Experimental study on effective nitrate removal from sewage by ZVI-based catalyzed reduction

doi:10.11949/j.issn.0438-1157.20181059

Abstract

Abstract:

It remains difficult to achieve effective nitrate removal with conventional biological nitrogen removal processes, for the high $N O 3 -$ -N concentration and low organic carbon in tail water from WWTP. Thus, ZVI-based catalyzed reduction was developed and applied in this study. The influence of catalytic activity of the catalysts, pH and $N O 3 -$ -N concentration on nitrate reduction by ZVI-based catalyzed reduction was studied, and the reaction mechanisms was investigated. The results show that the high-catalytic catalytic denitrification carrier with catalyst D can remove 92.23% of $N O 3 -$ -N, and the $N O 3 -$ -N removal rate can reach 92.09% when the wastewater is acidic to neutral. The $N O 3 -$ -N removal efficiency of above 86.13% was also achieved even under alkaline conditions, and no $N H 4 +$ -N accumulation was found. Increasing in $N O 3 -$ -N concentration (20—70 mg·L^–1) showed little impact on nitrate reduction efficiency (remaining ≥96.11%). The nitrogen removal efficiency by ZVI-based catalyzed reduction in the presence of catalyst D obtained the highest speed when compared to catalysts A, B and C, and the reduction reaction was in keeping with the first-order kinetics equation with a calculated reaction rate constant of k=0.0170 min^–1.

Key words: tail water from WWTP, nitrate, zero-valent iron (ZVI), ZVI-based carrier, catalyst, bimetallic, catalytzed reduction, reaction kinetics

摘要：

污水厂排水中硝酸盐氮( $N O 3 –$ -N)浓度偏高，难利用常规生物脱氮工艺实现 $N O 3 –$ -N的深度脱除。以铁基质高效催化脱氮载体为污水中 $N O 3 –$ -N的脱除材料，探究不同铁基质催化活性、pH和 $N O 3 –$ -N浓度等对污水中 $N O 3 –$ -N去除的影响及机制。研究结果表明：添加催化剂D的铁基质高效催化脱氮载体可脱除92.23%的 $N O 3 –$ -N，调节污水为酸性至中性条件时，其 $N O 3 –$ -N去除率均可达到92.09%以上，且氨氮( $N H 4 +$ -N)积累量先升高后降低；当污水为碱性条件时， $N O 3 –$ -N的去除率亦可达86.13%以上，且在碱性条件时无 $N H 4 +$ -N积累；原水中 $N O 3 –$ -N的浓度变化(20~70 mg·L^-1)对铁基质高效催化脱氮载体的脱氮性能影响较小， $N O 3 –$ -N去除率均达到96.11%以上。与催化剂A、B和C相比，添加催化剂D的铁基质高效催化脱氮载体脱氮速率最快， $N O 3 –$ -N降解反应过程符合一级反应动力学方程，反应速率常数k=0.0170 min^–1。

关键词: 污水厂排水, 硝酸盐氮, 零价铁, 铁基质高效催化脱氮载体, 催化剂, 双金属, 催化还原, 反应动力学

CLC Number:

X 703

Desheng LI, Chao ZHANG, Shihai DENG, Zhifeng HU, Jinlong LI, Yuanhui LIU. Experimental study on effective nitrate removal from sewage by ZVI-based catalyzed reduction[J]. CIESC Journal, 2019, 70(3): 1065-1074.

李德生, 张超, 邓时海, 胡智丰, 李金龙, 刘元辉. 基于铁基质高效催化还原污水中硝酸盐氮的实验研究[J]. 化工学报, 2019, 70(3): 1065-1074.

Figures/Tables 9

Fig.1 Surface property and inner constucture of ZVI-based carriers

Fig.2 Schematic diagram of experimental equipment

Table 1 Types of carriers and conditions of water quality in different groups

Treatment	Specie	$N H 4 +$ -N/(mg·L^–1)	$N O 3 -$ -N/(mg·L^–1)	pH	$N O 3 -$ -N removal ratio/%
1	carrier O	4.9±1.0	15.1±1.0	7.0±0.2	45.65
2	carrier A	4.9±1.0	15.1±1.0	7.0±0.2	80.49
3	carrier B	4.9±1.0	15.1±1.0	7.0±0.2	75.74
4	carrier C	4.9±1.0	15.1±1.0	7.0±0.2	47.93
5	carrier D	4.9±1.0	15.1±1.0	7.0±0.2	92.23
6	carrier D	5.0±1.0	15.0±1.0	3.0±0.1	94.97
7	carrier D	5.0±1.0	15.0±1.0	5.0±0.1	94.96
8	carrier D	5.0±1.0	15.0±1.0	7.0±0.2	92.09
9	carrier D	5.0±1.0	15.0±1.0	9.0±0.1	86.61
10	carrier D	5.0±1.0	15.0±1.0	11.0±0.1	86.13
11	carrier D	4.9±1.0	20.0±1.0	7.0±0.2	99.64
12	carrier D	4.9±1.0	30.0±1.0	7.0±0.2	98.76
13	carrier D	4.9±1.0	50.0±1.0	7.0±0.2	97.46
14	carrier D	4.9±1.0	70.0±1.0	7.0±0.2	96.11

Table 1 Types of carriers and conditions of water quality in different groups

Treatment	Specie	$N H 4 +$ -N/(mg·L^–1)	$N O 3 -$ -N/(mg·L^–1)	pH	$N O 3 -$ -N removal ratio/%
1	carrier O	4.9±1.0	15.1±1.0	7.0±0.2	45.65
2	carrier A	4.9±1.0	15.1±1.0	7.0±0.2	80.49
3	carrier B	4.9±1.0	15.1±1.0	7.0±0.2	75.74
4	carrier C	4.9±1.0	15.1±1.0	7.0±0.2	47.93
5	carrier D	4.9±1.0	15.1±1.0	7.0±0.2	92.23
6	carrier D	5.0±1.0	15.0±1.0	3.0±0.1	94.97
7	carrier D	5.0±1.0	15.0±1.0	5.0±0.1	94.96
8	carrier D	5.0±1.0	15.0±1.0	7.0±0.2	92.09
9	carrier D	5.0±1.0	15.0±1.0	9.0±0.1	86.61
10	carrier D	5.0±1.0	15.0±1.0	11.0±0.1	86.13
11	carrier D	4.9±1.0	20.0±1.0	7.0±0.2	99.64
12	carrier D	4.9±1.0	30.0±1.0	7.0±0.2	98.76
13	carrier D	4.9±1.0	50.0±1.0	7.0±0.2	97.46
14	carrier D	4.9±1.0	70.0±1.0	7.0±0.2	96.11

Fig.3 Changes of concentrations of NO3--N (a), NH4+-N (b) and NO2--N (c) under various catalysts

Fig.4 Effects of pH on nitrate removal under catalytic carrier D

Fig.5 Proportions of various nitrogen in 360 min under different pH

Fig.6 Effects of NO3–-N concentration in inlet on NO3–-N removal efficiency

Fig.7 Linear regression analysis of catalytic carrier O under various reaction orders

Fig.8 Linear regression analysis of catalytic carrier D under various reaction order

References 30

1	修瑞瑞, 何世颖, 宋海亮, 等. 改性硅藻土负载纳米零价铁去除水中硝酸盐氮 [J]. 化工学报, 2016, 67(9): 3888-3894.
	XiuR R, HeS Y, SongH L, et al. Removal of nitrate nitrogen by nanoscale zero-valent iron supported on modified diatomite [J]. CIESC Journal, 2016, 67(9): 3888-3894.
2	李德生, 胡倩怡, 崔玉玮, 等. 化学催化法脱除模拟地下水中硝酸盐氮 [J]. 化工学报, 2015, 66(6): 2288-2294.
	LiD S, HuQ Y, CuiY W, et al. Chemical catalytic method for removal of nitrate nitrogen in simulated groundwater [J]. CIESC Journal, 2015, 66(6): 2288-2294.
3	BertinA, InostrozaP A, QuiñonesR A. A theoretical estimation of the concentration of steroid estrogens in effluents released from municipal sewage treatment plants into aquatic ecosystems of central-southern Chile [J]. Science of the Total Environment, 2009, 407(17): 4965-4971.
4	孙向辉, 李力. 水体富营养化及其植物修复技术研究进展 [J]. 安徽农业科学, 2014, 42(18): 5902-5905.
	SunX H, LiL. Research progress on eutrofication of water system and phytoremediation [J]. Journal of Anhui Agricultural Sciences, 2014, 42(18): 5902-5905.
5	张自杰. 排水工程: 下册[M]. 4版. 北京：中国建筑工业出版社, 2000: 308-312.
	ZhangZ J. Drainage Engineering: Volume Ⅱ[M]. 4th ed. Beijing: China Architecture & Building Press, 2000: 308-312.
6	谢荣, 赵博玮, 李建政, 等. 木质填料床A/O系统处理低C/N比养猪废水的效能与脱氮机制 [J]. 化工学报, 2015, 66(11): 4661-4668.
	XieR, ZhaoB W, LiJ Z, et al. Treatment of piggery wastewater with low C/N ratio and mechanism for denitrification in wood-packed-bed A/O process [J]. CIESC Journal, 2015, 66(11): 4661-4668.
7	WisniewskiC, PersinF, CherifT, et al. Denitrification of drinking water by the association of an electrodialysis process and a membrane bioreactor: feasibility and application [J]. Desalination, 2001, 139(1): 199-205.
8	杨朗, 李志丰. 低浓度氨氮废水的离子交换法脱氮 [J]. 环境工程学报, 2012, 6(8): 2715-2719.
	YangL, LiZ F. Ammonia-nitrogen removal from low concentration wastewater by ion exchange[J]. Chinese Journal of Environmental Engineering, 2012, 6(8): 2715-2719.
9	迟峰. 反渗透法脱除地下水中硝酸盐的研究 [D]. 上海: 华东理工大学, 2011.
	ChiF. The research on nitrate removal from groundwater by reverse osmosis[D]. Shanghai: East China University of Science and Technology, 2011.
10	张立辉, 曹国民, 盛梅, 等. 地下水硝酸盐去除技术进展 [J]. 净水技术, 2010, 29(5): 4-10.
	ZhangL H, CaoG M, ShengM, et al. Progress of the technological processes for nitrate removal in groundwater [J]. Water Purification Technology, 2010, 29(5): 4-10.
11	俞勇, 方建, 喻盛华. 硝化/反硝化滤池用于反渗透浓水处理的设计和调试 [J]. 中国给水排水, 2017, 33(18): 135-138.
	YuY, FangJ, YuS H. Design and commissioning of nitrification/denitrification filter in reverse osmosis brine treatment [J]. China Water & Wastewater, 2017, 33(18): 135-138.
12	张星星, 孟凡生, 王业耀, 等. 零价铁修复硝酸盐污染地下水的影响因素[J]. 环境工程, 2010, 28(s1): 70-73.
	ZhangX X, MengF S, WangY Y, et al. Research on influencing factors of nitrate removal of groundwater by ZVI [J]. Environmental Engineering, 2010, 28(s1): 70-73.
13	范潇梦, 关小红, 马军. 零价铁还原水中硝酸盐的机理及影响因素 [J]. 中国给水排水, 2008, 24(14): 5-9.
	FanX M, GuanX H, MaJ. Mechanisms and affecting factors of nitrate reduction by zero-valent iron. [J]. China Water & Wastewater, 2008, 24(14): 5-9.
14	ChenY M, LiC W, ChenS S. Fluidized zero valent iron bed reactor for nitrate removal [J]. Chemosphere, 2005, 59(6): 753-759.
15	ChoeS, LiljestrandH M, KhimJ. Nitrate reduction by zero-valent iron under different pH regimes [J]. Applied Geochemistry, 2004, 19(3): 335-342.
16	肖晶晶, 郭萍, 霍炜洁, 等. 反硝化微生物在污水脱氮中的研究及应用进展 [J]. 环境科学与技术, 2009, 32(12): 97-102.
	XiaoJ J, GuoP, HuoW J, et al. Application of denitrifying microbes to wastewater denitrification [J]. Environmental Science & Technology, 2009, 32(12): 97-102.
17	李铁龙, 刘海水, 金朝晖, 等. 纳米铁去除水中硝酸盐氮的批实验 [J]. 吉林大学学报, 2006, 36(2): 264-268.
	LiT L, LiuH S, JinZ H, et al. Batch experiment on reduction of nitrate in water by nanoscale zero valent iron carriers [J]. Journal of Jilin University, 2006, 36(2): 264-268.
18	郑西来, 唐凤琳, 辛佳, 等. 污染地下水零价铁原位反应带修复技术: 理论·应用·展望 [J]. 环境科学研究, 2016, 29(2): 155-163.
	ZhengX L, TangF L, XinJ, et al. Development of a zero-valent iron-based in-situ reactive zones technique for remediation of contaminated groundwater [J]. Research of Environmental Sciences, 2016, 29(2): 155-163.
19	LiaoC H, KangS F, HsuY W. Zero-valent iron reduction of nitrate in the presence of ultraviolet light, organic matter and hydrogen peroxide [J]. Water Research, 2003, 37(17): 4109-4118.
20	ZhouJ, DuanS H, ChenY, et al. Nitrogen removal efficiency of iron-carbon micro-electrolysis system treating high nitrate nitrogen organic pharmaceutical wastewater [J]. Journal of Central South University, 2009, 16(s1): 368-373.
21	KeumY S, LiQ X. Reduction of nitroaromatic pesticides with zero-valent iron [J]. Chemosphere, 2004, 54(3): 255-263.
22	李德生. 好氧低碳氮比污水氨氮直接脱氮生物载体及制备方法: 103145234A[P]. 2013-06-12.
	LiD S. Biological particulate carrier and its preparation method directly disposing ammonia nitrogen fromaerobic low carbon nitrogen ratio wastewater: 103145234A[P]. 2013-06-12.
23	国家环境保护总局. 水和废水监测分析方法[M]. 4版. 北京: 中国环境科学出版社, 2002: 258-284.
	The Environmental Protection Agency of State. The Monitoring and Analysis Methods of Water and Wastewater [M]. 4th ed. Beijing: China Environmental Science Press, 2002: 258-284.
24	HuangY H, ZhangT C. Nitrite reduction and formation of corrosion coatings in zerovalent iron systems [J]. Chemosphere, 2006, 64(6): 937-943.
25	邓时海, 李德生, 卢阳阳, 等. 集成模块系统同步硝化反硝化处理低碳氮比污水的试验 [J]. 中国环境科学, 2014, 34(9): 2259-2265.
	DengS H, LiD S, LuY Y, et al. Performance characteristics of simultaneous nitrification and denitrification (SND) for low carbon to nitrogen (C/N) ratio wastewater in an integrated device [J] China Environmental Science, 2014, 34(9): 2259-2265.
26	刘新超, 贾磊, 俞勤, 等. 零价铁还原脱氮技术研究进展 [J]. 四川环境, 2016, 35(4): 118-122.
	LiuX C, JiaL, YuQ, et al. Review of reductive denitrification by zero-valent iron [J]. Sichuan Environment, 2016, 35(4): 118-122.
27	王迪. 还原铁粉去除地下水中硝酸盐及亚硝酸盐的研究 [D]. 哈尔滨: 东北林业大学, 2013.
	WangD. Study on removal of nitrate and nitrite in the groundwater ofreduced iron powder [D]. Harbin: Northeast Forestry University, 2013.
28	ChoeS, ChangY Y, HwangK Y, et al. Kinetics of reductive denitrification by nanoscale zero-valent iron [J]. Chemosphere, 2000, 41(8): 1307-1311.
29	LiX Q, ElliottD W, ZhangW X. Zero-valent iron nanocarriers for abatement of environmental pollutants: materials and engineering aspects [J]. Critical Reviews in Solid State & Materials Sciences, 2006, 31(4): 111-122.
30	郝志伟, 李亮, 马鲁铭. 零价铁还原法脱除地下水中硝酸盐的研究 [J]. 中国给水排水, 2008, 24(17): 36-39.
	HaoZ W, LiL, MaL M. Study on removal of nitrate from groundwater by zero-valent iron reduction process [J]. China Water & Wastewater, 2008, 24(17): 36-39.

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