基于铁基质高效催化还原污水中硝酸盐氮的实验研究

doi:10.11949/j.issn.0438-1157.20181059

摘要/Abstract

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

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

中图分类号:

X 703

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.

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.

图/表 9

图1 铁基质高效催化脱氮载体的表面形态和内部结构

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

图2 实验装置示意图

Fig.2 Schematic diagram of experimental equipment

表1 不同分组实验中载体种类及水质条件

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

表1 不同分组实验中载体种类及水质条件

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

图3 不同催化剂条件下NO3--N (a)、NH4+-N (b)和NO2--N (c) 的浓度变化

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

图4 pH对催化载体D脱氮效果的影响

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

图5 不同pH体系在360 min时各氮产物所占比例

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

图6 原水NO3–-N浓度对NO3–-N还原效率的影响

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

图7 脱氮载体O在不同反应级数条件下线性回归分析

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

图8 脱氮载体D在不同反应级数条件下线性回归分析

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

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