉制备含碳球团,考察了球团中渣相成分、渣量以及碳含量对铁水渗碳量的影响,并探讨了含碳球团内铁的熔融渗碳行为和机理。结果表明,熔融渗碳分为熔融还原渗碳以及铁熔体聚合过程渗碳2个阶段,前一阶段熔渣中Fe2+含量与铁的渗碳量处于动态平衡过程,主要受熔渣化学成分的影响;后一阶段的渗碳过程决定铁的物理渗碳极限,主要与铁、碳颗粒的接触条件有关,且熔渣中Fe2+的还原极限与渣相碱度和SiO_2绝对含量有关,铁的熔融渗碳量(质量分数)可以达到4%左右,满足铁锍分离要求。     

钒钛渣系与碳饱和铁水间的熔融还原研究

应用渣-金间元素反应动力学的实验装置,研究了1460～1620℃之间钒钛渣与含Si,Mn碳饱和铁水间V,Ti氧化物的熔融还原动力学及元素的平衡分配,得到了铁水温度及渣碱度的变化对V,Ti氧化物还原动力学的影响规律及V在渣-铁间的分配行为。实验发现,在所测定的反应时间内,反应可分为两个阶段,并从实验结果推测了各个阶段可能的控制步骤。1460℃下,当平衡渣碱度为1时,钒在渣-金间的分配系数有最低值。     

高钛渣碳热还原—浮选法提取Ti_2CO

通过高温碳热还原分别将高钛渣中的钛和铁还原至富钛相物质Ti2CO和金属铁,并使其中的熔渣相MOx不被还原,然后选用油酸作为捕收剂对Ti2CO/MOx模拟混合原料开展了浮选研究。结果表明,采用该工艺从还原产物中得到了产率79.88%、Ti2CO回收率87.74%的浮选效果。     

Al2O3对钙硅镁系微晶玻璃性能和析晶动力学的影响

冶金渣经过改质还原并回收金属铁元素后,利用剩余熔渣直接制备成微晶玻璃等高附加值材料,是实现冶金渣高效低碳资源化的有效途径之一.提取金属铁后的熔渣多以CaO-SiO2-MgO渣系为主,通常还需要补充适量Al2O3来改善微晶玻璃相关性能.本文通过向CaO-SiO2-MgO三元玻璃体系中引入不同比例Al2O3,来研究其对微晶...     

H2-C熔融还原条件下渣金间磷的分配比的试验研究

 通过300kg级氢-碳熔融还原热模拟试验,从热力学角度分析了氢-碳混合熔融还原条件下磷的分配比,运用熔渣规则溶液模型计算了氧化钙、二氧化硅、氧化镁、氧化铝、氧化亚铁、五氧化二磷六元熔渣组分的活度、活度系数,进而计算出一定温度条件下熔渣的磷容量以及渣金平衡时磷分配比的理论值。通过比较理论计算得出的磷分配比与试验中磷的分配比的差异,解析产生差异的原因,进而为氢-碳混合熔融还原炼铁新工艺冶炼高磷铁矿提供参数。试验结果表明：用熔渣规则溶液模型计算渣金间的磷的分配比是合适的,氢-碳熔融还原工艺可以利用高磷铁矿。     

还原剂与脱硫剂对硫酸渣直接还原焙烧同步脱硫的影响

研究了还原剂云南煤和脱硫剂SH对硫酸渣在直接还原焙烧过程中提铁降硫效果的影响.采用X射线衍射与扫描电镜方法分析了云南煤与脱硫剂SH的作用机理.结果表明:在高温还原气氛下,硫酸渣中的黄铁矿生成具有挥发性的气态单质硫和气态羰基硫、金属铁和非磁性的陨硫铁;硫酸渣中的赤铁矿和磁铁矿则被还原为金属铁;云南煤对硫酸渣在焙烧过程中的脱硫效果比较明显,但无法达到要求的指标;添加脱硫剂SH可以进一步降低还原铁中的硫,其机理是脱硫剂与硫酸渣中的黄铁矿在直接还原焙烧过程中反应生成金属铁和没有磁性的硫化钙,通过磨矿-磁选的方法将硫化钙与金属铁分离,从而达到脱硫目标.      

不同矿种H2-C熔融还原过程中CaO-SiO2-Al2O3-MgO系熔渣的起泡行为

 在1400℃下,通过300kg级氢碳熔融还原热模拟试验,用渣线测定装置研究了不同矿种在氢碳熔融还原过程中CaO-SiO2-Al2O3-MgO系熔渣的起泡行为,测定了熔渣的起泡高度、泡沫渣厚度、熔渣起泡率等参数。通过计算得到了气泡大小和熔渣的物理化学性质。结果表明,泡沫渣厚度随表观气体流速(反应速率)的增加而增加,表观气体流速相近时又随熔渣的黏度增大而增加。熔渣起泡率最高的矿种为生矿,为3.4。通过对泡沫渣厚度的因次分析,得到了泡沫渣厚度与熔渣黏度、密度、表面张力、气体表观流速、气泡大小及重力加速度的关系。     

熔渣导电性的研究

以固体电解质脱氧为例,分析了渣金反应的电化学机理。结合熔渣导电性方面已有的研究成果及应用情况的分析得出结论：一切有利于熔渣中电子和（或）空穴在金属与熔渣界面传递的措施,都将大大提高金属与渣相的反应速率。     

钒钛磁铁矿金属化球团固结机理研究

以转底炉工艺为基础,在实验室模拟条件下,研究了钒钛磁铁矿金属化球团的固结机理。讨论了配碳量(C/O)、还原温度、还原时间对球团金属化率和抗压强度的影响,确定了金属化球团的固结机理。研究发现:钒钛磁铁矿金属化球团的抗压强度主要与金属铁相的数量和形态以及金属化球团内孔隙的大小有关;金属化球团孔隙的大小主要取决于配碳量高低和脉石所形成的渣相对金属化球团内部孔隙的填充状态;金属铁相的数量和形态则取决于金属化球团的还原程度。随着还原温度升高和还原时间延长,金属化球团内部金属铁相密集度增加,渣相流动性改善,从而导致金属化球团孔隙减少且变小,球团强度增加。     

Influence of Partial Pressure of Sulfur and Oxygen on Distribution of Fe and Mn between Liquid Fe-Mn Oxysulfide and Molten Slag

The authors proposed an innovative process for recovering Mn from steelmaking slag. The process starts with the sulfurization of steelmaking slag to separate P from Mn by the formation of a liquid sulfide phase (matte). Then, the obtained matte is weakly oxidized to make a Mn-rich oxide phase without P. High-purity Fe-Mn alloys can therefore be produced by the reduction of the Mn-rich oxide phase. However, to the authors?? knowledge, the sulfurization of molten slag containing P and Mn has not been sufficiently investigated. It was recently found that P was not distributed to the matte in equilibrium with the molten slag. To gain knowledge of the process??s development, it is important to investigate the influence of the partial pressures of sulfur and oxygen on the equilibrium distribution of Mn and Fe between the matte and the molten slag. In the current work, a mineralogical microstructure analysis of the matte revealed that the existence of the oxysulfide and metal phases was dependent on the partial pressure of sulfur and oxygen. The Mn content of the matte increased with partial pressure of sulfur while the O content of the matte decreased. In contrast, the ratio of Mn/Fe in the matte was constant when the metal phase of the matte was observed at a log $ P_{{{\text{O}}_{2} }} $ below ?11. These results also corresponded to the relationship between the activity coefficient ratio of MnS/FeS and the mole fraction of MnS/FeS in the matte. The ?? _MnS/?? _FeS value decreased exponentially as the mole fraction of MnS/FeS increased.     

Thermodynamic Modeling of Arsenic in Copper Smelting Processes

Published data on the activity coefficients of arsenic in liquid copper, matte and, slag have been reviewed, assessed, and used in the development of thermodynamic databases for solution models of melts. The databases were validated against the literature data on the equilibrium distribution of arsenic between the matte and the slag. The models and databases were used in investigating the effects of matte grade, slag chemistry, SO₂ partial pressure, arsenic loading, and temperature on the equilibrium distribution of arsenic between the melts and gas phase during copper smelting and converting. The results obtained show that the continuous smelting processes operates close to equilibrium between condensed phases with most arsenic reporting to the gas phase. A comparison of the batch and continuous converting processes showed a considerable difference with respect to the elimination of the arsenic from condensed phases. These results indicate batch processes to be more efficient in the removal of arsenic through the gas stream.     

Thermodynamic modeling of lead distribution among matte, slag, and liquid copper

Recently, a thermodynamic database was developed for the calculation of equilibria involved in the production of copper. The present study is concerned with the further development of the thermodynamic models and the database of model parameters for the matte, slag, and blister copper phases with a view to including Pb in the database and permitting calculations in the seven-component system Pb-Cu-Ca-Fe-Si-O-S. Thermodynamic and phase equilibrium data available in the literature are reviewed, critically assessed, and optimized with the modified quasi-chemical model. When used with the Gibbs energy minimization software and other databases of the FACT thermodynamic computing system, the database developed in the present study can be used for the calculation of matte-slag-copper-gas phase equilibria during copper smelting and converting. The distribution of lead among these phases can be computed. For example, the distribution of lead among matte, silica-saturated slag, and copper has been calculated at metal saturation, or under fixed partial pressure of SO₂, and has been compared with the available experimental data. The Pb distributions among the equilibrium phases have been calculated under various conditions, which are difficult to study experimentally, such as at magnetite saturation or under various oxygen partial pressures and iron to silica ratios in the slag.     

Effect of Iron Phase Evolution on Copper Separation from Slag <Emphasis Type="Italic">Via</Emphasis> Coal-Based Reduction

Copper slag, a by-product of copper pyrometallurgy, inevitably contains a certain amount of copper. Oxygen-enriched smelting technologies increase the copper content in slag indirectly because of the production of higher-grade matte. The effect of iron phase evolution on the copper content in slag during the slag cleaning process in an electric furnace was investigated using the method of combining theory with experiments. Based on the analysis, the main factors that impede the separation of slag and copper/matte were determined. Subsequently, the properties of slag were analyzed after decreasing the magnetite content within the slag. The experimental results showed that decreases in magnetite content were beneficial for the separation of copper and slag because of the decrease of slag viscosity. Nevertheless, Cu-Fe alloys formed when magnetite was completely reduced to metallic iron, and the foaming slag was formed at 1250 °C. Furthermore, the distribution of copper in the reduced slags was studied in detail.     

A New Technology for Copper Slag Reduction to Get Molten Iron and Copper Matte

The change of iron composition as well as the removal of copper from iron was investigated in the reduction process,and a new way to deal with copper slag was proposed.The iron in copper slag exists mainly in the form of fayalite,and the copper sulfide content accounts for just about 50%.Therefore,the magnetic separation as well as grinding floatation method is not suitable,and a pyrogenic treatment on copper slag is necessary.The carburization and desulfurization process is restricted to a degree within the carbon composite pellets,and copper matte phase precipitates from copper slag in the reduction process,which is immiscible with molten iron and slag.The copper content decreases to 0.4% as the carbon content in molten iron reaches 3.84%,and the removal ratio of copper from molten iron approaches to 80%.The reduction and sulfurization process can be completed in one step,and the copper is separated from iron based on the ternary system of iron-matte-slag.     

A thermodynamic database for copper smelting and converting

The thermodynamic properties of the slag, matte, and liquid copper phases in the Cu-Ca-Fe-Si-O-S system have been critically assessed and optimized over the ranges of compositions of importance to copper smelting/converting based on thermodynamic and phase equilibria information available in the literature and using the modified quasichemical model. A thermodynamic database has been developed, which can be used for the calculation of matte-slag-copper-gas phase equilibria of interest for the production of copper. The model reproduces within experimental error limits all available experimental data on phase diagrams, matte-alloy miscibility gap and tie-lines, enthalpies of mixing, and activities of Cu and S in the matte and liquid alloy. The calculated solubilities of Cu in both S-free slag and slag equilibrated with matte are also in good agreement with experiment under all studied conditions, such as at SiO₂ saturation, in equilibrium with Fe, Cu, or Cu-Au alloys, at fixed oxygen or SO₂ partial pressures and at different contents of CaO in the slag. Sulfide contents (sulfide capacities) of the slags are predicted within experimental error limits from the modified Reddy-Blander model, with no adjustable parameters. As an example of the application of the database, the stability field of matte/slag equilibrium is calculated, and the matte and slag compositions are plotted vs iron to silica ratio in the slag at various SO₂ pressures over this field. The matte-slag two-phase field is limited by the calculated lines corresponding to precipitation of copper, silica, and magnetite.     

Thermodynamic prediction of melting of copper-electrolyte slime

Balance calculations of multicomponent equilibrium compositions in the gas–liquid–solid system under oxidizing smelting of the copper-free copper-electrolyte slime, during which sulfur, selenium, and tellurium dioxides transfer into the gas phase, while compounds of lead, copper, antimony, iron, and aluminum are concentrated in the composition of the silicate slag, are performed with the help of the Outotec’s Chemical Reaction and Equilibrium Software HSC Chemistry program. It is established that, under optimal conditions of oxidizing smelting of the charge (100 kg) of the electrolyte slime (O₂ ≈ 0.9 kg, SiO₂ ≥ 6%, CaO ~ 3%, t = 1200°C), lead, antimony, and arsenic almost completely transfer into the silicate slag, while copper and silver (above 91%) transfer into the matte. Selenium is distributed between the gas phase (49.8%), matte (24.1%), and metallic phase (26.1%), while tellurium is distributed between sublimates (14.4%), silicate slag (8.4%), and matte (77.2%).     

硫含量对KR脱硫渣中硫赋存状态的影响

KR脱硫渣中的CaO是转炉冶炼工艺中重要的造渣原料,将其回用于钢铁冶炼工艺可降低冶金企业的CaO原料消耗,减少企业KR脱硫渣堆积量,节约企业冶炼的经济成本.KR脱硫渣中的2CaO·SiO2 (C2S)在转炉脱磷冶炼过程中可与炉渣中的磷形成稳定的2CaO· SiO2-3CaO· P2O5固溶体,提高磷在渣中的稳定性.将K...     

KR脱硫渣矿相及硫在渣中分布

 为探讨KR脱硫渣的脱硫机理,利用现场取脱硫渣,通过炉渣淬火实验,对渣中矿相组成和硫在渣中分布进行研究与分析。研究结果表明：KR渣主要位于CaO-SiO2-CaF2-CaS四元系,渣中含有单一的CaS相、以CaO为主的CaO-CaF2-CaS相和以CaO、SiO2为主的CaO-SiO2-CaF2-CaS相,且CaS相中的硫含量明显高于其他2种矿相。通过统计渣相中CaS相的面积分数,并结合炉渣总的硫含量,得出渣相中的硫主要以单一的CaS形式存在。因此,通过提高渣相中CaS相的面积分数,可提高炉渣硫含量。