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.
The hydrolysis of aluminum (Al) is a promising method for on-demand hydrogen generation for low-power proton exchange membrane fuel cell (PEMFC) applications. In this study, Al composites were mechanochemically activated using bismuth (Bi) and nickel (Ni) as activation compounds. The main objective was to determine the effects of Bi and Ni on Al particles during mechanochemical processing, and the hydrolysis activity of the Al-Bi-Ni composites. Successfully formulated ternary Al-Bi-Ni composites were hydrolyzed with de-ionized water under standard ambient conditions to determine the reactivity of the composite (extent of hydrogen production). Scanning electron microscopy (SEM) showed that Bi and Ni were distributed relatively uniformly throughout the Al particles, resulting in numerous micro-galvanic interactions between the anodic Al and cathodic Bi/Ni during hydrolysis reaction. The addition of >1 wt% Ni resulted in incomplete activation of Al, and such composites were non-reactive. All successfully prepared composites had near-complete hydrogen yields. X-ray diffraction (XRD) showed that no mineralogical interaction occurred between Al, Bi, and/or Ni. The main phases detected were Al, Bi, and minute traces of Ni (ascribed to low Ni content). In addition, the effect of the mass ratio (mass Al:mass water) and water quality were also determined.
In this investigation, ternary Al-Bi-Zn composites were prepared through mechanochemical activation to determine the combined effects of low-cost Bi and Zn on the morphology change and reactivity of the Al composite during the hydrolysis reaction. Specifically, Zn was considered as a means to slow the hydrogen generation rate while preserving a high hydrogen yield. A steady hydrogen generation rate is preferred when coupled with a proton exchange membrane fuel cell (PEMFC). Scanning electron microscopy (SEM) analysis indicated that Bi and Zn were distributed relatively uniformly in Al particles. By doing so, galvanic coupling between anodic Al and the cathodic Bi/Zn sustains the hydrolysis reaction until the entire Al particle is consumed. X-ray diffraction analysis (XRD) showed no intermetallic phases between Al, Bi, and/or Zn formed. A composite containing 7.5 wt% Bi and 2.5 wt% Zn had a hydrogen yield of 99.5%, which was completed after approximately 2300 s. It was further found that the water quality used during hydrolysis could further slow the hydrogen generation rate.
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.
The incorporation of hydrogen, which is a relatively unexplored reductant used during ferromanganese (FeMn) production, is an attractive approach to lessen atmospheric gaseous carbon release. The influence of hydrogen on the pre-reduction of carbonate-rich United Manganese of Kalahari (UMK) ore from South Africa was investigated. Experiments were performed in 70 pct CO 30 pct CO2 (reference), 70 pct H2 30 pct H2O, and 100 pct H2 gas atmospheres at 700 °C, 800 °C, and 900 °C. Calculated phase stability diagrams and experimental results showed good correlation. The pre-reduction process involved two reactions proceeding in parallel, i.e., the pre-reduction of higher oxides and the decomposition of carbonates present in the ore. A thermogravimetric (TG) furnace was employed for the pre-reduction of the ore in various atmospheres. The calculated weight loss percentage was used to determine the degree and rate of pre-reduction. It was found that the oxidation state of higher Fe- and Mn-oxides was lowered when treated in 70 pct H2 30 pct H2O and 70 pct CO 30 pct CO2, whereas FeO was metalized when using 100 pct H2. As for the intrinsic carbonates, the majority thereof were decomposed in the CO/CO2 atmosphere at 900 °C, and ≥ 700 °C in the H2/H2O and H2 atmospheres. Additionally, the degree and rate of reduction were accelerated by increasing the pre-reduction temperature and by employing a hydrogen-containing gas atmosphere (70 pct H2 30 pct H2O, and 100 pct H2). Scanning electron microscopy and electron microprobe analysis revealed the presence of three phases in the pre-reduced ore: (i) Mn- and Fe-rich, (ii) Mg- and Ca-rich, and (iii) Mg-, Si-, K-, and Na-rich. It was also found that there were no appreciable differences in porosity and decrepitation of the ores treated in the CO/CO2 and hydrogen-containing atmospheres. The use of a hydrogen atmosphere showed potential for the pre-reduction of carbonate-containing manganese ores as it accelerated the decomposition of the carbonates as well as facilitated the metallization of Fe-oxides present in the ore.
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