Deposition of carbon from methane on manganese sources

Carbon has been deposited on HCFeMn slag from methane-containing gas with and without CO2, creating C-MnO composites and giving a hydrogen-rich off-gas as a by-product. The maximum deposited amount corresponds to 38 ± 6% of the carbon required for reduction of all manganese in the slag to metallic Mn. This was achieved at 1100 °C with a H2-concentration in the off gas of 76%. Temperature was an important parameter. At 790 °C, no deposited carbon was detected, at temperatures ≥ 1000 °C, deposition increased with temperature. A lower gas-flow leads to more methane decomposition. Experiments with CO2 in the process gas gave less deposited carbon than other experiments. This could be caused by dilution of methane or chemical reactions involving CO2, or a combination. Investigations of fines formation indicate that the deposited carbon sticks well to the HCFeMn-slag, and would not fall off easily during transport and handling. This demonstrates that biogas can potentially be a non-fossil source of carbon in manganese production.publishedVersio

SiC formation and SiO reactivity of methane at high temperatures

Methane (CH4) is a carbon source currently not in use in the production of silicon. Using a gaseous carbon source instead of conventional solid carbon sources presents an opportunity to rethink silicon production. Preliminary research into this topic has shown CH4 to have a very high SiO reactivity and it might even be a step on the way towards a closed silicon furnace. In this study SiC formation from SiO gas in CH4 containing atmospheres is investigated. A reference gas of pure Ar was compared to H2, CH4 and CO gases. SiC was produced by passing CH4 containing process gases through a layer of SiO producing pellets gas at 1650 °C and 1750 °C. A thermocouple, which measured the process gas temperature, was used to look for signs of thermal cracking of CH4. CH4 contents up to 8% was tested, the lack of a correlation between CH4 content and temperature showed that CH4 does not crack in the current setup despite the temperature being in the range 1650 °C–1750 °C. With a CH4 containing process gas, most of the SiC formed around the gas inlets and within the SiO producing raw material layer. The reaction between SiO and CH4 occurred instantaneously when the two gases met, and appeared to be favored over thermal cracking of CH4. At 1650 °C in H2 or CO containing process gases a thick layer of whiskers formed around the rim of the crucible. The whiskers were examined with STEM using EDS and EELS, which determined the whiskers to be made of SiC. These results suggest that relatively high CH4 pressures can be metastable at temperatures far away from the thermodynamic equilibrium. They also indicate CH4 to exhibit a very high SiO reactivity, which makes it a promising alternative for current carbon sources in the production of silicon.publishedVersio

The Effect of Pre-Oxidation on the Reducibility of Chromite Using Hydrogen: A Preliminary Study

The majority of ferrochrome (FeCr) is produced through the carbothermic reduction of chromite ore. In recent years, FeCr producers have been pressured to curve carbon emissions, necessitating the exploration of alternative smelting methods. The use of hydrogen as a chromite reductant only yields water as a by-product, preventing the formation of carbon monoxide (CO)-rich off-gas. It is however understood that only the Fe-oxide constituency of chromite can be metalized by hydrogen, whereas the chromium (Cr)-oxide constituency requires significantly higher temperatures to be metalized. Considering the alternation of chromite’s spinel structure when oxidized before traditional smelting procedures, the effects on its reducibility using hydrogen were investigated. Firstly, the effect of hydrogen availability was considered and shown to have a significant effect on Fe metallization. Subsequently, spinel alternation induced by pre-oxidation promoted the hydrogen-based reducibly of the Fe-oxide constituency, and up to 88.4% of the Fe-oxide constituency was metallized. The Cr-oxide constituency showed little to no reduction. The increase in Fe-oxide reducibility was ascribed to the formation of an exsolved Fe2O3-enriched sesquioxide phase, which was more susceptible to reduction when compared to Fe-oxides present in the chromite spinel. The extent of Fe metallization of the pre-oxidized chromite was comparable to that of unoxidized chromite under significantly milder reduction conditions.publishedVersio

The use of hydrogen as a potential reductant in the chromite smelting industry

The chromium (Cr) content of stainless steel originates from recycled scrap and/or ferrochrome (FeCr), which is mainly produced by the carbothermic reduction of chromite ore. Ever-increasing pressure on FeCr producers to curtail carbon emissions justifies migration from traditional FeCr production routes. The interaction between hydrogen and chromite only yields water, foregoing the generation of significant volumes of CO-rich off-gas during traditional smelting procedures. For this reason, the use of hydrogen as a chromite reductant is proposed. In addition to thermodynamic modelling, the influence of temperature, time, and particle size on the reduction of chromite by hydrogen was investigated. It was determined that, at the explored reduction parameters, the iron (Fe)-oxides presented in chromite could be metalized and subsequently removed by hot-acid leaching. The Cr-oxide constituency of chromite did not undergo appreciable metalization. However, the removal of Fe from the chromite spinel allowed the formation of eskolaite with the composition of (Cr1.4Al0.6)O3 in the form of an exsolved phase, which may adversely affect the reducibility of chromite. The study includes the limitations of incorporating hydrogen as a reductant into existing FeCr production infrastructure and proposes possible approaches and considerations.publishedVersio

Reduction Kinetics of Pre-Oxidized Ilmenite Pellets by H2-H2O Gas Mixtures

The reduction behavior of pelletized and pre-oxidized ilmenite is investigated in H2-H2O atmospheres containing between 0 and 7% H2O and at temperatures between 983 and 1183 K (710 and 910 °C). The reduction mechanism occurs in two stages wherein the rapid reduction of trivalent to divalent iron cations is followed by the slower metallization of iron. Both temperature and gas composition are critical to achieving high reaction rates; within the range of conditions studied, the driving force for metallization has a significant effect on the reduction rate. Based on the experimental data and thermodynamic calculations, a model is established to predict the progress of the reduction as a function of temperature, gas composition and time. The application of this model at variable temperatures permits the determination of the activation energy Ea = 51 kJ/mol for the metallization reaction.publishedVersio

Characterization of a Si-SiO2 mixture generated from SiO and CO

The reaction between SiO(g) and CO(g) is a relevant intermediate reaction in the silicon production process. One of the products generated from this gas mixture is called by its color, brown condensate. In this paper, SiO(g) and CO(g) are produced from SiO2-SiC pellets. The reaction between the two gases occurred on SiC particles. Inert gas was injected at different flows. The SiC particles were collected, and the brown condensate deposited on them was characterized by Electron Probe Micro-Analysis (EPMA), X-Ray Photoelectron Spectroscopy (XPS) and Focused Ion Beam (FIB) preparation samples for Transmission Electron Microscope (TEM) analysis. The brown condensate consists of a mixture of Si spheres embedded in a SiO2 matrix. The temperature of formation of the compound is between 1400-1780{degree sign}C (1673-2053 K), dependent on the inert gas flow. SiC crystallites are located at the Si-SiO2 interface. Carbides are believed to generate from the reaction between liquid silicon and CO(g). Carbides may also precipitate from reaction between dissolved carbon and liquid silicon, but to a minor extent. Both mechanisms are believed to happen above the melting point of silicon and in the softening range of silica.publishedVersio

Reduction Kinetics of Pre-Oxidized Ilmenite Pellets by H2-H2O Gas Mixtures

The reduction behavior of pelletized and pre-oxidized ilmenite is investigated in H2-H2O atmospheres containing between 0 and 7% H2O and at temperatures between 983 and 1183 K (710 and 910 °C). The reduction mechanism occurs in two stages wherein the rapid reduction of trivalent to divalent iron cations is followed by the slower metallization of iron. Both temperature and gas composition are critical to achieving high reaction rates; within the range of conditions studied, the driving force for metallization has a significant effect on the reduction rate. Based on the experimental data and thermodynamic calculations, a model is established to predict the progress of the reduction as a function of temperature, gas composition and time. The application of this model at variable temperatures permits the determination of the activation energy Ea = 51 kJ/mol for the metallization reaction

Pilot Scale Production of Manganese Ferroalloys Using Heat-Treated Mn-Nodules

Pilot-scale experiments are one way to investigate the process patterns and the reaction mechanisms of processes and raw materials. To understand a process fully, both theoretical considerations as well as small-scale investigations are needed; nevertheless, the complex patterns of chemical reactions and physical phenomena can best be studied in pilot-scale investigations. After studying the chemical and mineralogical properties, the strength and the melting behavior of Mn-nodules, presented in a previous paper, the process behavior of the ore is studied in a pilot scale experiment. The industrial process is simulated in a top-and bottom-electrode furnace operated at about 150 kW. The high-strength, low-melting Mn-nodules produced by Autlan were the main raw material mixed with Comilog ore and some lime. It was shown that the Mn-nodules behave in principle like other commercial Mn-raw materials. The ore will at the border of the high-temperature area produce a liquid in coexistence with a MnO phase. As the ore is reaching the cokebed zone, the ore is already fully reduced. The ore will not be reduced much more in the cokebed area. The slag will be tapped at the composition close to the liquidus composition, as observed for other Mn-raw materials, and thus, also follow the well-known rule of lower MnO content in the slag with higher basicity.publishedVersio

Road-map for gas in the Norwegian metallurgical industry: greater value creation and reduced emissions

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Characterization, thermodynamics and mechanism of formation of SiC-SiOx core–shell nanowires

Silicon carbide nanowires are valuable for electronic and optical applications, due to their high mechanical and electrical properties. Previous studies demonstrated that nanowires can be produced easily, by mixing a silicon-based compound (Si or SiO2) with a carbon source (C or SiC), in an inert gas atmosphere (Ar or He). The result of this reaction is an elevated number of core–shell SiC-SiOx nanowires. The mechanism of formation of these wires should be inquired, in order to control the process. In this work, SiO2 and SiC are chosen as raw materials for SiO(g) and CO(g) production. These two gases react at SiC surfaces and generate the core–shell nanowires. SEM, TEM and XPS analyses confirm the composition and the microstructure of the product. A three-step mechanism of formation is proposed. The formation of nanowires is compared with thermodynamics of reactions occurring in the Si-C-O system. It is found that nanowires develop in wide temperature and SiO partial pressure ranges (T: 924 °C to 1750 °C, pSiO = 0.50 to 0.74). Higher He flows will shift the reaction to lower temperatures and pSiO