Katri Avarmaa

MTDATA and the Prediction of Phase Equilibria in Oxide Systems: 30 Years of Industrial Collaboration

This paper gives an introduction to MTDATA, Phase Equilibrium Software from the National Physical Laboratory (NPL), and describes the latest advances in the development of a comprehensive database of thermodynamic parameters to underpin calculations of phase equilibria in large oxide, sulfide, and fluoride systems of industrial interest. The database, MTOX, has been developed over a period of thirty years based upon modeling work at NPL and funded by industrial partners in a project co-ordinated by Mineral Industry Research Organisation. Applications drawn from the fields of modern copper scrap smelting, high-temperature behavior of basic oxygen steelmaking slags, flash smelting of nickel, electric furnace smelting of ilmenite, and production of pure TiO2via a low-temperature molten salt route are discussed along with calculations to assess the impact of impurities on the uncertainty of fixed points used to realize the SI unit of temperature, the kelvin.

Distribution equilibria and slag chemistry of DON smelting

Equilibrium fluxing chemistry and metal value distributions of nickel matte smelting in the one-step direct nickel matte technology have been determined experimentally at 1350–1450°C in MgO-bearing iron silicate slags at silica saturation. The aim was to approach the detailed smelting chemistry at typical concentrations 2.5–10 wt-% iron in MgO-bearing iron silicate slags at silica saturation by quenching and X-ray microanalysis. The results obtained under controlled P(O2) and P(S2) as well as constant P(SO2) = 0.1 atm show that copper and nickel solubilities in the slag as well as matte-to-slag distributions favour matte when the slag is modified by magnesia. At the same time, along with increasing magnesia content of the slag, its iron activity is affected by the dissolution of MgO in the slag, and iron concentration of the formed nickel matte is lowered considerably, and its sulphur concentration increased at constant oxygen and sulphur pressures of the gas phase.

Recoveries of rare elements Ga, Ge, In and Sn from waste electric and electronic equipment through secondary copper smelting

The recycling and recovery of valuable metals from waste materials is one of the key issues in maintaining the sustainability of base and rare metals. Especially WEEE (Waste Electric and Electronic Equipment) can be considered as a high potential resource for a number of valuable and critical metals like gallium, germanium and indium. During the mechanical processing of WEEE, these metals are primary separated into the non-ferrous scrap fractions, including copper fraction. As a consequence, the behavior of these valuable metals and the possibility of their recycling in secondary copper smelting are of great interest. This study experimentally investigates the distribution behavior of indium, gallium, germanium and tin between metallic copper and lime-free / lime-containing alumina iron silicate slags (LCu/s[Me] = [Me]Copper/(Me)Slag), as well as between solid Al-Fe spinel and slags (Lsp/s[Me] = {Me}spinel/(Me)slag). Moreover, the copper-slag-spinel equilibrium systems are examined. The experiments were executed simulating high alumina-bearing copper scrap smelting in typical black copper smelting conditions of pO2 = 10-10-10-5 atm (1 atm = 1.01325 × 105 Pa) and T = 1300 °C. The experimental technique employed utilized a highly advanced equilibration-rapid quenching method followed by Electron Probe Micro-Analysis (EPMA). The results show that tin and indium can be efficiently recovered into the copper phase in reducing process conditions (pO2 below 10-7 atm), whereas gallium dissolved preferentially into the solid spinel phase in all conditions examined. Gallium dissolution into slag and spinel was found to occur as GaO1.5, whereas indium in spinel was determined to be as InO1.5. In addition, germanium was seen to distribute preferentially into the copper phase with LCu/s[Ge] = 2-4, although its concentrations in all phases present were relatively low. Thus, the main route for germanium can be considered to be vaporization.

Fundamental Process Equilibria of Base and Trace Elements in the DON Smelting of Various Nickel Concentrates

The converter-less nickel matte smelting technology (DON) adopted more than 20 years ago in Boliden Harjavalta smelter has been since that applied successfully to the processing of large number of nickel sulphide concentrates of various Ni-to-Cu ratios and MgO contents. The operational point of the technology is far from the conventional primary nickel smelting in the smelting-converting route. Therefore, a careful scouting of distribution equilibria of the base and trace elements in the smelting conditions of DON process has been conducted, in order to obtain quantitative information about the equilibria and thermodynamic properties of the nickel mattes at low iron concentrations, less than 10 wt% [Fe] in matte. The series of investigations has included novel experimental and analytical techniques for increasing the reliability and sensitivity of the phase equilibria as well as the element distribution observations carried out in typical high-grade nickel matte smelting conditions.

Equilibria of Gold and Silver between Molten Copper and FeOx-SiO2-Al2O3 Slag in WEEE Smelting at 1300 °C

Waste Electrical and Electronic Equipment (WEEE) offers a significant resource for precious metals such as gold and silver. To maximize precious metal recoveries and sustainable use their behavior during WEEE smelting with copper as the collector metal needs to be characterized. This study experimentally determines the distributions of gold and silver between metallic copper and FeOx-SiO2-Al2O3 slag (LCu/s[Me] = [Me]Copper/[Me]Slag) in alumina-saturation over the oxygen potential range of 10-5–10-10 atm at 1300 °C. The experiments were conducted employing equilibration / quenching followed by major element analysis by Electron Probe Micro-Analysis (EPMA) and trace element analysis by Laser Ablation Inductively Coupled Mass Spectrometry (LA-ICP-MS) techniques. Our results show silver distribution increased exponentially from 30 to 1000 as a function of decreasing oxygen partial pressure. Gold distribution was 105 at pO2 = 10-5 atm and >106 at pO2 = 10-6–10-10 atm.

Behavior of Nickel as a Trace Element and Time-Dependent Formation of Spinels in WEEE Smelting

For better understanding and maximal value utilization of the WEEE smelting process, the behavior and distribution of different trace elements must be known. In this study, the behavior of nickel as a trace element was studied in an equilibrium system with metallic copper—spinel saturated iron silicate slag (with 3 wt-% K2O)—iron aluminous spinel—gas. The experiments were conducted in alumina crucibles at 1300 °C, in oxygen pressure range of 10−10–10−5 atm. A time series of 15–60 min experiments was also conducted for investigating the formation rate of the primary spinel phase in the system. The results show that the distribution coefficient of nickel between metallic copper and liquid slag changes from approximately 70 to 0.4 along the increasing oxygen pressure range. In addition, a significant part of the nickel deports into the spinel phase. The spinel formation was investigated based on composition analysis results and visual observations from SEM-images.

The Influence of Aluminum on Indium and Tin Behaviour During Secondary Copper Smelting

Aluminum and copper are large volume metals in electronic appliances, while tin and indium exist as common minor elements. All of these non-ferrous metals are aimed to be separated and recycled from the end-of-life electronics into non-ferrous scrap fraction(s), and further through pyrometallurgical and/or hydrometallurgical processes to pure metals. Depending on the mechanical pre-treatment processes, aluminum and copper liberation from each other varies. This study focuses on the influence of alumina on indium and tin distributions between copper alloy and iron silicate slags with 0, 9 and ~16 wt% of Al2O3. The experiments were executed with an equilibration-quenching-EPMA technique in an oxygen pressure range of 10−10–10−5 atm at 1300 ℃. The metal-slag distribution coefficient of indium remains constant as a function of alumina in slag, while that of tin increases. Therefore, aluminum in feed or alumina addition to the slag improves the recovery of tin into copper. Nevertheless, oxygen pressure has clearly more significant influence on the behavior of both the metals in the smelting conditions.

Properties of Na2O–SiO2 slags in Doré smelting

ABSTRACT Solubilities of metals in sodium silicate slags have been studied at 1000–1300°C in oxygen pressures of P(O2) = 10−4 to 0.5 atm, in Doré alloy smelting of copper anode slimes. The boundary conditions for the slags were silica saturation, magnesia saturation with about 10 wt% and without BaO. The trace elements studied were copper, gold, palladium, rhodium, and tellurium. The analytical methods used in the phase composition analyses of equilibrated samples, quenched in brine, were electron probe X-ray microanalysis and laser ablation-inductively coupled plasma-mass spectrometry. Thermodynamic features of the slags, trace element solubilities with the given constraints, and their oxidation mechanisms were determined. The data allow optimizing the anode slime-smelting for the metals’ maximum recovery in sodium silicate fluxing.