Abstract
Siderite, as an abundant iron ore, has not been effectively utilized, with a low utilization rate. In this study, the in-situ kinetics and mechanism of siderite during suspension magnetization roasting (SMR) were investigated to improve the selective conversion of siderite to magnetite and CO, enriching the theoretical system of green SMR using siderite as a reductant. According to the gas products analyses, the peak value of the reaction rate increased with increasing temperature, and its curves presented the feature of an early peak and long tail. The mechanism function of the siderite pyrolysis was the contraction sphere model (R3): f(α) =3(1 − α)2/3; Eα was 46.4653 kJ/mol; A was 0.5938 s−1; the kinetics equation was k=0.5938exp[− 46.4653/(RT)]. The in-situ HT-XRD results indicated that siderite was converted into magnetite and wüstite that exhibited a good crystallinity in SMR under a N2 atmosphere. At 620 °C, the saturation magnetization (Ms), remanence magnetization (Mr), and coercivity (Hc) of the product peaked at 53.63×10−3 A·m2/g, 10.23× 10−3A×m2/g, and 12.40×103 A/m, respectively. Meanwhile, the initial particles with a smooth surface were transformed into particles with a porous and loose structure in the roasting process, which would contribute to reducing the grinding cost.
摘要
菱铁矿是一种储量丰富的铁矿石,但其利用率较低,尚未得到高效开发利用。菱铁矿选择&性转化为磁铁矿和CO 是高效利用菱铁矿的关键。本文研究了悬浮磁化焙烧过程中菱铁矿的原&位动力学和机理,丰富了菱铁矿作为还原剂的绿色悬浮磁化焙烧理论体系。气体产物分析表明,反应&速率峰值随温度的升高而增大,且反应速率曲线呈现“早峰长尾”的特征。菱铁矿热解反应的机&理模型为收缩球模型(R3):f(α)=3(1−α)2/3,Eα为46.4653 kJ/mol;A 为0.5938 s−1&;动力学方程为&k=0.5938exp[−46.4653/(RT)]。原位HT-XRD 结果表明,在N 2&气氛下菱铁矿的最终产物为磁铁矿和方铁&矿,它们具有良好结晶度。在620 °C 时,固相产物的磁性达到峰值,其中饱和磁化强度(M s)、剩磁&磁化强度(M r)和矫顽力(Hc)分别为53.63×10−3A·m2/g,10.23×10−3A·m2/g 和12.40×103A/m。经过焙烧,&菱铁矿颗粒的致密结构遭到破坏,转变为疏松多孔的结构,降低了颗粒的力学强度,有利于降低后续&磨矿作业的能耗。
Article PDF
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.Avoid common mistakes on your manuscript.
References
CHEN Dong, GUO Hong-wei, LV Ya-nan, et al. Green technology-based utilization of refractory siderite ores to prepare electric arc furnace burden [J]. Steel Research International, 2021, 92(9): 2100046. DOI: https://doi.org/10.1002/srin.202100046.
ZHANG Ying-chun, YANG Xiu-hong, SHI Ni-cheng, et al. Study on the comprehensive utilization of siderite [J]. Metal Mine, 2001, 295(1): 48–49, 53. (in Chinese)
LUO Li-qun. Explerative research on beneficiation of siderite and its development prospect [J]. Metal Mine, 2006, 355 (1): 68–72. (in Chinese)
ZHANG Chen, LI Li-xia, YUAN Zhi-tao, et al. Probing the effect of particle imperfections on the sliming of siderite in carbonate-bearing iron ore [J]. Minerals Engineering, 2019, 143: 106014. DOI: https://doi.org/10.1016/j.mineng.2019.106014.
BAI Shao-jun, WEN Shu-ming, LIU Dian-wen, et al. Separation of phosphorus and magnetic mineral fines from siderite reductive ore by applying magnetic flocculation [J]. Separation Science and Technology, 2014, 49(9): 1434–1441. DOI: https://doi.org/10.1080/01496395.2013.877036.
HAO Hai-qing, LI Li-xia, SOMASUNDARAN P, et al. Adsorption of pregelatinized starch for selective flocculation and flotation of fine siderite [J]. Langmuir, 2019, 35(21): 6878–6887. DOI: https://doi.org/10.1021/acs.langmuir.9b00669.
YIN Wan-zhong, HAN Yue-xin, XIE Feng. Floatation separation research on siderite-containing iron concentrate [J]. Advanced Materials Research, 2010, 92: 103–109. DOI: https://doi.org/10.4028/www.scientific.net/amr.92.103.
YU Jian-wen, HAN Yue-xin, LI Yan-jun, et al. Recent advances in magnetization roasting of refractory iron ores: A technological review in the past decade [J]. Mineral Processing and Extractive Metallurgy Review, 2020, 41(5): 349–359. DOI: https://doi.org/10.1080/08827508.2019.1634565.
ZHANG Xiao-long, HAN Yue-xin, SUN Yong-sheng, et al. Innovative utilization of refractory iron ore via suspension magnetization roasting: A pilot-scale study [J]. Powder Technology, 2019, 352: 16–24. DOI: https://doi.org/10.1016/j.powtec.2019.04.042.
SUN Yong-sheng, ZHANG Xiao-long, HAN Yue-xin, et al. A new approach for recovering iron from iron ore tailings using suspension magnetization roasting: A pilot-scale study [J]. Powder Technology, 2020, 361: 571–580. DOI: https://doi.org/10.1016/j.powtec.2019.11.076.
TANG Zhi-dong, GAO Peng, LI Yan-jun, et al. Recovery of iron from hazardous tailings using fluidized roasting coupling technology [J]. Powder Technology, 2020, 361: 591–599. DOI: https://doi.org/10.1016/j.powtec.2019.11.074.
TANG Zhi-dong, HAN Yue-xin, GAO Peng, et al. Fluidization characteristics of a U-type reduction chamber in a suspension roaster [J]. Powder Technology, 2019, 345: 64–73. DOI: https://doi.org/10.1016/j.powtec.2018.12.088.
YUAN Shuai, ZHANG Qi, YIN Heng, et al. Efficient iron recovery from iron tailings using advanced suspension reduction technology: A study of reaction kinetics, phase transformation, and structure evolution [J]. Journal of Hazardous Materials, 2021, 404: 124067. DOI: https://doi.org/10.1016/j.jhazmat.2020.124067.
ZHANG Xiao-long, HAN Yue-xin, LI Yan-jun, et al. Effect of heating rate on pyrolysis behavior and kinetic characteristics of siderite [J]. Minerals, 2017, 7(11): 211. DOI: https://doi.org/10.3390/min7110211.
GOTOR F J, MACÍAS M, ORTEGA A, et al. Comparative study of the kinetics of the thermal decomposition of synthetic and natural siderite samples [J]. Physics and Chemistry of Minerals, 2000, 27(7): 495–503. DOI: https://doi.org/10.1007/s002690000093.
ZHANG Qi, SUN Yong-sheng, HAN Yue-xin, et al. Pyrolysis behavior of a green and clean reductant for suspension magnetization roasting [J]. Journal of Cleaner Production, 2020, 268: 122173. DOI: https://doi.org/10.1016/j.jclepro.2020.122173.
SUN Yong-sheng, ZHU Xin-ran, HAN Yue-xin, et al. Green magnetization roasting technology for refractory iron ore using siderite as a reductant [J]. Journal of Cleaner Production, 2019, 206: 40–50. DOI: https://doi.org/10.1016/j.jclepro.2018.09.113.
ZHANG Qi, SUN Yong-sheng, HAN Yue-xin, et al. Producing magnetite concentrate via self-magnetization roasting in N2 atmosphere: Phase and structure transformation, and extraction kinetics [J]. Journal of Industrial and Engineering Chemistry, 2021, 104: 571–581. DOI: https://doi.org/10.1016/j.jiec.2021.09.008.
HE Kun, ZHENG Zhong, CHEN Zhi-wei. Multistep reduction kinetics of Fe3O4 to Fe with CO in a micro fluidized bed reaction analyzer [J]. Powder Technology, 2020, 360: 1227–1236. DOI: https://doi.org/10.1016/j.powtec.2019.10.094.
ZHAO Qiang, XUE Ji-lai, CHEN Wen. Mechanism of improved magnetizing roasting of siderite-hematite iron ore using a synergistic CO-H2 mixture [J]. Journal of Iron and Steel Research International, 2020, 27(1): 12–21. DOI: https://doi.org/10.1007/s42243-019-00242-w.
ALKAÇ D, ATALAY Ü. Kinetics of thermal decomposition of Hekimhan-Deveci siderite ore samples [J]. International Journal of Mineral Processing, 2008, 87(3–4): 120–128. DOI: https://doi.org/10.1016/j.minpro.2008.02.007.
FENG Zhi-li, YU Yong-fu, LIU Gen-fan, et al. Kinetics of the thermal decomposition of wangjiatan siderite [J]. Journal of Wuhan University of Technology-Material Edition Science, 2011, 26(3): 523–526. DOI: https://doi.org/10.1007/s11595-011-0261-x.
YU Da-wei, ZHU Ming-qian, UTIGARD T A, et al. TGA kinetic study on the hydrogen reduction of an iron nickel oxide [J]. Minerals Engineering, 2013, 54: 32–38. DOI: https://doi.org/10.1016/j.mineng.2013.03.018.
ALVAREZ-AULAR A, CARTAYA L, MALDONADO A, et al. Experimental and DFT studies for the kinetics and mechanism of the pyrolysis of 2-(4-substituted-phenoxy) tetrahydro-2H-pyranes in the gas-phase [J]. Journal of Analytical and Applied Pyrolysis, 2018, 134: 52–60. DOI: https://doi.org/10.1016/j.jaap.2018.05.006.
MONASCAL Y, GALLARDO E, CARTAYA L, et al. Homogeneous, unimolecular gas-phase pyrolysis kinetics of 4- and 2-hydroxyacetophenone [J]. Journal of Analytical and Applied Pyrolysis, 2017, 124: 499–503. DOI: https://doi.org/10.1016/j.jaap.2017.01.031.
AL-QALLAF M A, DIB H H, AL-AWADI N A, et al. Arylidenepyridylhydrazines: Synthesis, and kinetics and mechanism of their gas-phase pyrolysis [J]. Journal of Analytical and Applied Pyrolysis, 2017, 124: 446–453. DOI: https://doi.org/10.1016/j.jaap.2017.02.021.
VLAEV L T, MARKOVSKA I G, LYUBCHEV L A. Non-isothermal kinetics of pyrolysis of rice husk [J]. Thermochimica Acta, 2003, 406(1–2): 1–7. DOI: https://doi.org/10.1016/S0040-6031(03)00222-3.
LI Peng, YU Qing-bo, QIN Qin, et al. Kinetics of CO2/coal gasification in molten blast furnace slag [J]. Industrial & Engineering Chemistry Research, 2012, 51(49): 15872–15883. DOI: https://doi.org/10.1021/ie301678s.
BEURIA P C, BISWAL S K, MISHRA B K, et al. Study on kinetics of thermal decomposition of low LOI goethetic hematite iron ore [J]. International Journal of Mining Science and Technology, 2017, 27(6): 1031–1036. DOI: https://doi.org/10.1016/j.ijmst.2017.06.018.
HE Kun, ZHANG Shui-chang, MI Jing-kui, et al. Pyrolysis involving n-hexadecane, water and minerals: Insight into the mechanisms and isotope fractionation for water-hydrocarbon reaction [J]. Journal of Analytical and Applied Pyrolysis, 2018, 130: 198–208. DOI: https://doi.org/10.1016/j.jaap.2018.01.009.
LIU Hai-bo, SHU Dao-bing, SUN Fu-wei, et al. Effect of manganese substitution on the crystal structure and decomposition kinetics of siderite [J]. Journal of Thermal Analysis and Calorimetry, 2019, 136(3): 1315–1322. DOI: https://doi.org/10.1007/s10973-018-7767-9.
LI Yan-jun, ZHANG Qi, YUAN Shuai, et al. High-efficiency extraction of iron from early iron tailings via the suspension roasting-magnetic separation [J]. Powder Technology, 2021, 379: 466–477. DOI: https://doi.org/10.1016/j.powtec.2020.10.005.
CELIKDEMIR M, SARIKAYA M, DEPCI T, et al. Influence of microwave heating and thermal auxiliary on decomposition of siderite [J]. IOP Conference Series: Earth and Environmental Science, 2016, 44: 052002. DOI: https://doi.org/10.1088/1755-1315/44/5/052002.
GHIMIRE S, DHO J. Anisotropic lattice disorder and enhanced magnetic anisotropy in Fe3O4 films on (110) SrTiO3 [J]. Journal of Magnetism and Magnetic Materials, 2018, 468: 209–214. DOI: https://doi.org/10.1016/j.jmmm.2018.05.078.
DHO J, KIM B, KI S. Substrate effects on in-plane magnetic anisotropy and verwey transition temperatures of (100) magnetite (Fe3O4) films [J]. IEEE Transactions on Magnetics, 2016, 52(7): 1–4. DOI: https://doi.org/10.1109/tmag.2016.2521604.
ZHENG Yi-fan, LIU Hua-zhang, LIU Zong-jian, et al. In situ X-ray diffraction study of reduction processes of Fe3O4- and Fe1−xO-based ammonia-synthesis catalysts [J]. Journal of Solid State Chemistry, 2009, 182(9): 2385–2391. DOI: https://doi.org/10.1016/j.jssc.2009.06.030.
TOGAWA T, SANO T, WADA Y, et al. The effect of the crystal orientation on the rate of formation of cation-excess magnetite [J]. Solid State Ionics, 1996, 89(3–4): 279–286. DOI: https://doi.org/10.1016/0167-2738(96)00358-X.
PONOMAR V P, BRIK O B, CHEREVKO Y I, et al. Kinetics of hematite to magnetite transformation by gaseous reduction at low concentration of carbon monoxide [J]. Chemical Engineering Research and Design, 2019, 148: 393–402. DOI: https://doi.org/10.1016/j.cherd.2019.06.019.
YANG He, RONG Yi, HAN Chong, et al. Magnetizing roast and magnetic separation of iron in rare-earth tailings [J]. Journal of Central South University, 2016, 23(8): 1899–1905. DOI: https://doi.org/10.1007/s11771-016-3245-3.
PONOMAR V P, DUDCHENKO N O, BRIK A B. Synthesis of magnetite powder from the mixture consisting of siderite and hematite iron ores [J]. Minerals Engineering, 2018, 122: 277–284. DOI: https://doi.org/10.1016/j.mineng.2018.04.018.
PONOMAR V P. Thermomagnetic properties of the goethite transformation during high-temperature treatment [J]. Minerals Engineering, 2018, 127: 143–152. DOI: https://doi.org/10.1016/j.mineng.2018.08.016.
YUNUS N A, ANI M H, SALLEH H M, et al. Effect of reduction roasting by using bio-char derived from empty fruit bunch on the magnetic properties of Malaysian iron ore [J]. International Journal of Minerals, Metallurgy, and Materials, 2014, 21(4): 326–330. DOI: https://doi.org/10.1007/s12613-014-0912-y.
Author information
Authors and Affiliations
Corresponding author
Additional information
Foundation item
Projects(51874071, 52022019, 51734005) supported by the National Natural Science Foundation of China; Project (161045) supported by the Fok Ying Tung Education Foundation for Yong Teachers in the Higher Education Institutions of China
Contributors
The overarching research goals were developed by ZHANG Qi and SUN Yong-sheng. ZHANG Qi provided measured data, analyzed the results, and edited the draft of the manuscript. SUN Yong-sheng provided the concept, conducted the literature review, and reviewed the manuscript. QIN Yong-hong, GAO Peng, and YUAN Shuai edited and revised the final version.
Conflict of interest
ZHANG Qi, SUN Yong-sheng, QIN Yong-hong, GAO Peng, and YUAN Shuai declare that they have no conflict of interest.
Rights and permissions
About this article
Cite this article
Zhang, Q., Sun, Ys., Qin, Yh. et al. Siderite pyrolysis in suspension roasting: An in-situ study on kinetics, phase transformation, and product properties. J. Cent. South Univ. 29, 1749–1760 (2022). https://doi.org/10.1007/s11771-022-5059-9
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11771-022-5059-9
Key words
- siderite
- suspension magnetization roasting
- reaction kinetics
- phase transformation
- magnetic transition
- microstructure evolution