富高岭石煤矸石中铝和硅的浸出及动力学研究

doi:10.16552/j.cnki.issn1001-1625.2024.0793

摘要/Abstract

摘要： 富高岭石煤矸石含有大量SiO₂和Al₂O₃,以该煤矸石为研究对象,采用盐酸酸浸法浸出其中的Al₂O₃,采用NaOH碱浸法浸出酸浸渣中的SiO₂,考察酸浸浓度、酸浸温度、酸浸时间及液固比对焙烧活化后煤矸石中Al₂O₃浸出率的影响,并探究碱浸条件对酸浸渣中SiO₂浸出率的影响。结果表明,采用单变量实验优化酸浸和碱浸条件时,在最佳条件下煤矸石中Al₂O₃的浸出率达92.6%,酸浸渣中SiO₂的浸出率达99.1%。动力学研究表明,煤矸石酸浸过程的动力学符合内扩散和化学反应混合控制模型,碱浸过程动力学符合化学反应控制模型。酸浸混合控制模型和碱浸化学反应控制模型的表观反应速率常数对数ln k_c和ln k_b与T^-1之间呈良好的线性关系,并得到了酸浸过程动力学速率方程和碱浸过程动力学速率方程。该研究结果可用于指导工业煤矸石中铝和硅的浸出生产。

关键词: 富高岭石结构, 煤矸石, Al, Si, 浸出, 动力学, 活化能

Abstract: Kaolinite-rich coal gangue contains a large amount of SiO₂ and Al₂O₃. In this work, the coal gangue was selected to leach the Al₂O₃ by using hydrochloric acid and then to leach the SiO₂ from the acid leaching slag by NaOH alkaline. The effects of acid leaching concentration, acid leaching temperature, acid leaching time and liquid-solid ratio on the leaching rate of Al₂O₃ from calcined coal gangue were investigated, and the effects of alkaline leaching conditions on the leaching rate of SiO₂ from acid leaching slag were also explored. The results show that when the conditions of acid leaching and alkali leaching are optimized by single variable experiment, the leaching rate of Al₂O₃ in coal gangue is 92.6%, and the leaching rate of SiO₂ in acid leaching residue is 99.1%. The study of the kinetic models of acid leaching and alkaline leaching processes shows that, the kinetics model of the acid leaching process of coal gangue is in accordance with the mixed control model of internal diffusion and chemical reaction, while the alkaline leaching agreed well with the chemical reaction control model. There is a good linear relationship between the logarithm of the apparent reaction rate constants ln k_c and ln k_b versus T^-1, for the acid leaching mixed control model and the alkaline leaching chemical reaction control model, respectively. In this paper, the kinetic rate equations of acid leaching process and alkali leaching process are also obtained. The results of this study can be used to guide the production of aluminum and silicon leaching from industrial coal gangue.

Key words: kaolinite-rich structure, coal gangue, Al, Si, leaching, kinetics, activation energy

中图分类号:

TF803.21

汪洋洋, 姚隆帆, 戴露霏, 李忠, 孟凡会. 富高岭石煤矸石中铝和硅的浸出及动力学研究[J]. 硅酸盐通报, 2025, 44(1): 202-211.

WANG Yangyang, YAO Longfan, DAI Lufei, LI Zhong, MENG Fanhui. Leaching and Kinetics of Aluminum and Silicon from Kaolinite-Rich Coal Gangue[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2025, 44(1): 202-211.

参考文献

[1] SHI X Y, CAI Q X, QI C C, et al. Co-utilization of reactivated cement pastes with coal gangue[J]. Construction and Building Materials, 2021, 270: 121423.
[2] LV B, ZHAO Z Y, DENG X W, et al. Sustainable and clean utilization of coal gangue: activation and preparation of silicon fertilizer[J]. Journal of Material Cycles and Waste Management, 2022, 24(4): 1579-1590.
[3] LI M, ZHANG J X, LI A L, et al. Reutilisation of coal gangue and fly ash as underground backfill materials for surface subsidence control[J]. Journal of Cleaner Production, 2020, 254: 120113.
[4] YANG Q C, ZHANG F, DENG X J, et al. Extraction of alumina from alumina rich coal gangue by a hydro-chemical process[J]. Royal Society Open Science, 2020, 7(4): 192132.
[5] LI Y F, LIU S H, GUAN X M. Multitechnique investigation of concrete with coal gangue[J]. Construction and Building Materials, 2021, 301: 124114.
[6] VALEEV D, KUNILOVA I, SHOPPERT A, et al. High-pressure HCl leaching of coal ash to extract Al into a chloride solution with further use as a coagulant for water treatment[J]. Journal of Cleaner Production, 2020, 276: 123206.
[7] 赵梓, 赵爱春, 刘宸嘉, 等. 硫酸铵焙烧活化-硫酸浸出粉煤灰提铝熟料的动力学研究[J]. 湿法冶金, 2024, 43(2): 129-133.
ZHAO Z, ZHAO A C, LIU C J, et al. Kinetics of aluminum extraction clinker from fly ash by ammonium sulfate roasting activation-sulfuric acid leaching[J]. Hydrometallurgy of China, 2024, 43(2): 129-133 (in Chinese).
[8] JOHNSTON C J, PEPPER R A, MARTENS W N, et al. Improvement of aluminium extraction from low-grade kaolinite by iron oxide impurities: role of clay chemistry and morphology[J]. Minerals Engineering, 2022, 176: 107346.
[9] YANG Q, LI Q, ZHANG G F, et al. Investigation of leaching kinetics of aluminum extraction from secondary aluminum dross with use of hydrochloric acid[J]. Hydrometallurgy, 2019, 187: 158-167.
[10] VALEEV D, PANKRATOV D, SHOPPERT A, et al. Mechanism and kinetics of iron extraction from high silica boehmite-kaolinite bauxite by hydrochloric acid leaching[J]. Transactions of Nonferrous Metals Society of China, 2021, 31(10): 3128-3149.
[11] GUO Y X, LV H B, YANG X, et al. AlCl₃·6H₂O recovery from the acid leaching liquor of coal gangue by using concentrated hydrochloric inpouring[J]. Separation and Purification Technology, 2015, 151: 177-183.
[12] LUO J, LI G H, JIANG T, et al. Conversion of coal gangue into alumina, tobermorite and TiO₂-rich material[J]. Journal of Central South University, 2016, 23(8): 1883-1889.
[13] PENG B X, LI X R. Release and transformation characteristics of modes of occurrence of chlorine in coal gangue during combustion[J]. Energy & Fuels, 2018, 32(9): 9926-9933.
[14] YANG Z Y, ZHENG Y S, MA Z J, et al. Medium-temperature calcination and acid pressure leaching extract the Al₂O₃ from coal gangue: activation mechanism and kinetic analysis[J]. RSC Advances, 2024, 14(16): 11266-11275.
[15] ZHENG G Y, XIA J P, LIU C L, et al. Dissolution of aluminum and titanium during high-temperature acidification of coal gangues and relative kinetics[J]. Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, 2023, 45(2): 5411-5424.
[16] XIAO J, ZHANG L Y, YUAN J, et al. Co-utilization of spent pot-lining and coal gangue by hydrothermal acid-leaching method to prepare silicon carbide powder[J]. Journal of Cleaner Production, 2018, 204: 848-860.
[17] 刘成龙, 许爱华, 夏举佩, 等. 煤矸石浸渣制备白炭黑工艺优化及性能分析[J]. 精细化工, 2019, 36(11): 2177-2184.
LIU C L, XU A H, XIA J P, et al. Process optimization and performance analysis for preparation of silica from coal gangue leaching residue[J]. Fine Chemicals, 2019, 36(11): 2177-2184 (in Chinese).
[18] WEI J, ZHU P H, SUN H. Ambient-dried silica aerogel powders derived from coal gangue by using one-pot method[J]. Materials, 2022, 15(4): 1454.
[19] 李星海, 杨晓宇, 张玉娥, 等. 煤矸石中提取纳米SiO₂粉体材料的研究[J]. 化工新型材料, 2014, 42(11): 196-198.
LI X H, YANG X Y, ZHANG Y E, et al. Study on nanometer SiO₂ powder extracted from coal gangue[J]. New Chemical Materials, 2014, 42(11): 196-198 (in Chinese).
[20] HAO R W, LI X L, XU P J, et al. Thermal activation and structural transformation mechanism of kaolinitic coal gangue from Jungar Coalfield, Inner Mongolia, China[J]. Applied Clay Science, 2022, 223: 106508.
[21] GUO Y X, YAN K Z, CUI L, et al. Improved extraction of alumina from coal gangue by surface mechanically grinding modification[J]. Powder Technology, 2016, 302: 33-41.
[22] KASSA A E, SHIBESHI N T, TIZAZU B Z. Kinetic analysis of dehydroxylation of Ethiopian kaolinite during calcination[J]. Journal of Thermal Analysis and Calorimetry, 2022, 147(22): 12837-12853.
[23] 曹丽琼, 张丽宏, 郭彦霞, 等. 碳含量对煤矸石活化及酸浸提铝的影响[J]. 洁净煤技术, 2020, 26(4): 203-208.
CAO L Q, ZHANG L H, GUO Y X, et al. Effect of carbon content on the activation of coal gangue and acid leaching for aluminum extraction[J]. Clean Coal Technology, 2020, 26(4): 203-208 (in Chinese).
[24] ZHANG Y J, SUN J M, LÜ G Z, et al. Kinetics of alumina extraction from coal gangue by hydrochloric acid leaching[J]. Transactions of Nonferrous Metals Society of China, 2023, 33(6): 1932-1942.
[25] CHEN H C, ZHANG L, PAN J H, et al. Study on the leaching behavior differences of rare earth elements from coal gangue through calcination-acid leaching[J]. Separation and Purification Technology, 2024, 344: 127222.
[26] 姚隆帆, 孟凡会, 戴露霏, 等. 富含高岭石结构的煤矸石活化及合成NaY分子筛[J]. 石油学报(石油加工), 2024, 40(2): 317-326.
YAO L F, MENG F H, DAI L F, et al. Activation of kaolinite-rich coal gangue and synthesis of NaY molecular sieve[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2024, 40(2): 317-326 (in Chinese).
[27] KWON E H, LEE J, HAN J W. Modified unreacted core model for reduction of manganese ore by CO gas[J]. Metals and Materials International, 2022, 28(6): 1517-1524.
[28] WESENAUER F, JORDAN C, PICHLER M, et al. An unreacted shrinking core model serves for predicting combustion rates of organic additives in clay bricks[J]. Energy & Fuels, 2020, 34(12): 16679-16692.
[29] 赵雪淞, 刘鑫, 李彩霞, 等. 混酸提纯制备高纯石英砂及浸出动力学分析[J]. 硅酸盐学报, 2021, 49(3): 581-589.
ZHAO X S, LIU X, LI C C, et al. Preparation of high-purity quartz sand by leaching with mixed acids[J]. Journal of The Chinese Ceramic Society, 2021, 49(3): 581-589 (in Chinese).
[30] 郭文超, 朱晓波, 张治国, 等. 煤矸石焙烧活化-酸浸提取氧化铝的实验研究[J]. 煤炭转化, 2023, 46(6): 80-89.
GUO W C, ZHU X B, ZHANG Z G, et al. Experimental study on extraction of alumina from coal gangue by roasting activation-acid leaching[J]. Coal Conversion, 2023, 46(6): 80-89 (in Chinese).
[31] FALAYI T, MASHIFANA T, NTULI F. Silicon and aluminium leaching kinetics from acidic gold mine tailings[J]. IOP Conference Series: Materials Science and Engineering, 2019, 652(1): 012046.
[32] KONG J, WEI D H, XING P F, et al. Clean preparation of high-purity silicon from rice husk ash by a modified metallurgical method[J]. JOM, 2021, 73(6): 1919-1927.