离子型稀土矿山氨氮废水生物脱氮技术研究进展

doi:10.19965/j.cnki.iwt.2024-0059

摘要/Abstract

摘要：

南方离子型稀土矿通常采用硫酸铵作浸矿剂进行提取开采，矿山开采后的很长一段时期都将产生大量的矿山地表氨氮废水，该废水的主要水质特征为有机碳源极缺、NH₄ ⁺-N和NO₃ ^--N共存，废水脱氮成本高昂。以我国离子型稀土资源开采量最大的赣州市稀土矿区为例，分析了离子型稀土矿山氨氮废水的水量水质特征；比较了现有的离子型稀土矿山废水处理工程实践的工艺技术特点，并进行了理论成本分析；在分析常规厌氧氨氧化等新型生物脱氮技术在稀土矿山氨氮废水处理中的优势与不足的基础上，围绕水质特征与降低成本目标，提出了短程反硝化-短程硝化-厌氧氨氧化耦合工艺为离子型稀土矿山氨氮废水脱氮最优工艺。

关键词: 离子型稀土矿山, 氨氮废水, 短程反硝化, 短程硝化, 厌氧氨氧化

Abstract:

Ammonium sulfate is a commonly used leaching agent in the mining process of southern ion-type rare earth mines, which causes large quantities of mine ammonia-nitrogen wastewater under the leaching action of rainwater even after stopping mining for a long time. The typical characteristics of ion-type rare earth mine ammonia-nitrogen wastewater are extreme low C/N, coexistence of ammonia and nitrate, which increased the cost and difficulty of nitrogen removal. Taking Ganzhou rare earth mining area, which had the largest amount of ionic rare earth resources in China, as an example, the water quantity and quality characteristics of ammonia-nitrogen wastewater from ion-type rare earth mines were analyzed. The process technology characteristics of existing ion-type rare earth mine wastewater treatment engineering practices were compared, and theoretical cost analysis was conducted. Based on the analysis of the advantages and disadvantages of new biological nitrogen removal technologies such as Anammox in the treatment of ammonia-nitrogen wastewater from rare earth mines, a combined process of partial denitrification-partial nitrification-Anammox was proposed to improve the effluent quality and reduce energy, which was proved to be the best process for removing nitrogen from ammonia-nitrogen wastewater of ionic rare earth mines.

Key words: ion-type rare earth mine, ammonia-nitrogen wastewater, partial denitrification, partial nitrification, Anammox

中图分类号:

X703

范存文, 郭佩洁, 胡予佳, 刘新福, 邱清荣, 苏昊, 张大超. 离子型稀土矿山氨氮废水生物脱氮技术研究进展[J]. 工业水处理, 2025, 45(1): 9-16.

Cunwen FAN, Peijie GUO, Yujia HU, Xinfu LIU, Qingrong QIU, Hao SU, Dachao ZHANG. Process on biological nitrogen removal technology of ammonia- nitrogen wastewater from ion-type rare earth mines[J]. Industrial Water Treatment, 2025, 45(1): 9-16.

https://www.iwt.cn/CN/Y2025/V45/I1/9

图/表 7

图1 2022—2023年赣州某离子型稀土矿区稀土矿山废水水质每日变化

Fig.1 Daily change of rare earth mine wastewater quality in an ion-type rare earth mining area in Ganzhou in 2022-2023

图2 2022年赣州某离子型稀土矿区稀土矿山废水水质每月变化

Fig.2 Monthly change of rare earth mine wastewater quality in an ion-type rare earth mining area in Ganzhou in 2022

表1 赣州离子型稀土矿区废水处理站建设情况

Table 1 Construction of wastewater treatment station in Ganzhou of ion-type rare earth mine

废水处理站名称	设计规模/（m³·d^-1）	工艺名称	脱氮原理	碳源形式
黄沙站	40 000	双级渗滤耦合系统	硝化-反硝化	外加
乡际联站	6 000	RO+吹脱+AOA	硝化-反硝化	外加
关西站	6 000	两级OA	硝化-反硝化	外加
临塘（一）站	4 000	单级渗滤耦合系统	硝化-反硝化	外加
临塘（二）站	6 000	速分生化	硝化-反硝化	外加
马山迳站	3 500	单级渗滤耦合系统	硝化-反硝化	外加
上下营站	3 500	单级渗滤耦合系统	硝化-反硝化	外加
青龙岩站	12 000	折点氯化法	化学氧化	无

图3 短程硝化-反硝化工艺与传统脱氮工艺比较

Fig.3 Comparison of partial nitrification-denitrification process and traditional denitrification process

图4 短程反硝化-短程硝化-厌氧氨氧化耦合工艺原理

Fig.4 Principle of PD-PN-Anammox combined process

图5 短程反硝化-短程硝化-厌氧氨氧化耦合工艺中试装置示意

Fig.5 Schematic diagram of pilot plant for the combined process of PD-PN-Anammox

图6 组合工艺脱氮成本示意

Fig.6 Cost schematic diagram of combined process for nitrogen removal

参考文献 50

1	HUANG Xiaowei， LONG Zhiqi， WANG Liangshi，et al. Technology development for rare earth cleaner hydrometallurgy in China［J］. Rare Metals，2015，34（4）：215-222. doi:10.1007/s12598-015-0473-x
2	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 Zongyu， HUANG Xiaowei， WANG Meng，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.
3	池汝安，刘雪梅. 风化壳淋积型稀土矿开发的现状及展望［J］. 中国稀土学报，2019，37（2）：129-140.
	CHI Ru’an， LIU Xuemei. Prospect and development of weathered crust elution-deposited rare earth ore［J］. Journal of the Chinese Society of Rare Earths，2019，37（2）：129-140.
4	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（4）：461-468.
	CHEN Min， ZHANG Dachao， ZHU Qingjiang，et al. Ionic rare earth mine of abandoned land of ecological restoration of research progress［J］. Journal of the Chinese Society of Rare Earths，2017，35（4）：461-468.
5	YAN Huashan， LIANG Taomao， LIU Qingsheng，et al. Compound leaching behavior and regularity of ionic rare earth ore［J］. Powder Technology，2018，333：106-114. doi:10.1016/j.powtec.2018.04.010
6	LIU Wenshen， GUO Meina， LIU Chang，et al. Water，sediment and agricultural soil contamination from an ion-adsorption rare earth mining area［J］. Chemosphere，2019，216：75-83. doi:10.1016/j.chemosphere.2018.10.109
7	苏昊. 稀土（镧离子）对短程硝化和厌氧氨氧化过程的影响及机制［D］. 赣州：江西理工大学，2021.
	SU Hao. Effect and mechanism of rare earth（lanthanum ion） on short-cut nitrification and anaerobic ammonium oxidation［D］. Ganzhou：Jiangxi University of Science and Technology，2021.
8	池汝安，田君. 风化壳淋积型稀土矿化工冶金［M］. 北京：科学出版社，2006：642-650.
9	邓国庆，杨幼明. 离子型稀土矿开采提取工艺发展述评［J］. 稀土，2016，37（3）：129-133.
	DENG Guoqing， YANG Youming. A review of the mining technologies of ion-absorbed rare earth mineral［J］. Chinese Rare Earths，2016，37（3）：129-133.
10	刘斯文，黄园英，朱晓华，等. 离子型稀土采矿对矿山及周边水土环境的影响［J］. 环境科学与技术，2015，38（6）：25-32.
	LIU Siwen， HUANG Yuanying， ZHU Xiaohua，et al. Environmental effects of ion-absorbed type rare earth extraction on the water and soil in mining area and its peripheral areas［J］. Environmental Science & Technology，2015，38（6）：25-32.
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 Yongxiu， ZHANG Ling， ZHOU Xinmu. 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	GB 3838—2002 地表水环境质量标准［S］. doi:10.7717/peerj.13400/supp-2
	GB 3838—2002 Environmental quality standards for surface water ［S］. doi:10.7717/peerj.13400/supp-2
13	GB 26451—2011 稀土工业污染物排放标准［S］. doi:10.1016/b978-0-12-802328-0.00019-x
	GB 26451—2011 Emission standards of pollutants from rare earths industry ［S］. doi:10.1016/b978-0-12-802328-0.00019-x
14	郑平. 新型生物脱氮理论与技术［M］. 北京：科学出版社，2004：35-74.
15	JIA Yating， ZHOU Miaomiao， CHEN Yuancai，et al. Insight into short-cut of simultaneous nitrification and denitrification process in moving bed biofilm reactor：Effects of carbon to nitrogen ratio［J］. Chemical Engineering Journal，2020，400：125905. doi:10.1016/j.cej.2020.125905
16	魏良良. SBR短程硝化反硝化工艺处理氨氮高盐废水的研究［D］. 南昌：南昌大学，2019.
	WEI Liangliang. Study on treatment of ammonia nitrogen and high salinity wastewater by SBR short-cut nitrification and denitrification process［D］. Nanchang：Nanchang University，2019.
17	LIN Lan， ZHANG Yanlong， LI Yuyou. Enhancing start-up strategies for anammox granular sludge systems：A review［J］. Science of the Total Environment，2023，902：166398. doi:10.1016/j.scitotenv.2023.166398
18	ZHANG Shunan， CHEN Junli， LIU Feng，et al. Effect of free ammonia and free nitrous acid on nitrogen removal of heterotrophic nitrification and aerobic denitrification bacteria［J］. Journal of Water Process Engineering，2023，56：104316. doi:10.1016/j.jwpe.2023.104316
19	GONG Siyuan， QIN Yujie， ZHENG Shaohong，et al. The rapid start-up of CANON process through adding partial nitration sludge to ANAMMOX system［J］. Journal of Environmental Management，2023，338：117821. doi:10.1016/j.jenvman.2023.117821
20	HIEN N NHU， VAN TUAN D， NHAT P T，et al. Application of oxygen limited autotrophic nitritation/denitrification（OLAND） for anaerobic latex processing wastewater treatment［J］. International Biodeterioration & Biodegradation，2017，124：45-55. doi:10.1016/j.ibiod.2017.07.009
21	YUAN Chuansheng， WANG Bo， PENG Yongzhen，et al. Enhanced nutrient removal of simultaneous partial nitrification，denitrification and phosphorus removal（SPNDPR） in a single-stage anaerobic/micro-aerobic sequencing batch reactor for treating real sewage with low carbon/nitrogen［J］. Chemosphere，2020，257：127097. doi:10.1016/j.chemosphere.2020.127097
22	李丹. 稀土矿区低碳氨氮废水SBR短程硝化的应用研究［D］. 赣州：江西理工大学，2019.
	LI Dan. Study on application of SBR shortcut nitrification in low carbon ammonia nitrogen wastewater from rare earth mining area［D］. Ganzhou：Jiangxi University of Science and Technology，2019.
23	ZHANG Li， WANG Yueping， SODA S，et al. Effect of fulvic acid on bioreactor performance and on microbial populations within the anammox process［J］. Bioresource Technology，2020，318：124094. doi:10.1016/j.biortech.2020.124094
24	ANTWI P， ZHANG Dachao， LUO Wuhui，et al. Performance，microbial community evolution and neural network modeling of single-stage nitrogen removal by partial-nitritation/anammox process［J］. Bioresource Technology，2019，284：359-372. doi:10.1016/j.biortech.2019.03.008
25	ZHANG Dachao， XU Shi， ANTWI P，et al. Accelerated start-up，long-term performance and microbial community shifts within a novel upflow porous-plated anaerobic reactor treating nitrogen-rich wastewater via ANAMMOX process［J］. RSC Advances，2019，9（45）：26263-26275. doi:10.1039/c9ra04225c
26	TANG Linqin， SU Chengyuan， CHEN Yu，et al. Influence of biodegradable polybutylene succinate and non-biodegradable polyvinyl chloride microplastics on anammox sludge：Performance evaluation，suppression effect and metagenomic analysis［J］. Journal of Hazardous Materials，2021，401：123337. doi:10.1016/j.jhazmat.2020.123337
27	ANTWI P， ZHANG Dachao， SU Hao，et al. Nitrogen removal from landfill leachate by single-stage anammox and partial-nitritation process：Effects of microaerobic condition on performance and microbial activities［J］. Journal of Water Process Engineering，2020，38：101572. doi:10.1016/j.jwpe.2020.101572
28	ZHANG Zhengzhe， ZHANG Yu， CHEN Yinguang. Recent advances in partial denitrification in biological nitrogen removal：From enrichment to application［J］. Bioresource Technology，2020，298：122444. doi:10.1016/j.biortech.2019.122444
29	WANG Depeng， ZHENG Qi， HUANG Kailong，et al. Metagenomic and metatranscriptomic insights into the complex nitrogen metabolic pathways in a single-stage bioreactor coupling partial denitrification with anammox［J］. Chemical Engineering Journal，2020，398：125653. doi:10.1016/j.cej.2020.125653
30	XU Xinxin， MA Bin， LU Wenkang，et al. Effective nitrogen removal in a granule-based partial-denitrification/anammox reactor treating low C/N sewage［J］. Bioresource Technology，2020，297：122467. doi:10.1016/j.biortech.2019.122467
31	ZHANG Yakun， XIONG Zhensheng， YANG Liming，et al. Successful isolation of a tolerant co-flocculating microalgae towards highly efficient nitrogen removal in harsh rare earth element tailings（REEs） wastewater［J］. Water Research，2019，166：115076. doi:10.1016/j.watres.2019.115076
32	詹鸿峰. 耐酸微藻的分离及其对南方离子型稀土矿山废水的处理特性研究［D］. 赣州：江西理工大学，2021.
	ZHAN Hongfeng. Isolation of acid-tolerant microalgae and its treatment characteristics for ionic rare earth mine wastewater in South China［D］. Ganzhou：Jiangxi University of Science and Technology，2021.
33	WANG Shiqi， GAO Bai， LIU Shengfeng，et al. Nitrogen removal performance and bacterial flora analysis of a nitrification-sulphur autotrophic denitrification coupled with permeable reaction wall（NSAD+PRW） treating rare earth mine groundwater［J］. Journal of Water Process Engineering，2023，55：104136. doi:10.1016/j.jwpe.2023.104136
34	SU Hao， ZHANG Dachao， ANTWI P，et al. Effects of heavy rare earth element（yttrium） on partial-nitritation process，bacterial activity and structure of responsible microbial communities［J］. Science of the Total Environment，2020，705：135797. doi:10.1016/j.scitotenv.2019.135797
35	SU Hao， ZHANG Dachao， ANTWI P，et al. Unraveling the effects of light rare-earth element〔Lanthanum（Ⅲ）〕 on the efficacy of partial-nitritation process and its responsible functional genera［J］. Chemical Engineering Journal，2021，408：127311. doi:10.1016/j.cej.2020.127311
36	SU Hao， ZHANG Dachao， ANTWI P，et al. Exploring potential impact（s） of cerium in mining wastewater on the performance of partial-nitrification process and nitrogen conversion microflora［J］. Ecotoxicology and Environmental Safety，2021，209：111796. doi:10.1016/j.ecoenv.2020.111796
37	XIAO Chunqiao， WAN Kai， HU Jinggang，et al. Performance changes in the anammox process under the stress of rare-earth element Ce（Ⅲ） and the evolution of microbial community and functional genes［J］. Bioresource Technology，2023，384：129349. doi:10.1016/j.biortech.2023.129349
38	SU Hao， ZHANG Dachao， ANTWI P，et al. Adaptation，restoration and collapse of anammox process to La（Ⅲ） stress：Performance，microbial community，metabolic function and network analysis［J］. Bioresource Technology，2021，325：124731. doi:10.1016/j.biortech.2021.124731
39	徐师，张大超，吴梦，等. 硫酸盐还原菌在处理酸性矿山废水中的应用［J］. 有色金属科学与工程，2018，9（1）：92-97.
	XU Shi， ZHANG Dachao， WU Meng，et al. Application of sulfate-reducing bacteria in treating acid mine wastewater［J］. Nonferrous Metals Science and Engineering，2018，9（1）：92-97.
40	徐师. 厌氧氨氧化处理离子型稀土矿山尾水中氨氮的实验研究［D］. 赣州：江西理工大学，2018.
	XU Shi. Experimental study on treatment of ammonia nitrogen in ionic rare earth mine tail water by anaerobic ammonia oxidation［D］. Ganzhou：Jiangxi University of Science and Technology，2018.
41	徐师，张大超，肖隆文，等. 厌氧氨氧化反应快速启动方法的研究进展［J］. 环境工程，2018，36（6）：18-21.
	XU Shi， ZHANG Dachao， XIAO Longwen，et al. Research progress on quick start-up process of the anaerobic ammonia oxidation process［J］. Environmental Engineering，2018，36（6）：18-21.
42	CHEN Xiang， LAI Cheng， WANG Xinyi，et al. High-rate partial denitrification via effluent residual nitrate controlling and microbial mechanism of nitrite accumulation by carbon dosage optimization［J］. Water Science and Technology，2022，86（5）：1222-1231. doi:10.2166/wst.2022.203
43	邓玉坤. 短程反硝化工艺对稀土矿山废水处理的中试研究［J］. 工业水处理，2024，44（8）：149-155.
	DENG Yukun. Pilot study on treatment of rare earth mine wastewater by partial denitrification［J］. Industrial Water Treatment，2024，44（8）：149-155.
44	赖城，周豪，张大超，等. 重稀土元素钇对短程反硝化工艺的影响［J］. 中国环境科学，2021，41（7）：3221-3228.
	LAI Cheng， ZHOU Hao， ZHANG Dachao，et al. Effect of heavy rare earth element yttrium on partial denitrification process［J］. China Environmental Science，2021，41（7）：3221-3228.
45	赖城. 稀土矿山氨氮尾水短程反硝化实验研究［D］. 赣州：江西理工大学，2021.
	LAI Cheng. Experimental study on short-range denitrification of ammonia nitrogen tail water in rare earth mines［D］. Ganzhou：Jiangxi University of Science and Technology，2021.
46	朱清江. 短程硝化—厌氧氨氧化工艺耐盐特性及处理稀土矿山氨氮废水研究［D］. 赣州：江西理工大学，2017.
	ZHU Qingjiang. Study on salt tolerance of short-cut nitrification-anaerobic ammonia oxidation process and treatment of ammonia nitrogen wastewater from rare earth mines［D］. Ganzhou：Jiangxi University of Science and Technology，2017.
47	ZHANG Dachao， SU Hao， ANTWI P，et al. High-rate partial-nitritation and efficient nitrifying bacteria enrichment/out-selection via pH-DO controls：Efficiency，kinetics，and microbial community dynamics［J］. Science of the Total Environment，2019，692：741-755. doi:10.1016/j.scitotenv.2019.07.308
48	张大超，苏昊，赖城，等. 一种离子型稀土矿废水处理装置：CN211847610U［P］. 2020-11-03.
49	SU Hao， DENG Yukun， ZHAO Jiejun，et al. Excellent，steady and economical nitrogen removal in highly variable mining wastewater via three-stage partial-denitrification/partial-nitrification/anammox system：A pilot-scale demonstration［J］. Journal of Water Process Engineering，2023，54：103896. doi:10.1016/j.jwpe.2023.103896
50	CHI Weili， YANG Hong， ZHANG Shude，et al. Nitrogen removal performance and bacterial flora analysis of a partial nitrification-anaerobic ammonium oxidation-denitrification system treating rare earth element tailings wastewater［J］. Journal of Environmental Chemical Engineering，2022，10（3）：107961. doi:10.1016/j.jece.2022.107961

[1]	黄声宇, 吴小琼, 赵全保, 霍惠雯. 吹脱法处理高浓度氨氮废水研究进展[J]. 工业水处理, 2024, 44(9): 31-40.
[2]	李亚峰, 伍健伯, 张驰. 厌氧氨氧化颗粒污泥形成的研究进展[J]. 工业水处理, 2024, 44(9): 23-30.
[3]	邓玉坤. 短程反硝化工艺对稀土矿山废水处理的中试研究[J]. 工业水处理, 2024, 44(8): 149-155.
[4]	谢健强, 张建美, 吕钰楠, 雷抗. 短程反硝化用于污水脱氮的机制、影响因素和工艺研究进展[J]. 工业水处理, 2024, 44(7): 19-28.
[5]	赵莹莹, 陈涛, 沈耀良, 刘文如. 硼对受高氨氮冲击后短程硝化系统效能恢复的影响研究[J]. 工业水处理, 2024, 44(6): 172-178.
[6]	陈浩, 杨玉婷, 刘文如, 沈耀良. 一体式短程反硝化-厌氧氨氧化工艺研究进展[J]. 工业水处理, 2024, 44(5): 14-23.
[7]	张受卫, 冀青杰, 李良浩, 陈周燕. 核电厂非放射性生产废水处理方案研究[J]. 工业水处理, 2024, 44(4): 205-209.
[8]	于雅楠, 张潇, 岳秀萍, 赵博玮, 周爱娟, 崔颖, 邢剑波. 不同粒径零价铁对微氧脱氮系统的影响[J]. 工业水处理, 2024, 44(4): 84-97.
[9]	骆子琛, 李星燃, 王建芳. 有机物对ANAMMOX性能及微生物影响的研究进展[J]. 工业水处理, 2024, 44(2): 39-47.
[10]	张建美, 朱永茂, 谢健强, 吕钰楠, 梅江雪, 蒋兴超. 一株适用于短程反硝化的细菌筛选及其脱氮特性[J]. 工业水处理, 2024, 44(2): 87-94.
[11]	罗佳欣, 张大超, 苏昊, 张润环. 厌氧氨氧化菌固定化技术及其研究进展[J]. 工业水处理, 2024, 44(11): 35-41.
[12]	顾晓扬, 汪晓军, 陈振国. 老龄垃圾渗滤液厌氧氨氧化处理工程运行效能分析[J]. 工业水处理, 2024, 44(11): 182-187.
[13]	陈圩, 杨萧帆, 王成刚, 邝乃强, 陈纯福, 张立秋. 沸石原位生物再生强化短程硝化处理高氨氮废水[J]. 工业水处理, 2024, 44(10): 165-173.
[14]	丁凡, 梁东博, 李东岳, 李朋, 李军, 陈筱秋. 游离亚硝酸预处理实现MBBR短程硝化的快速启动[J]. 工业水处理, 2023, 43(4): 113-120.
[15]	李芸, 熊星星, 崔楠, 黄志远. 短程反硝化的微生物富集策略及应用研究进展[J]. 工业水处理, 2023, 43(3): 39-47.

选择文件类型/文献管理软件名称

选择包含的内容