Research progress on the effects of iron on microbiological nitrogen removal in wastewater

doi:10.16085/j.issn.1000-6613.2019-0909

Abstract

Abstract:

Microbiological nitrogen removal is an economical and effective method for nitrogen pollution control in water. Microbial nitrogen removal processes, at present, mainly contain anammox, nitrification, denitrification, simultaneous nitrification and denitrification and so on. Iron is a ubiquitous metallic element in environment and also one of the important trace elements for microorganisms. In microbiological nitrogen removal systems, the addition of iron salts or iron-containing solid compounds will have certain impacts on microorganisms and the nitrogen removal processes, and such impacts of iron differ for different microorganisms and nitrogen removal processes. Here, the effects of iron on the removal of nitrogen-containing pollutants by different nitrogen removal processes including anammox, nitrification, denitrification and simultaneous nitrification and denitrification, as well as the relationship between iron and enzyme activity, electron transfer, proliferation and enrichment of nitrogen removal microorganisms , and formation of biofilm, floc and granule in biological reactor for nitrogen removal, are comprehensively reviewed. This will help to comprehensively understand about the role of iron in microbial nitrogen removal systems and the mechanism involved, and provide a reference for the enhancement of microbial denitrification processes and improvement of microbial denitrification efficiency by the addition of iron.

Key words: iron, microbiological nitrogen removal, process enhancement, mechanism of impact

摘要：

微生物脱氮是一种经济有效的治理水体氮污染的手段。目前微生物脱氮过程主要有厌氧氨氧化、硝化、反硝化及同时硝化反硝化等。铁是环境中普遍存在的金属元素，也是微生物所需的重要微量元素之一。在微生物脱氮系统中，铁盐或者含铁固体化合物等的投加会对微生物及脱氮工艺过程等产生一定的影响，且对于不同种类的微生物与不同的脱氮工艺，铁所产生的影响也将不同。本文全面综述了近些年的研究报道中铁对厌氧氨氧化、硝化、反硝化及同时硝化反硝化等不同脱氮过程中含氮污染物去除效果的影响，铁与脱氮微生物的酶活性、电子传递、增殖富集及脱氮反应器中生物膜、污泥絮体及颗粒形成等之间的作用关系，旨在全面理解铁对微生物脱氮系统的作用与内在机制，为实现利用铁强化微生物脱氮过程、提高微生物脱氮效率提供借鉴。

关键词: 铁, 微生物脱氮, 过程强化, 作用机制

CLC Number:

Ran LÜ,Bin LI,Ying XIAO,Jingwen ZHANG,Yuliang MAI. Research progress on the effects of iron on microbiological nitrogen removal in wastewater[J]. Chemical Industry and Engineering Progress, 2020, 39(2): 709-719.

吕冉,李彬,肖盈,张靖雯,麦裕良. 铁对废水微生物脱氮的影响研究进展[J]. 化工进展, 2020, 39(2): 709-719.

Figures/Tables 5

投加形式	投加量	厌氧氨氧化菌/污泥	反应器（有效容积）	对脱氮效果的影响	参考文献
毫米级零价铁mZVI；纳米级零价铁nZVI	25g	城市污水处理厂厌氧池收集的污泥	上流式厌氧污泥床反应器（4.75L）	氮负荷率约630mg/(L·d)。稳定阶段，投加mZVI、nZVI和不投加铁，总氮去除速率分别为543mg/(L·d)、560mg/(L·d)和532mg/(L·d)；氨氮去除率分别为92.6%、93.8%和91.8%；亚硝酸盐氮去除率分别为93.5%、96.6%和91.2%	[8]
Fe(Ⅱ)（EDTA-FeNa₂）	0.06～0.18 mmol/L	实验室规模厌氧氨氧化反应器污泥，70%～75%厌氧氨氧化菌KSU-1	上流式固定床反应器（0.3L）	氮负荷率为5590g/(m³·d)时，0.06mmol/L及0.09mmol/L Fe(Ⅱ)对脱氮均有促进作用，氮去除速率由对照组[0.03mmol/L Fe(Ⅱ)]的3349g/(m³·d)提高至4429g/(m³·d)[0.09mmol/L Fe(Ⅱ)]。氮负荷率为12500g/(m³·d)时，氮去除速率由7033g/(m³·d)[0.03mmol/L Fe(Ⅱ)]提高至0.12 mmol/L Fe(Ⅱ)时的9135g/(m³·d)，0.18mmol/L Fe(Ⅱ)时氮去除速率降至8198g/(m³·d)	[13]
Fe²⁺	1mg/L	CANON反应器污泥与生物滤池生物膜的混合污泥	生物滤池（1L）	进水总氮约105mg/L。在Fe²⁺的长期作用下，氮的去除速率由最初投加Fe²⁺时的约0.51kg/(m³·d)最终增至0.58kg/(m³·d)	[14]
Fe²⁺	1～50mg/L	厌氧氨氧化与硝化污泥污泥混合	生物滤池（1L）	进水氨氮与亚硝酸盐氮各50mg/L。未投加Fe²⁺时，总氮去除速率为0.51kg/(m³·d)；氨氮、亚硝酸盐氮与总氮去除率分别为58.9%、60.9%和58.2%。1～5mg/LFe²⁺能够促进脱氮，总氮去除速率增至0.57kg/(m³·d)；氨氮、亚硝酸盐氮与总氮去除率分别增至94.4%、93.0%和80.8%。10～50mg/LFe²⁺则会不同程度地抑制脱氮	[15]
Fe³⁺	3.68mg/L	稳定运行的实验室规模反应器中污泥	上流式厌氧污泥反应器（1L）	进水氨氮125.9～168.3mg/L，亚硝酸盐氮149.0～182.5mg/L。添加Fe³⁺时的平均氮去除率和最大氮去除速率分别为67.4%和4.9kg/(m³·d)[对照组相应值分别为64.7%和4.1kg/(m³·d)]	[16]
Fe₃O₄	2g	实验室规模上流式厌氧污泥床反应器的厌氧氨氧化污泥	厌氧连续搅拌反应器（2L）	进水氨氮和亚硝酸盐浓度分别为100.5mg/L和132.1mg/L。反应器稳定运行阶段，最大总氮去除率约98%，大于对照组约87%	[17]
Fe电极（阳极） (?60mm×90mm)		上流式厌氧氨氧化反应器污泥	上流式厌氧反应器（0.7L）	进水氨氮和亚硝酸盐氮浓度均为650mg/L。氨氮、亚硝酸盐氮和总氮去除速率分别为609.9mg/(L·d)、638.4mg/(L·d)和1209.6mg/(L·d)；未设Fe-石墨电极的对照组中相应值分别仅为493.9mg/(L·d)、524.2mg/(L·d)和973.3mg/(L·d)	[18]

投加形式	投加量	厌氧氨氧化菌/污泥	反应器（有效容积）	对脱氮效果的影响	参考文献
毫米级零价铁mZVI；纳米级零价铁nZVI	25g	城市污水处理厂厌氧池收集的污泥	上流式厌氧污泥床反应器（4.75L）	氮负荷率约630mg/(L·d)。稳定阶段，投加mZVI、nZVI和不投加铁，总氮去除速率分别为543mg/(L·d)、560mg/(L·d)和532mg/(L·d)；氨氮去除率分别为92.6%、93.8%和91.8%；亚硝酸盐氮去除率分别为93.5%、96.6%和91.2%	[8]
Fe(Ⅱ)（EDTA-FeNa₂）	0.06～0.18 mmol/L	实验室规模厌氧氨氧化反应器污泥，70%～75%厌氧氨氧化菌KSU-1	上流式固定床反应器（0.3L）	氮负荷率为5590g/(m³·d)时，0.06mmol/L及0.09mmol/L Fe(Ⅱ)对脱氮均有促进作用，氮去除速率由对照组[0.03mmol/L Fe(Ⅱ)]的3349g/(m³·d)提高至4429g/(m³·d)[0.09mmol/L Fe(Ⅱ)]。氮负荷率为12500g/(m³·d)时，氮去除速率由7033g/(m³·d)[0.03mmol/L Fe(Ⅱ)]提高至0.12 mmol/L Fe(Ⅱ)时的9135g/(m³·d)，0.18mmol/L Fe(Ⅱ)时氮去除速率降至8198g/(m³·d)	[13]
Fe²⁺	1mg/L	CANON反应器污泥与生物滤池生物膜的混合污泥	生物滤池（1L）	进水总氮约105mg/L。在Fe²⁺的长期作用下，氮的去除速率由最初投加Fe²⁺时的约0.51kg/(m³·d)最终增至0.58kg/(m³·d)	[14]
Fe²⁺	1～50mg/L	厌氧氨氧化与硝化污泥污泥混合	生物滤池（1L）	进水氨氮与亚硝酸盐氮各50mg/L。未投加Fe²⁺时，总氮去除速率为0.51kg/(m³·d)；氨氮、亚硝酸盐氮与总氮去除率分别为58.9%、60.9%和58.2%。1～5mg/LFe²⁺能够促进脱氮，总氮去除速率增至0.57kg/(m³·d)；氨氮、亚硝酸盐氮与总氮去除率分别增至94.4%、93.0%和80.8%。10～50mg/LFe²⁺则会不同程度地抑制脱氮	[15]
Fe³⁺	3.68mg/L	稳定运行的实验室规模反应器中污泥	上流式厌氧污泥反应器（1L）	进水氨氮125.9～168.3mg/L，亚硝酸盐氮149.0～182.5mg/L。添加Fe³⁺时的平均氮去除率和最大氮去除速率分别为67.4%和4.9kg/(m³·d)[对照组相应值分别为64.7%和4.1kg/(m³·d)]	[16]
Fe₃O₄	2g	实验室规模上流式厌氧污泥床反应器的厌氧氨氧化污泥	厌氧连续搅拌反应器（2L）	进水氨氮和亚硝酸盐浓度分别为100.5mg/L和132.1mg/L。反应器稳定运行阶段，最大总氮去除率约98%，大于对照组约87%	[17]
Fe电极（阳极） (?60mm×90mm)		上流式厌氧氨氧化反应器污泥	上流式厌氧反应器（0.7L）	进水氨氮和亚硝酸盐氮浓度均为650mg/L。氨氮、亚硝酸盐氮和总氮去除速率分别为609.9mg/(L·d)、638.4mg/(L·d)和1209.6mg/(L·d)；未设Fe-石墨电极的对照组中相应值分别仅为493.9mg/(L·d)、524.2mg/(L·d)和973.3mg/(L·d)	[18]

铁投加形式及投加量	反应器类型（有效容积）	细菌或污泥	硝酸盐氮初始浓度	硝酸盐氮还原速率	参考文献
ZVI，2g	瓶子（0.25L）	铁还原菌CC76	15mg/L	0.28mg/(L·h)	[33]
还原铁粉（200目），每10天添加一次，投加量为10g	升流式厌氧反应器（4L）	实验室培养的自养型亚硝化污泥	平均 101.84mg/L	29.3g/(m³·d)	[34]
Fe²⁺，Fe/N摩尔比为2	血清瓶（0.1L）	实验室规模高负荷脱氮反应器中反硝化颗粒污泥	98.89mg/L	27.59mg/(g VSS·d)	[31]
Fe²⁺，约30mg/L（与约70mg/L的Mn²⁺共存）	血清瓶（0.25L）	假单胞菌H117	约17mg/L	0.2153mg/(L·h)	[35]
Fe²⁺，800mg/L；或Fe(Ⅱ) [Fe(Ⅱ)EDTA)，1500mg/L]	上流式生物滤池反应器（4.71L）	微杆菌属W5	约30mg/L	—	[36]
Fe²⁺，约1250～1600mg/L	上流式厌氧污泥床反应器（0.8L）	用于处理造纸废水的大型上流式厌氧污泥床反应器中厌氧颗粒污泥	约106～ 112mg/L	0.073kg/(m³·d)	[37]
Fe(OH)₂或FeS，电子供体/电子受体摩尔比为2	密闭玻璃瓶（0.3L）	污水处理厂厌氧消化池污泥	50mg/L	8.16mmol/(L·d) 或1.37mmol/(L·d)	[38]
Fe(OH)₂、FeS和S⁰共同作电子供体，总电子供体/受体物质的量之比1.15	上流式厌氧污泥床反应器（4L）	污水处理厂厌氧消化池污泥	50mg/L	7.01mmol/(L·d)	[38]
黄铁矿FeS₂	聚丙烯瓶（0.05L）	脱氮硫杆菌	2.46mmol/L	0.54mmol/(kg_pyrite·d)	[39]
磁黄铁矿Fe_1-_xS（x=0～0.125）	上流式生物滤池反应器（1.8L）	从厌氧污泥中富集的自养反硝化菌	21.11mg/L	19.22mg/(L·d)	[40]
菱铁矿FeCO₃	上流式生物滤池反应器（0.2417L）	弗氏柠檬酸杆菌PXL1	150mg/L	127.4～209.9mg/(kg_siderite·d)	[41]
零价铁屑（同碳合成IC-ME载体材料）	玻璃瓶（与IC-ME耦合）（0.5L）	煤化工废水处理厂氧化池污泥	90～98 mg/L	—	[42]

微生物脱氮过程	化学反应方程式	参考文献
厌氧氨氧化	$2 F e 2 + + 2 H + + N O 3 - → 2 F e 3 + + H 2 O + N O 2 -$	[8,17,52]
	$6 F e 3 + + 2 H 2 O + N H 4 + → 6 F e 2 + + 8 H + + N O 2 -$
	$3 F e (O H) 3 + 5 H + + N H 4 + → 3 F e 2 + + 9 H 2 O + 0.5 N 2$
	$6 F e (O H) 3 + 10 H + + N H 4 + → 6 F e 2 + + 16 H 2 O + N O 2 -$
	$8 F e (O H) 3 + 14 H + + N H 4 + → 8 F e 2 + + 21 H 2 O + N O 3 -$
	$N H 4 + + 1.32 N O 2 - + 0.066 H C O 3 - + 0.13 H + → 1.02 N 2 + 0.26 N O 3 - + 0.066 C H 2 O 0.5 N 0.15 + 2.03 H 2 O$
	$4 F e 0 + 10 H + + N O 3 - → 4 F e 2 + + 3 H 2 O + N H 4 +$
氢自养反硝化	$F e 0 + 2 H 2 O → F e 2 + + H 2 + 2 O H -$	[29]
	$0.33 N O 3 - + H 2 + 0.08 C O 2 + 0.34 H + → 0.015 C 5 H 7 O 2 N + 0.16 N 2 + 1.11 H 2 O$
铁型反硝化	$5 F e 0 + 12 H + + 2 N O 3 - → 5 F e 2 + + 6 H 2 O + N 2$	[31,32,33,38,39]
	$10 F e 2 + + 24 H 2 O + 2 N O 3 - → 10 F e (O H) 3 + 18 H + + N 2$
	$6 F e 2 + + 14 H 2 O + 2 N O 2 - → 6 F e (O H) 3 + 10 H + + N 2$
	$10 F e S + 16 H 2 O + 18 N O 3 - → 10 F e (O H) 3 + 10 S O 4 2 - + 2 H + + 9 N 2$
	$10 F e (O H) 2 + 6 H 2 O + 2 N O 3 - → 10 F e (O H) 3 + 2 O H - + N 2$
	$5 F e 2 S + 10 H 2 O + 15 N O 3 - → 5 F e (O H) 3 + 10 S O 4 2 - + 5 H + + 152 N 2$
	$10 F e C O 3 + 24 H 2 O + 2 N O 3 - → 10 F e (O H) 3 + 10 H C O 3 - + 8 H + + N 2$

微生物脱氮过程	化学反应方程式	参考文献
厌氧氨氧化	$2 F e 2 + + 2 H + + N O 3 - → 2 F e 3 + + H 2 O + N O 2 -$	[8,17,52]
	$6 F e 3 + + 2 H 2 O + N H 4 + → 6 F e 2 + + 8 H + + N O 2 -$
	$3 F e (O H) 3 + 5 H + + N H 4 + → 3 F e 2 + + 9 H 2 O + 0.5 N 2$
	$6 F e (O H) 3 + 10 H + + N H 4 + → 6 F e 2 + + 16 H 2 O + N O 2 -$
	$8 F e (O H) 3 + 14 H + + N H 4 + → 8 F e 2 + + 21 H 2 O + N O 3 -$
	$N H 4 + + 1.32 N O 2 - + 0.066 H C O 3 - + 0.13 H + → 1.02 N 2 + 0.26 N O 3 - + 0.066 C H 2 O 0.5 N 0.15 + 2.03 H 2 O$
	$4 F e 0 + 10 H + + N O 3 - → 4 F e 2 + + 3 H 2 O + N H 4 +$
氢自养反硝化	$F e 0 + 2 H 2 O → F e 2 + + H 2 + 2 O H -$	[29]
	$0.33 N O 3 - + H 2 + 0.08 C O 2 + 0.34 H + → 0.015 C 5 H 7 O 2 N + 0.16 N 2 + 1.11 H 2 O$
铁型反硝化	$5 F e 0 + 12 H + + 2 N O 3 - → 5 F e 2 + + 6 H 2 O + N 2$	[31,32,33,38,39]
	$10 F e 2 + + 24 H 2 O + 2 N O 3 - → 10 F e (O H) 3 + 18 H + + N 2$
	$6 F e 2 + + 14 H 2 O + 2 N O 2 - → 6 F e (O H) 3 + 10 H + + N 2$
	$10 F e S + 16 H 2 O + 18 N O 3 - → 10 F e (O H) 3 + 10 S O 4 2 - + 2 H + + 9 N 2$
	$10 F e (O H) 2 + 6 H 2 O + 2 N O 3 - → 10 F e (O H) 3 + 2 O H - + N 2$
	$5 F e 2 S + 10 H 2 O + 15 N O 3 - → 5 F e (O H) 3 + 10 S O 4 2 - + 5 H + + 152 N 2$
	$10 F e C O 3 + 24 H 2 O + 2 N O 3 - → 10 F e (O H) 3 + 10 H C O 3 - + 8 H + + N 2$

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