离子型稀土开发面临的问题与绿色提取研究进展

doi:10.16085/j.issn.1000-6613.2018-1687

摘要/Abstract

摘要：

离子型稀土开采先后经历了池浸、堆浸和原地浸矿，目前主要采用硫酸铵原地浸出、碳酸氢铵沉淀的工艺提取稀土，这种方式具有工艺简单、生产成本低的优点，但存在土壤盐碱化、氨氮超标、植被破坏、水土流失等环境污染问题，严重制约生态的可持续发展。本文介绍了离子型稀土开采涉及的环保政策，分析了原地浸矿收液的多种不确定性因素，以致稀土资源利用率低，一般在50%～75%，阐述了浸矿过程中布设注液井网造成地表植被破坏、注液过度饱和引起山体滑坡以及水土中氨氮超标等“三废”问题。综述了离子型稀土新型浸矿剂、原地浸矿人工防渗技术、原矿浸萃一体化工艺、矿山修复新工艺等绿色开发技术研究进展。分析表明，突破离子型稀土开发中环境污染的瓶颈，须进一步改变提取工艺、改进生产装备，并提出了离子型稀土绿色提取与环境保护的发展方向。

关键词: 离子型稀土, 浸取剂, 氨氮污染, 绿色提取

Abstract:

Ion adsorption rare earths mining has experienced pool leaching, heap leaching and in situ leaching processes. Nowadays, rare earth is recovered by leaching process with (NH₄)₂SO₄ solution in industry, and enriched by precipitating with NH₄HCO₃. This method has the advantages of simple process and low production cost. But the environmental problems such as soil salinization, ammonia nitrogen pollution, surface vegetation destruction and soil erosion are often accompanied, which seriously restrict the sustainable development of the ecological environment. In this paper, the environmental protection policies about ionic rare earth mining were introduced, and the reasons for the low utilization rate of rare earth resources (generally 50%—75%) were analyzed, mainly because of the uncertainty of liquid recovery project. In the leaching process, the destruction of vegetation on the surface caused by the arrangement of injection well pattern, the landslide caused by excessive saturation of injection, the problems of three wastes such as the excessive ammonia and nitrogen in soil and water, were expounded. The new methods and theories of in-situ leaching of ion adsorption rare earth ores, the new technology of ion adsorption rare earth ore leaching extraction integration, and the new technology of mine restoration were described. The analysis showed that to break through the environmental bottleneck of the development of ionic rare earth, it is necessary to further change the extraction process and improve the production preparation. Moreover, the development directions of green extraction process have been proposed.

Key words: ion adsorption rare earths, leaching agent, ammonia nitrogen pollution, green extraction

中图分类号:

TD983
TD955

郭钟群, 赵奎, 金解放, 袁伟, 梁晨. 离子型稀土开发面临的问题与绿色提取研究进展[J]. 化工进展, 2019, 38(07): 3425-3433.

Zhongqun GUO, Kui ZHAO, Jiefang JIN, Wei YUAN, Chen LIANG. Problems facing ion adsorption type rare earth exploitation andresearch progresses on green extraction[J]. Chemical Industry and Engineering Progress, 2019, 38(07): 3425-3433.

图/表 4

参考文献 56

1	HUANG X W , LONG Z Q , WANG L S , et al . Technology development for rare earth cleaner hydrometallurgy in China [J]. Rare Metals, 2015, 34(4): 215-222.
2	YE T , LEI J . Intrinsically robust hydrophobicity[J]. Nature Materials, 2013, 12(4): 291-292.
3	张优灵, 高银留, 尹荔松 . 我国稀土无机转光剂的研究进展[J]. 化工进展, 2014, 33(s1): 258-260.
	ZHANG Y L , GAO Y L , YIN L S , et al . Research progress of rare earth inorganic light conversion agent in China[J]. Chemical Industry and Engineering Progress, 2014, 33(s1): 258-260.
4	池汝安, 田君 . 风化壳淋积型稀土矿评述[J]. 中国稀土学报, 2007, 25(6): 641-650.
	CHI R A , TIAN J . Review of weathered crust rare earth ore [J]. Journal of the Chinese Rare Earth Society, 2007, 25(6): 641-650.
5	郭钟群, 金解放, 赵奎, 等 . 离子吸附型稀土开采工艺与理论研究现状[J]. 稀土, 2018, 39(1): 132-141.
	GUO Z Q , JIN J F , ZHAO K , et al . Status of leaching technology and theory of ion adsorption type rare earth ores[J]. Chinese Rare Earths, 2018, 39(1): 132-141.
6	TIAN J , YIN J Q , CHI R A , et al . Kinetics on leaching rare earth from the weathered crust elution-deposited rare earth ores with ammonium sulfate solution [J]. Hydrometallurgy, 2010, 101(3/4): 166-170.
7	罗仙平, 钱有军, 梁长利 . 从离子型稀土矿浸取液中提取稀土的技术现状与展望[J]. 有色金属科学与工程, 2012, 3 (5): 50-53.
	LUO X P , QIAN Y J , LIANG C L . Research progress and developing trend of rare earth extraction from ionic rare earth leach solution [J]. Nonferrous Metals Science and Engineering, 2012, 3 (5): 50-53.
8	WANG G S , LAI Y M , PENG C L . Adsorption of rare earth yttrium and ammonium ions on kaolinite surfaces: a DFT study[J]. Theoretical Chemistry Accounts, 2018, 137(4): 53.
9	陈涛, 李宁, 晏波, 等 . 稀土湿法冶炼废水污染治理技术与对策[J]. 化工进展, 2014, 33(5): 1306-1311.
	CHEN T , LI N , YAN B , et al . Pollution control technologies and measures of rare earths hydrometallurgy wastewater [J]. Chemical Industry and Engineering Progress, 2014, 33(5): 1306-1311.
10	魏娟萍, 王海宁, 晏江波 . 南方离子型稀土矿开采的环境损伤及防治[J]. 有色金属科学与工程, 2016, 7(1): 125-132.
	WEI J P , WANG H N , YAN J B , et al . Environmental damages and control measures in exploiting ion-absorbed rare earth of south China [J]. Nonferrous Metals Science and Engineering, 2016, 7(1): 125-132.
11	李永绣, 张玲, 周新木 . 南方离子型稀土的资源和环境保护性开采模式[J]. 稀土, 2010,31(2): 80-85.
	LI Y X , ZHANG L , ZHOU X M . Resource and environment protected exploitation model for ion-type rare earth deposit in southern of China [J]. Chinese Rare Earths, 2010, 31(2): 80-85.
12	肖子捷, 刘祖文, 张念 . 离子型稀土采选工艺环境影响分析与控制技术[J]. 稀土, 2014, 35 (6): 56-61.
	XIAO Z J , LIU Z W , ZHANG N . Environmental impact analysis and control technology of ion rare earth mining in south of Jiangxi Province [J]. Chinese Rare Earths, 2014, 35 (6): 56-61.
13	汤洵忠, 李茂楠, 杨殿 . 离子型稀土矿原地浸析采场滑坡及其对策[J]. 金属矿山, 2000(7): 5-8.
	TANG X Z , LI M N , YANG D . Stope Slide in in-situ leaching of ionic type rare earth ore and its countermeasures[J]. Metal Mine, 2000(7): 5-8.
14	黄紫彬, 蔡昶, 袁宪强, 等 . 浅析原地浸矿开采的离子型稀土矿山安全问题[J]. 稀土, 2013, 34(4): 99-102.
	HUANG Z B , CAI C , YUAN X Q , et al . Analysis of safety problems of ion type rare earth mine during in-situ leaching[J]. Chinese Rare Earths, 2013, 34(4): 99-102.
15	ZHOU D , LI Z Z , LUO X P , et al . Leaching of rare earth elements from contaminated soils using saponin and rhamnolipid bio-surfactant[J]. Journal of Rare Earths, 2017, 35(9): 911-919.
16	杨秀英, 刘祖文, 胡方洁, 等 . 土壤稀土元素和氮化物污染对植物生长及生理的影响[J]. 中国稀土学报, 2019, 37(1): 1-11.
	YANG X Y , LIU Z W , HU F J , et al . Soil rare earth element and nitride pollution on plant growth and physiology[J]. Journal of the Chinese Rare Earth Society, 2019, 37(1): 1-11.
17	LI H K , LEI J , WU J . Evolution analysis of vegetation cover under the disturbance of rare earth mining: a case in lingbei mining area[J]. Journal of Applied Science and Engineering, 2017, 20(3): 393-400.
18	刘祖文, 张军 . 离子型稀土矿区土壤氮化物污染机理[M]. 北京: 冶金工业出版社, 2018: 2-3.
	LIU Z W , ZHANG J . Mechanism of soil nitrogen pollution in ionic rare earth mining area[M]. Beijing: Metallurgical Industry Press, 2018: 2-3.
19	张军, 胡方洁, 刘祖文, 等 . 离子型稀土矿区土壤中铵态氮迁移规律研究[J]. 稀土, 2018, 39(3): 108-116.
	ZHANG J , HU F J , LIU Z W , et al . Study on the migration of ammonium nitrogen in the soil of the ionic type rare earth ore area [J]. Chinese Rare Earths, 2018, 39(3): 108-116.
20	郭钟群, 金解放, 赵奎, 等 . 离子型稀土溶浸液毛细上升规律及影响因素研究[J]. 有色金属工程, 2018, 8(2): 78-82.
	GUO Z Q , JIN J F , ZHAO K , et al . The capillary rise laws of leaching solution of ion-absorbed rare earth and its effective factors[J]. Nonferrous Metals Engineering, 2018, 8(2): 78-82.
21	丁嘉榆 . 离子型稀土矿开发的历史回顾——纪念赣州有色冶金研究所建所60周年[J]. 有色金属科学与工程, 2012,3(4): 14-19.
	DING J Y . Historical review of the ionic rare earth mining: in honor of the 60 anniversary of GNMRI [J]. Nonferrous Metals Science and Engineering, 2012, 3(4): 14-19.
22	赖兰萍, 欧阳红, 伍莺, 等 . 离子型稀土矿无氨浸出研究[J]. 金属矿山, 2014(10): 95-97.
	LAI L P , YANG Y H OU , WU Y , et al . No ammonia leaching study of ionic rare-earth ore[J]. Metal Mine, 2014(10): 95-97.
23	罗仙平, 陈晓明, 梁长利, 等 .一种风化壳淋积型离子稀土矿的浸出方法: CN201310193492.6[P]. 2013-08-21.
	LUO X P , CHEN X M , LIANG C L , et al . A kind of weathered crust elution-deposited rare earth ore leaching method: CN201310193492.6 [P]. 2013-08-21.
24	TIAN J , TANG X K , YIN J Q , et al . Enhanced leaching process of a low-grade weathered crust elution-deposited rare earth ore with carboxymethyl sesbania gum[J]. Hydrometallurgy, 2013, 139: 124-131
25	唐学昆, 田君, 尹敬群, 等 . 田菁胶助浸低品位风化壳淋积型稀土矿研究[J]. 有色金属科学与工程, 2013, 4(2): 85-89.
	TANG X K , TIAN J , YIN J Q , et al . Research on aid-leaching rare earth from low-grade weathered crust elution-deposited rare earth ore with sesbania gum [J]. Nonferrous Metals Science and Engineering, 2013, 4(2): 85-89.
26	QIU T S , FANG X H , CUI L F , et al . Behavior of leaching and precipitation of weathering crust ion-absorbed type by magnetic field[J]. Journal of Rare Earths, 2008, 26(2):274-278.
27	胡珊玲, 林燕, 余建平 . 超声波强化浸取离子型稀土矿中稀土[J]. 冶金分析, 2012, 32(11): 22-25.
	HU S L , LIN Y , YU J P . Strengthened leaching of rare earths in ionic rare earth ore by ultrasonic[J]. Metallurgical Analysis, 2012, 32(11): 22-25.
28	李㼆婷, 涂安斌, 张越非, 等 . 混合铵盐用于风化壳淋积型稀土矿浸取稀土的动力学研究[J]. 化工矿物与加工, 2009, 38(2): 19-24.
	LI Y T , TU A B , ZHANG Y F , et al . Kinetics of leaching rare earth from a weathered crust elution-deposited rare earth ore in South China with mixed ammonium salt[J]. Industrial Minerals & Processing, 2009, 38(2): 19-24.
29	姚慧琴, 欧阳克氙, 饶国华 . 用复合浸出剂浸取风化壳淋积型稀土矿中的稀土研究[J]. 江西科学, 2005, 23 (16): 721-726.
	YAO H Q ， OUYANG K X ， RAO G H . A study on leaching rare earth from the weathered eution deposited rare earth ore with compound leaching reagent[J]. Jiangxi Science, 2005, 23( 16) : 721-726.
30	王瑞祥, 杨幼明, 杨斌, 等 . 一种离子吸附型稀土提取方法: CN 201310199034.3[P]. 2013-08-28.
	WANG R X , YANG Y M , YANG B , et al . A kind of method fot extraction of rare earth from ion-adsorption type rare earth: CN201310199034.3[P]. 2013-08-28.
31	池汝安, 李琼, 徐志高, 等 . 一种风化壳淋积型稀土矿浸矿剂及其提取稀土的方法: CN201310481335.5[P]. 2014-01-01.
	CHI R A , LI Q , XU Z G , et al . A kind of leaching agent and extraction method from rare earth weathered crust elution-deposited rare earth ore: CN201310481335.5[P]. 2014-01-01.
32	李永绣, 谢爱玲, 李昳林, 等 . 一种利用离子型稀土尾矿中的粗粒粘土处理极低稀土浓度废水的方法: CN201310400389.4 [P]. 2013-12-18.
	LI Y X , XIE A L , LI Y L , et al . A method for treating extremely low rare earth concentration waste water by coarse grained clay in ion type rare earth tailings : CN201310400389.4 [P]. 2013-12-18.
33	李永绣, 王悦, 谢爱玲, 等 . 从低浓度含铵稀土溶液中去除氨氮并回收稀土的方法: CN201310355981.7 [P]. 2013-12-25.
	LI Y X , WANG Y , XIE A L , et al . A method for removing ammonia nitrogen and recovering rare earth from low concentration ammonium containing rare earth solution: CN201310355981.7 [P]. 2013-12-25.
34	王满合, 曾明, 王良士, 等 . 氟碳铈矿氧化焙烧-盐酸催化浸出新工艺研究[J]. 中国稀土学报, 2018, 31(3): 148-154.
	WANG M H , ZENG M , WANG L S , et al . Catalytic leaching process of bastnaesite with hydrochloric acid after oxidation roasting pretreatment [J]. Journal of the Chinese Rare Earth Society, 2018, 31(3): 148-154.
35	邱廷省, 伍红强, 方夕辉, 等 . 风化壳淋积型稀土矿提取除杂技术现状及进展[J]. 稀土, 2012, 33(4): 81-85.
	QIU T S , WU H Q , FANG X H , et al . The current situation and trends of the technology for impurity removal of weathering crust ion-absorbed type rare earth ores[J]. Chinese Rare Earths, 2012, 33(4): 81-85.
36	FENG X J , TAO T , ZHU Y C . Transport kinetics of pollutants in in-situ leaching of ionic type rare-earth ore[J]. Procedia Environmental Sciences, 2012(12): 917-925.
37	WANG X J , ZHUO Y L , DENG S Q , et al . Experimental research on the impact of ion exchange and infiltration on the microstructure of rare earth orebody[J]. Advances in Materials Science and Engineering, 2017(1): 1-8.
38	吴爱祥, 尹升华, 李建锋 . 离子型稀土矿原地溶浸溶浸液渗流规律的影响因素[J]. 中南大学学报(自然科学版), 2005, 36(3): 506-510.
	WU A X , YIN S H , LI J F . Influential factors of permeability rule of leaching solution in ion- absorbed rare earth deposits with in-situ leaching[J]. Journal of Central South University(Science and Technology), 2005, 36(3): 506－510.
39	冯宗玉, 黄小卫, 王猛, 等 . 典型稀土资源提取分离过程的绿色化学进展及趋势[J]. 稀有金属, 2017, 41(5): 604-612.
	FENG Z Y , HUANG X W , WANG M , et al . Progress and trend of green chemistry in extraction and separation of typical rare earth resources[J]. Chinese Journal of Rare Metals, 2017, 41(5): 604-612.
40	黄小卫, 于瀛, 冯宗玉, 等 . 一种从离子型稀土原矿回收稀土的方法: CN201010128302.9 [P]. 2011-09-21.
	HUANG X W , YU Y , FENG Z Y , et al . A method of recovery of rare earth from ionic type rare-earth ore: CN201010128302.9 [P]. 2011-09-21.
41	黄小卫, 冯宗玉, 赵龙胜, 等 . 从低浓度稀土溶液中萃取富集回收稀土的方法: CN201610644810.X [P]. 2018-02-16.
	HUANG X W , FENG Z Y , ZHAO L S , et al . A method for extraction and recovery of rare earth from low concentration rare earth solution: CN201610644810.X [P]. 2018-02-16.
42	肖燕飞, 黄小卫, 冯宗玉, 等 . 镁盐浸出离子吸附型稀土矿的环境影响评价及展望[J]. 中国稀土学报, 2015, 33(1): 1-9.
	XIAO Y F , HUANG X W , FENG Z Y , et al . Environmental impact assessment and prospect for ion-adsorption type rare earths ore leaching by magnesium salt[J]. Journal of the Chinese Rare Earth Society, 2015, 33(1): 1-9.
43	XIAO Y F , FENG Z Y , HUANG X W , et al . Recovery of rare earths from weathered crust elution-deposited rare earth ore without ammonia-nitrogen pollution: Ⅰ.Leaching with magnesium sulfate[J]. Hydrometallurgy, 2015, 153: 58-65.
44	XIAO Y F , FENG Z Y , HU G H , et al . Leaching and mass transfer characteristics of elements from the ion-adsorption type rare earth ore[J]. Rare Metals， 2015, 34(5) : 357-365.
45	陈敏, 张大超, 朱清江, 等 . 离子型稀土矿山废弃地生态修复研究进展[J]. 中国稀土学报, 2017, 35(5): 461-468.
	CHEN M , ZHANG D C , ZHU Q J , et al . Ionic rare earth mine of abandoned land of ecological restoration of research progress[J]. Journal of the Chinese Rare Earth Society, 2017, 35(5): 461-468.
46	钱春香, 王明明, 许燕波 . 土壤重金属污染现状及微生物修复技术研究进展[J]. 东南大学学报（自然科学版）, 2013, 43(3): 669-674.
	QIAN C X , WANG M M , XU Y B . Current situation of soil contamination by heavy metals and research progress in bio-remediation technique [J]. Journal of Southeast University(Natural Science Edition), 2013, 43(3): 669-674.
47	李永绣 . 离子型吸附型稀土资源与绿色提取[M]. 北京: 化学工业出版社, 2014: 278-280.
	Li Y X . Ion adsorption rare earth resources and their green extraction [M]. Beijing: Chemical Industry Press, 2014: 278-280.
48	陈振金, 郑大增 . 稀土尾矿场土地复垦技术研究[J]. 上海环境科学, 1998, 17(9):28-31.
	ChEN Z J , ZHENG D Z . Study on land reclamation of rare earth trailing sites[J]. Shanghai Environmental Sciences, 1998, 17(9):28-31.
49	李德荣, 董闻达, 廖汉民, 等 . 治理稀土尾砂中百喜草的生长和促苗措施的研究[J]. 江西农业大学学报, 2001, 23(1): 93-95.
	LI D R , DONG W D , LIAO H M , et al . A study on the growth and seedling improvement of Bahia Grass in the tail mineral slag of rare earth [J]. Acta Agriculturae Universitatis Jiangxiensis, 2001, 23(1): 93-95.
50	曹学章, 李小青, 池明茹, 等 . 4种草用于南方稀土尾砂地种植的适宜性之比较[J]. 江西农业大学学报, 2012, 34(3): 603-608.
	CAO X Z , LI X Q , CHI M R , et al . Comparison of planting suitability of four herbaceous plants on rare earth tailings in South China[J]. Acta Agriculturae Universitatis Jiangxiensis, 2012, 34(3): 603-608.
51	鲁向晖, 唐安华, 白桦, 等 . 桉树修复对江西稀土尾砂区土壤养分的影响[J]. 南方农业学报, 2016, 47(7): 1100-1104.
	LU X H , TANG A H , BAI H , et al . Effect of eucalyptus revegetation on soil nutrient in rare earth tailings[J]. Journal of Southern Agriculture, 2016, 47(7): 1100-1104.
52	蔡奇英, 刘以珍, 管毕财, 等 . 南方离子型稀土矿的环境问题及生态重建途径[J]. 国土与自然资源研究, 2013(5): 52-54.
	CAI Q Y , LIU Y Z , GUAN B C , et al . Environmental issues and ecological restoration of ion-absorbed-type rare earth deposit in south China [J]. Territory and natural resources study, 2013(5): 52-54.
53	LUO C G , DENG Y W , LIANG J , et al . Exogenous rare earth element-yttrium deteriorated soil microbial community structure[J]. Journal of Rare Earths, 2018, 36(4): 430-439.
54	周际海, 黄荣霞, 樊后保, 等 . 污染土壤修复技术研究进展[J]. 水土保持研究, 2016, 23(3): 366-372.
	ZHOU J H , HUANG R X , FAN H B , et al . A review on the progresses of remediation technologies for contaminated soils[J]. Research of Soil and Water Conservation, 2016, 23(3): 366-372.
55	陈熙, 刘以珍, 李金前, 等 . 稀土尾矿土壤细菌群落结构对植被修复的响应[J]. 生态学报, 2016, 36(13): 3943-3950.
	CHEN X , LIU Y Z , LI J Q , et al . Response of a rare earth tailing soil bacterial community structure to vegetation restoration[J]. Acta Ecologica Sinica, 2016, 36(13): 3943-3950.
56	陈莺燕, 刘文深, 丁铿博, 等 . 有机改良剂及生物炭对离子型稀土矿尾砂地生态修复的改良探究[J]. 环境科学学报, 2018, 38(12): 4769-4778.
	CHEN Y Y , LIU W S , DING K B , et al . Effects of organic amendments and biochar on ecological remediation of ionic rare earth mine tailings [J]. Acta Scientiae Circumstantiae, 2018, 38(12): 4769-4778.

修复方法	优势	不足
物理修复
淋洗法	适用于小面积地区或某些严重污染的土	易形成二次污染，可能要剥离土进行异地修复
电动修复法	对湿度较高的土效果好，适合饱和及非饱和土	须在酸性条件下进行，耗费时间长
直接换土法	方便直接高效，适用于修复后利用价值高的土	换土工程量大，造价高
化学修复
化学固化	土壤结构不受扰动，适合大面积地区操作	固化剂成本高，加入的化学试剂或发生的化学反应可能造成生态环境的二次污染
生物修复
植物修复法	成本低、土壤免受扰动，具有良好的生态效益、社会效益及经济效益	多数植物只能积累1或2种污染元素，实际污染情况大多为几种重金属复合污染，具有局限性
微生物修复法	成本低、土壤免受扰动，具有良好的生态效益、社会效益及经济效益	菌株的筛选、环境对微生物的变异作用研究不足

修复方法	优势	不足
物理修复
淋洗法	适用于小面积地区或某些严重污染的土	易形成二次污染，可能要剥离土进行异地修复
电动修复法	对湿度较高的土效果好，适合饱和及非饱和土	须在酸性条件下进行，耗费时间长
直接换土法	方便直接高效，适用于修复后利用价值高的土	换土工程量大，造价高
化学修复
化学固化	土壤结构不受扰动，适合大面积地区操作	固化剂成本高，加入的化学试剂或发生的化学反应可能造成生态环境的二次污染
生物修复
植物修复法	成本低、土壤免受扰动，具有良好的生态效益、社会效益及经济效益	多数植物只能积累1或2种污染元素，实际污染情况大多为几种重金属复合污染，具有局限性
微生物修复法	成本低、土壤免受扰动，具有良好的生态效益、社会效益及经济效益	菌株的筛选、环境对微生物的变异作用研究不足