A. Spanring

State of the Art Refractory Corrosion Test Work for the Nonferrous Metals Industry

This study is a result of a collaboration between Stillwater Mining Company and RHI AG aimed at the determination of refractory products to improve the lining life in the customer’s vessel by using optimized corrosion testing methods at RHI’s Technology Center.

Influence of Arsenic on the Chemical Wear of Magnesia-Chromite Refractories in Copper Smelting Furnaces

Arsenic can be found in different sulfidic copper concentrates and residues, which for several years have commonly been used in copper metallurgy, as the “arsenic-free” resources are getting rare. Due to the high toxicity the removal of arsenic in the copper smelting process is a very important topic. The typical chemical slag and sulfur attack on the refractory material is getting enhanced by the presence of arsenic. This work deals with post-mortem investigations of a magnesia-chromite brick and castable used in copper smelting furnaces showing an additional and increased chemical attack by arsenic. The knowledge on the wear behaviour is not only based on a detailed chemical and mineralogical characterization, but also on thermochemical FactSageTM calculations, which are carried out on provided post-mortem samples. Post-mortem investigations on used refractory materials represent an important prerequisite for the product development, as well as for special engineered lining concepts to support our customers.

High Temperature Phase Formation at the Slag/Refractory Interphase at Ferronickel Production

Corrosion mechanisms between high melting synthetic ferronickel slags and refractory were investigated. The used slags were prepared by mixing and melting of specific oxides. Substrates of the applied refractory material and specimens of FeNi slags were heated in a hot stage microscope up to 1650 °C. The experiments were performed under a defined gas atmosphere of 60% CO and 40% CO2. A further examination of the formed phases between slag and refractory occurred by scanning electron microscope. The investigations indicate that the slag penetrates between magnesia grains and partly dissolves magnesia. Spot analyses show that iron diffuses into the magnesia grains, which transform to magnesiawustite, meanwhile SiO2 forms different types of olivine like forsterite and monticellite. Thermodynamic calculations confirm the formation of these phases. The combination of practical lab scale experiments and thermodynamic calculations should finally contribute to an improvement of the refractory lifetime and performance.

Refractory Challenges in Lead Recycling Furnaces

The refractory linings in lead furnaces are exposed to several stresses rather complex in their interaction. In the present study the magnesia-chromite brick out of a lead recycling furnace suffered from a high chemical attack by the process slag. The high CaO, BaO and sulfur bearing silicate slag, as well as a high Na2O supply from soda resulted both in a deep-reaching infiltration of the brick microstructure and a severe corrosion of the brick components. Both the sintered magnesia and chromite were attacked chemically. The FactSage calculations showed the formation of high amounts of liquid phase in the infiltrated microstructure. Further phenomena affecting the refractory performance such as iron oxide attack, redox effects, and boron attack are also discussed in the paper. The obtained information and insights serve as a basis for improving refractory materials (i.e., choice of refractories for individual process and new developments) and consequently furnace operations.

Zinc and Refractories ‒ A Nasty Relation

Zinc is a component of many input materials used in various pyrometallurgical processes, for example primary lead and zinc production from Pb/Zn ores and recycling processes dealing with zinc-containing residues (e.g., copper recycling, WAELZ process). Hence, zinc and its compounds are present in the respective metallurgical vessels and interact with the refractory lining. In the present work the zinc attack on the refractories out of various primary and secondary furnaces is briefly introduced and discussed. At the prevailing processing temperatures in the metallurgical vessels, zinc oxide is highly corrosive for the brick components. The knowledge of the wear behavior is based not only on a detailed chemical and mineralogical characterization carried out on provided post mortem samples, but also on FactSage calculations. This together with results obtained by practical testing in the RHI pilot plant represents an important prerequisite for product development and brick selection for the individual customer application.

Example of the Refractory Corrosion Test Work with Nickel Matte

In order to improve the refractory lining life at one of the RHI key customer test procedures were developed within a two years collaboration project. In the first year of cooperation detailed refractory corrosion work in the rotary kiln with Ca-ferritic slag was performed. The main results of the second year of cooperation, reported in this article, involve a detailed testing work with nickel matte and pre-selected refractory brands which was performed in TBRC. A first part of this work was a complete chemical and mineralogical characterization as well as FactSage calculations carried out on provided matte samples. According to these results testing in the TBRC was realized at different process temperatures with several magnesia-chromite bricks. Based on the mineralogical investigation a high chemothermal load caused by sulfidic matte resulted in a deep reaching infiltration of the brick microstructure and partly corrosion of main brick components.

Modelling Simulation and Comparison of Refractory Corrosion at RHI’s Technology Center

In order to determine the most suitable refractory products and improve the lining lifetime for the diverse furnaces used in the nonferrous metal industry, corrosion tests are performed at RHF’s Technology Center. The practical facilities include the cup test, induction furnace, rotary kiln, and drip slag test described in this paper, which enable a comprehensive understanding of the chemo-thermal brick wear on a pilot scale. The corrosion trials are performed with actual slags generated during operations at a customer’s plant. To determine the highest influencing wear parameter, every single test is combined with a detailed mineralogical investigation and thermochemical calculations performed using FactSage. Based on the results, tailored refractory solutions for the nonferrous metal industry can be provided in combination with trials conducted at the customer’s site.