Feammox系统内氮素转化途径的研究

doi:10.11949/0438-1157.20191529

摘要/Abstract

摘要：

铁氨氧化（anaerobic ammonium oxidation coupled to Fe(Ⅲ) reduction，Feammox）是指在厌氧条件下，氨氮氧化耦合三价铁还原的一种新型污水生物脱氮工艺。为确定Feammox反应系统中存在的氮转化的途径，在厌氧条件下接种普通活性污泥驯化培养Feammox，探究了不同途径对氨氮转化的贡献率并进行了相关性分析。研究结果表明：在厌氧间歇反应器ASBR中，经过120 d的富集培养， $N H 4 + - N$ 最大去除率达53.8%，最大去除量约26.9 mg/L，其中Feammox反应途径对 $N H 4 + - N$ 去除的贡献率为57.7%，厌氧氨氧化(Anammox)约占42.3%。在典型周期分析发现，在0~7 h内对 $N H 4 + - N$ 去除量为14.74 mg/L，Anammox反应速率较快，起主导作用；7~24 h 对 $N H 4 + - N$ 去除量为12.16 mg/L，以Feammox反应为主；在整个运行周期内铁盐反硝化（nitrate-dependent Fe(Ⅱ) oxidizing，NDFO）去除 $N O 3 - - N$ 约5 mg/L。由相关性分析可得， $N H 4 + - N$ 浓度与Fe(Ⅲ)、 $N O 2 - - N$ 浓度呈显著性正相关（P_Fe<0.05、 $P N O 2$ <0.01），而 $N O 3 - - N$ 与Fe(Ⅲ)呈负相关（P<0.5）。实验结果表明在Feammox、Anammox以及NDFO共同作用下，该系统实现了污水自养型脱氮。

关键词: 活性污泥, 厌氧, Feammox, Anammox, NDFO, 相关性分析, 自养型脱氮, 分子生物学

Abstract:

Ferroammonium oxidation (anaerobic ammonium oxidation coupled to Fe (Ⅲ) reduction, Feammox) refers to a new type of sewage biological denitrification process under the condition of anaerobic, ammonia-nitrogen oxidation coupled with ferric iron reduction. To explore nitrogen conversion pathways and their contribution to nitrogen removal in Feammox, the activated sludge was used as seed sludge to acclimate. After 120 d of operation, the maximum conversion efficiency of $N H 4 + - N$ reached 53.8% and the maximum conversion amount was 26.9 mg/L, in which Feammox accounted for about 57.7% and Anammox about 42.3%. In typical cycle operation, nitrogen conversion was 14.74 mg/L within 0—7 h, in which Anammox dominated. During 7—24 h the nitrogen conversion was 12.16 mg/L, mainly by Feammox. The nitrate removal through NDFO during the whole operation was about 5 mg/L. Based on the correlation analysis, $N H 4 + - N$ concentration was significantly positively related to Fe(Ⅲ) and $N O 2 - - N$ (P_Fe<0.05, $P N O 2$ <0.01), while $N O 3 - - N$ was negatively related to Fe(Ⅲ) (P < 0.5). Synergy of Feammox, Anammox and NDFO achieved the autotrophic nitrogen removal from wastewater.

Key words: activated sludge, anaerobic, Feammox, Anammox, NDFO, correlation analysis, autotrophic nitrogen removal, molecular biology

中图分类号:

TQ 028.8

吴悦溪, 曾薇, 刘宏, 李健敏, 彭永臻. Feammox系统内氮素转化途径的研究[J]. 化工学报, 2020, 71(5): 2265-2272.

Yuexi WU, Wei ZENG, Hong LIU, Jianmin LI, Yongzhen PENG. Exploration of nitrogen transformation pathway in Feammox[J]. CIESC Journal, 2020, 71(5): 2265-2272.

图/表 11

表1 氧化还原反应式标准吉布斯自由能变化

Table 1 ΔGθ of probable redox reaction

反应类型	反应方程式	ΔG^θ/(kJ/mol)	可能性
异化铁还原	$F e O O H + 3 H + + e - → F e 2 + + H 2 O$	-64.6	可能
Anammox	$N H 4 + + N O 2 - → N 2 + 2 H 2 O$	-335.0	可能
Feammox	$N H 4 + + 6 F e 3 + + 2 H 2 O → N O 2 - + 6 F e 2 + + 8 H +$	-24.3	可能
NDFO	$10 F e 2 + + 2 N O 3 - + 24 H 2 O → 10 F e (O H) 3 + N 2 + 18 H +$	-75.9	可能

表1 氧化还原反应式标准吉布斯自由能变化

Table 1 ΔGθ of probable redox reaction

反应类型	反应方程式	ΔG^θ/(kJ/mol)	可能性
异化铁还原	$F e O O H + 3 H + + e - → F e 2 + + H 2 O$	-64.6	可能
Anammox	$N H 4 + + N O 2 - → N 2 + 2 H 2 O$	-335.0	可能
Feammox	$N H 4 + + 6 F e 3 + + 2 H 2 O → N O 2 - + 6 F e 2 + + 8 H +$	-24.3	可能
NDFO	$10 F e 2 + + 2 N O 3 - + 24 H 2 O → 10 F e (O H) 3 + N 2 + 18 H +$	-75.9	可能

图1 ASBR反应器结构图1—进水管；2—排水管；3—排气孔；4—pH计；5—DO计；6—水浴；7—搅拌桨

Fig.1 Schematic diagram of ASBR reactor

图2 批次实验装置图1—取样口；2—pH计；3—排气孔

Fig.2 Experimental device for batch tests

表2 模拟废水成分(Ⅰ)

Table 2 Simulating wastewater composition(Ⅰ)

模拟废水常量元素	浓度/(mg/L)	模拟废水常量元素	浓度/(mg/L)
$N H 4 + - N$	50±5	NaHCO₃	500
Fe(Ⅲ)	30±3	KH₂PO₄	30
$N O 2 -$ -N(70~100 d)	5	CaCl₂	136
$N O 2 -$ -N(100~120 d)	10	MgCl₂·7H₂O	200

表2 模拟废水成分(Ⅰ)

Table 2 Simulating wastewater composition(Ⅰ)

模拟废水常量元素	浓度/(mg/L)	模拟废水常量元素	浓度/(mg/L)
$N H 4 + - N$	50±5	NaHCO₃	500
Fe(Ⅲ)	30±3	KH₂PO₄	30
$N O 2 -$ -N(70~100 d)	5	CaCl₂	136
$N O 2 -$ -N(100~120 d)	10	MgCl₂·7H₂O	200

表3 模拟废水成分(Ⅱ)

Table 3 Simulating wastewater composition(Ⅱ)

模拟废水

微量元素

浓度/(mg/L)

模拟废水

微量元素

Na₂MoO₄·2H₂O

ZnSO₄·7H₂O

NiCl₂·6H₂O

CoCl₂·6H₂O

H₃BO₄

图3 Feammox反应器进出水氮素及铁形态动态变化

Fig.3 Nitrogen and iron transformation in Feammox reaction

图4 典型周期内氮、铁元素转化特性

Fig.4 Transformation characteristics of nitrogen and iron in typical cycles

图5 N-Fe循环途径

Fig.5 Circulation way of N-Fe

图6 Anammox验证实验

Fig.6 Anammox validation test

图7 NDFO验证实验

Fig.7 NDFO validation test

图8 Feammox各指标相关性

Fig.8 Correlation analyses of each index in Feammox reaction

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