SHAN Tianqi;YANG Ce;LIU Jinchang;FU Zongpin;ZHAO Yunpeng;

• 1:Key Laboratory of Coal Processing and Efficient Utilization
• 2:Ministry of Education
• 3:China University of Mining & Technology
• 4:School of Chemical and Environmental Engineering

Abstract：

Gasification slag is the main solid waste produced in the modern coal chemical process. To efficiently extract and utilize the strategic metal resources contained in the coal gasification slag, and realize its high-value utilization, has become a current research hotspot. Currently,the occurrence state and migration rules of strategic metal elements in gasification slag are not well understood. In this study,ICP-MS,SEM-EDS and XRD were employed to analyze the content and mineral phase composition of strategic metals including Li,Ga,Ge and In in gasification slag. Subsequently,the occurrence state of these strategic metals in gasification slag was investigated using a step-by-step chemical extraction method. Moreover,the chemical morphology evolution of Li,Ga,Ge and In during gasification was simulated by Factsage thermodynamic software. The results indicate that compared to Yulin coal,Li and Ga are enriched in both fine slag and coarse slag. Ge and In are highly volatile during the gasification process and are mostly enriched in the gasification fine slag as the syngas cools. The strategic metals Li,Ga,Ge and In in the gasification slag mainly exist in the form of metal oxidation state,organic binding state and residue state,and a small part of Li exists in the ion exchange state and acid soluble state. The strategic metals Li,Ga,Ge and In in the gasification slag primarily exist in the form of metal oxidation state,organic binding state and residue state,with a small portion of Li existing in the ion exchange state and acid soluble state. These findings contribute to elucidating the occurrence state of strategic metal elements in coal gasification slag and the migration law of gasification process,thereby providing a theoretical reference for the comprehensive utilization of coal gasification slag.

Key Words： coal gasification;gasification slag;strategic metal;migration mechanism;occurrence state

Abstract:

Keywords:

Foundation: 国家重点研发计划资助项目（2021YFC2902601）;; 江苏省高校优势学科资助项目

Authors: SHAN Tianqi;YANG Ce;LIU Jinchang;FU Zongpin;ZHAO Yunpeng;

DOI: 10.13226/j.issn.1006-6772.25021302

References：

• [1]代世峰，刘池洋，赵蕾，等.煤系中战略性金属矿产资源：意义和挑战[J].煤炭学报，2022,47(5):1743-1749.DAI Shifeng,LIU Chiyang,ZHAO Lei,et al.Strategic metal resources in coal-bearing strata:Significance and challenges[J].Journal of China Coal Society,2022,47(5):1743-1749.
• [2]徐正震，梁精龙，李慧，等.含锂资源中锂的提取研究现状及展望[J].矿产综合利用，2021(5):32-37.XU Zhengzhen,LIANG Jinglong,LI Hui,et al.Research status and prospects of lithium extraction from lithium containing resources[J].Multipurpose Utilization of Mineral Resources,2021(5):32-37.
• [3]刘大锐，许立军，李世春，等.粉煤灰中战略金属锂的回收研究进展[J].无机盐工业，2023,55(1):56-63.LIU Darui,XU Lijun,LI Shichun,et al.Research progress of recovery of strategic metal lithium from fly ash[J].Inorganic Chemicals Industry,2023,55(1):56-63.
• [4]徐飞，秦身钧，李神勇，等.煤及煤灰中锂的地球化学及其提取研究进展[J].煤炭科学技术，2021,49(9):220-229.XU Fei,QIN Shenjun,LI Shenyong,et al.Research progress on geochemistry and extraction of lithium from coal and coal ash[J].Coal Science and Technology,2021,49(9):220-229.
• [5]蒋炜，刘铁成，李伟，等.中国新能源汽车市场的高速增长对锂资源的需求与挑战[J].矿产勘查，2023,14(10):1814-1824.JIANG Wei,LIU Tiecheng,LI Wei,et al.The rapid growth of new energy vehicle market demands of China and challenges for lithium resources[J].Mineral Exploration,2023,14(10):1814-1824.
• [6]苏慧，朱兆武，王丽娜，等.矿石资源中锂的提取与回收研究进展[J].化工学报，2019,70(1):10-23.SU Hui,ZHU Zhaowu,WANG Lina,et al.Research progress in extraction and recovery of lithium from hard-rock ores[J].CIESCJournal,2019,70(1):10-23.
• [7]吴静，任秀莲，魏琦峰.盐湖卤水中锂的分离提取研究进展[J].无机盐工业，2020,52(12):1-6.WU Jing,Ren Xiulian,Wei Qifeng.Research progress on separation and extraction of lithium from salt-lake brine[J].Inorganic Chemicals Industry,2020,52(12):1-6.
• [8]赵泽森，崔莉，郭彦霞，等.粉煤灰中战略金属镓的提取与回收研究进展[J].化工学报，2021,72(6):3239-3251.ZHAO Zesen,CUI Li,GUO Yanxia,et al.Research progress on extraction and recovery of strategic metal gallium from coal fly ash[J].CIESC Journal,2021,72(6):3239-3251.
• [9]WANG W F,QIN Y,LIU X H,et al.Distribution,occurrence and enrichment causes of gallium in coals from the Jungar Coalfield,Inner Mongolia[J].Science China Earth Sciences,2011,54(7):1053-1068.
• [10]钞晓光，李依帆，张云峰，等.煤中锗的资源分布及其提取工艺研究进展[J].矿产综合利用，2020(4):21-25.CHAO Xiaoguang,LI Yifan,ZHANG Yunfeng,et al.Research progress on resource distribution and extraction technology of germanium in coal[J].Multipurpose Utilization of Mineral Resources,2020(4):21-25.
• [11]武飞乐，李世春.粉煤灰中铝、镓、锂回收技术研究进展[J].中国有色冶金，2023,52(2):116-125.WU Feile,LI Shichun.Research progress of aluminum,gallium and lithium recovery technologies for fly ash[J].China Nonferrous Metallurgy,2023,52(2):116-125.
• [12]周智华，莫红兵，徐国荣，等.稀散金属铟富集与回收技术的研究进展[J].有色金属，2005(1):71-76,80.ZHOU Zhihua,MO Hongbing,XU Guorong,et al.Progress in indium recovery and pre-concentration technology[J].Nonferrous Metals,2005(1):71-76,80.
• [13]REZAEI H,ZIAEDIN SHAFAEI S,ABDOLLAHI H,et al.Asustainable method for germanium,vanadium and lithium extraction from coal fly ash:Sodium salts roasting and organic acids leaching[J].Fuel,2022,312:122844.
• [14]PAN J H,HASSAS B V,REZAEE M,et al.Recovery of rare earth elements from coal fly ash through sequential chemical roasting,water leaching,and acid leaching processes[J].Journal of Cleaner Production,2021,284:124725.
• [15]CHEN H C,ZHANG L,PAN J H,et al.Study on modes of occurrence and enhanced leaching of critical metals(lithium,niobium,and rare earth elements) in coal gangue[J].Journal of Environmental Chemical Engineering,2022,10(6):108818.
• [16]QIN Q Z,DENG J S,GENG H H,et al.An exploratory study on strategic metal recovery of coal gangue and sustainable utilization potential of recovery residue[J].Journal of Cleaner Production,2022,340:130765.
• [17]陈肖役，韩瑞，张宁宁，等.煤气化渣中有害重金属元素的赋存特征及其风险评估[J/OL].洁净煤技术，1-12[2025-01-13].http：//kns.cnki.net/kcms/detail/11.3676.TD.20241106.1528.002.ht ml.CHEN Xiaoyi,HAN Rui,ZHANG Ningning,et al.Occurrence characteristics and risk assessment of harmful heavy metals in coal gasification slag[J/OL].Clean Coal Technology,1-12[2025-01-13].http：//kns.cnki.net/kcms/detail/11.3676.TD.20241106.1528.002.html.
• [18]温家乐，李健，闫琪，等.煤气化渣特性分析及资源化利用途径[J].化工科技，2024,32(6):68-74.WEN Jiale,LI Jian,YAN Qi,et al.Characterization of coal gasification slag and resource utilization pathway[J].Science&Technology in Chemical Industry,2024,32(6):68-74.
• [19]李梦杰，李鹏，范桂侠.煤气化渣的高值化利用研究进展[J].煤化工，2023,51(1):47-53.LI Mengjie,LI Peng,FAN Guixia.Research progress on high value utilization of coal gasification slag[J].Coal Chemical Industry,2023,51(1):47-53.
• [20]吴彬，刘春，郭小凤.煤气化灰渣综合利用研究进展[J].陕西煤炭，2024,43(3):104-108.WU Bin,LIU Chun,GUO Xiaofeng.Research progress of comprehensive utilization of coal gasification ash[J].Shaanxi Coal,2024,43(3):104-108.
• [21]HE G,LIN J,ZHANG Y,et al.Enabling a rapid and just transition away from coal in China[J].One Earth,2020,3(2):187-194.
• [22]PAN J H,ZHOU C C,TANG M C,et al.Study on the modes of occurrence of rare earth elements in coal fly ash by statistics and a sequential chemical extraction procedure[J].Fuel,2019,237:555-565.
• [23]张苏江，周毅，邓文兵，等.粉煤灰中锗的资源赋存与分离提取研究进展[J/OL].矿产综合利用，1-15[2025-01-13].http：//kns.cnki.net/kcms/detail/51.1251.td.20240726.1151.004.html.ZHANG Sujiang,ZHOU Yi,DENG Wenbing,Research progress on resource occurrence,separation and extraction of germanium from flyash[J/OL].mineral resources,1-15[2025-01-13].http：//kns.cnki.net/kcms/detail/51.1251.td.20240726.1151.004.html.
• [24]马晶，马玉龙，朱莉，等.煤气化渣结构组成及其主要金属元素赋存形态[J].化工进展，2024,43(10):5857-5866.MA Jing,MA Yulong,ZHU Li,et al.Structure composition of coal gasification slag and speciation of main metals in coal gasification slag[J].Chemical Industry and Engineering Progress,2024,43(10):5857-5866.
• [25]CHOU J D,WEY M Y,CHANG S H.Evaluation of the distribution patterns of Pb,Cu and Cd from MSWI fly ash during thermal treatment by sequential extraction procedure[J].Journal of Hazardous Materials,2009,162(2-3):1000-1006.
• [26]DAI S F,LI D H,REN D Y,et al.Geochemistry of the Late Permian No.30 coal seam,Zhijin Coalfield of southwest China:Influence of a siliceous low-temperature hydrothermal fluid[J].Applied Geochemistry,2004,19(8):1315-1330.
• [27]王伟成，吴昊，王兴军，等.水煤浆气化过程中元素的迁移与富集特性[J].化工进展，2024,43(10):5942-5949.WANG Weicheng,WU Hao,WANG Xingjun,et al.Characteristics of migration and enrichment of elements during coal water slurry gasification[J].Chemical Industry and Engineering Progress,2024,43(10):5942-5949.
• [28]ZHANG Y F,QU J S,ZHANG J B,et al.Distribution,occurrence,and leachability of typical heavy metals in coal gasification slag[J].Science of The Total Environment,2024,926:172011.
• [29]梁胜男.大同矿区煤中有益微量元素的分布赋存和富集特征.[D].徐州：中国矿业大学，2020.
• [30]ZHANG J Y,ZUO J,JIANG Y S,et al.Kinetic analysis on the mesoporous formation of coal gasification slag by acid leaching and its thermal stability[J].Solid State Sciences,2020,100:106084.
• [31]DAI G F,ZHENG S J,WANG X B,et al.Combustibility analysis of high-carbon fine slags from an entrained flow gasifier[J].Journal of Environmental Management,2020,271:111009.
• [32]ZHAO X L,ZENG C,MAO Y Y,et al.The surface characteristics and reactivity of residual carbon in coal gasification slag[J].Energy&Fuels,2010,24(1):91-94.
• [33]郭旸.宁东煤气化细渣残碳富集及氧化/活化过程中重金属迁移与演化机理[D].徐州：中国矿业大学，2023.
• [34]龚本根.粉煤灰及其利用过程中微量元素迁移转化规律和环境影响研究[D].武汉：华中科技大学，2018.
• [35]GUO Y,LI H C,QIU G F,et al.Processing of coal gasification fine slag by different physical separation methods:Fate of typical heavy metals and comparison analysis on products[J].Separation and Purification Technology,2023,306:122675.
• [36]樊建江，杨慧芳，李平，等.粉煤气化过程中微量元素的迁移与富集特性[J].石油学报（石油加工），2019,35(5):1001-1006.FAN Jianjiang,YANG Huifang,LI Ping,et al.Migration and enrichment of trace elements during the pulverized coal gasification[J].Acta Petrolei Sinica (Petroleum Processing Section),2019,35(5):1001-1006.
• [37]赵继尧，唐修义，黄文辉.中国煤中微量元素的丰度[J].中国煤田地质，2002(S1):6-14,18.ZHAO Jiyao,TANG Xiuyi,HUANG Wenhui.Abundance of trace elements in China coal[J].Coal Geology of China,2002(S1):6-14,18.
• [38]LIU S Q,QI C,JIANG Z,et al.Mineralogy and geochemistry of ash and slag from coal gasification in China:A review[J].International Geology Review,2018,60(5-6):717-735.
• [39]WANG Y F,TANG Y G,HUAN B B,et al.Mineralogical examination of the entrained-flow coal gasification residues and the feed coals from northwest China[J].Advanced Powder Technology,2021,32(11):3990-4003.
• [40]MIAO Z K,WU J J,ZHANG Y X,et al.Chemical characterizations of different sized mineral-rich particles in fine slag from Entrained-flow gasification[J].Advanced Powder Technology,2020,31(9):3715-3723.
• [41]GUO Y,ZHANG Y X,ZHAO X,et al.Multifaceted evaluation of distribution,occurrence,and leaching features of typical heavy metals in different-sized coal gasification fine slag from Ningdong region,China:A case study[J].Science of The Total Environment,2022,831:154726.
• [42]SHAO P,HOU H J,WANG W L,et al.Geochemistry and mineralogy of fly ash from the high-alumina coal,Datong Coalfield,Shanxi,China[J].Ore Geology Reviews,2023,158:105476.
• [43]代世峰，任德贻，唐跃刚.煤中常量元素的赋存特征与研究意义[J].煤田地质与勘探，2005,33(2):1-5.DAI Shifeng,REN Deyi,TANG Yuegang.Modes of occurrence of major elements in coal and their study significance[J].Coal Geology&Exploration,2005,33(2):1-5.
• [44]张复新，王立社.内蒙古准格尔黑岱沟超大型煤型镓矿床的形成与物质来源[J].中国地质，2009,36(2):417-423.ZHANG Fuxin,WANG Lishe.The formation and material sources of the superlarge Hada Gol Ga-bearing coal deposit in Jungar Banner,Inner Mongolia[J].Geology in China,2009,36(2):417-423.
• [45]覃轩.大同煤田煤中微量元素富集特征及共生关系成因研究[J].煤炭科学技术，2019,47(11):189-195.QIN Xuan.Study on enrichment characteristics of trace elements and genesis of symbiotic relationship of coal in Datong Coalfield[J].Coal Science and Technology,2019,47(11):189-195..