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氫基預還原鉻鐵礦的還原進程與固結機理研究

Reduction process and pellet consolidation mechanism of hydrogen based pre-reduced chromite

  • 摘要: 鉻鐵礦預還原是鉻鐵合金生產過程中減污降碳的重要手段,當前鉻鐵礦預還原仍采用配碳球團氧化焙燒的方法,能耗和碳排放居高不下,因此在“雙碳”背景下,鉻鐵礦氫基預還原工藝路線的開發意義重大。本研究通過在水平管式爐中對鉻鐵礦球團進行不同條件下的恒溫還原,深入分析了氫基還原焙燒鉻鐵礦過程中球團的還原進程和固結機理,結果表明:在鉻鐵礦還原中,還原溫度、還原時間、H2:CO比率與鐵的金屬化率和脫氧率成正比;當鉻鐵礦球團在溫度為1300℃的純H2條件下還原3小時后,Fe的金屬化率達到85.9%。XRD和SEM結果顯示,鉻鐵礦礦相結構為復雜尖晶石結構(Mg, Fe)(Cr, Fe, Al)2O4,其中Fe3+位點的Fe原子優先還原,而僅有少量的Cr原子被還原,表明H2對Cr的還原能力較弱。球團強度方面,強度隨著鐵金屬化率的增加呈現先升高后降低的趨勢,研究表明鐵金屬化率的升高降低了粘結相中Fe2+的比率,使球團中粘結相的熔點升高,顆粒間粘結力下降,導致球團強度降低。球團強度的提升主要是由高溫條件下熔融金屬Fe和粘結相的粘結作用所致。當還原溫度保持在1200℃以上時,球團的平均強度高于1000N,滿足球團入爐的強度要求。該研究有望為鉻鐵礦氫基預還原工藝路線的開發提供理論支撐。

     

    Abstract: Ferrochrome alloy is a critical raw material in the production of stainless steel, corrosion-resistant steels, and high-temperature alloys, with global demand continuously rising. However, its production is highly energy-intensive, primarily due to the high-temperature reduction requirement of Cr2O3 (>1600?°C) and the elevated melting point of chromium-containing melts (1900~2050?°C). Pre-reduction of chromite ore is an effective approach to lowering energy consumption and carbon emissions in ferrochrome production. At present, carbon-bearing pellet oxidation roasting remains the mainstream method, which results in high energy use and CO2 emissions. The advancement of hydrogen metallurgy offers a promising alternative, and under the “dual carbon” policy framework, developing a hydrogen-based pre-reduction process for chromite holds significant strategic value. In this study, pre-reduction experiments were conducted on chromite pellets using a horizontal tube furnace. A self-developed proton flow meter in combination with a multi-gas mixing system was employed to precisely control the furnace atmosphere. The pellets were first heated to the target temperature under an argon atmosphere, followed by isothermal reduction in a H2–CO mixed gas atmosphere. Upon completion of reduction, argon was reintroduced during cooling to room temperature to prevent reoxidation. The effects of reduction parameters—including the H2/CO ratio, temperature, and time—on iron metallization rate, Fe2+ conversion, and compressive strength were systematically investigated. Post-reduction, the compressive strength of pellets was tested using a universal testing machine in accordance with the national standard GB/T 14201-2018. Coupled with chemical analysis, XRD phase identification, and SEM microstructural characterization, the mineral phase transformation and microstructural evolution mechanisms of the pellets were clarified, and the synergistic mechanism between reduction and consolidation was revealed. The results show that the reduction temperature, time, and H2:CO ratio are positively correlated with the iron metallization and deoxygenation rates. Under pure H? at 1300?°C for 3 hours, the Fe metallization rate reached 85.9%. XRD and SEM analyses revealed that the chromite phase exhibits a complex spinel structure of the form (Mg, Fe)(Cr, Fe, Al)2O4. Fe atoms at Fe3+ sites were preferentially reduced, whereas only a limited amount of Cr was reduced, indicating the relatively weak reducing ability of H2 for Cr. In terms of mechanical performance, pellet strength first increased and then decreased with rising iron metallization. The decline in Fe2+ content in the bonding phase at higher metallization levels led to an increase in the bonding phase's melting point, resulting in poor fluidity and reduced softening and solidification ability. Strength enhancement was mainly attributed to the bonding effect between molten metallic Fe and the bonding phase at high temperatures. When the reduction temperature exceeded 1200?°C, the average compressive strength of the pellets remained above 1000?N, meeting the strength requirements for furnace charging. However, further increases in the metallization degree continued to reduce Fe2? content in the bonding phase, elevating its melting point, weakening interparticle bonding, and thus decreasing pellet strength. The reduction process of chromite pellets can be divided into four distinct stages: preheating, solid-state reduction, softening and consolidation, and over-reduction-induced weakening. This study is expected to provide theoretical support for the development of hydrogen-based pre-reduction processes for chromite ore.

     

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