Study on heterogeneous catalytic ozonation for removal of COD and ammonia nitrogen

doi:10.19965/j.cnki.iwt.2022-0119

Abstract

Abstract:

With the accelerated development of urbanization and industry in China， pollutant emissions have increased， and the relevant discharge standards for wastewater treatment have become more and more stringent， and the advanced treatment of urban wastewater has become a research hotspot. COD and ammonia nitrogen are the two most important pollutants contained in urban wastewater. The application of heterogeneous catalytic ozonation process in the advanced treatment of COD and ammonia nitrogen removal in a wastewater treatment plant was explored through small-scale and pilot tests. The effects of ozone dosage and contact time and their interactions were investigated by the response surface method based on the central combination design. A quadratic response surface model with COD and ammonia nitrogen removal as response values was also developed， and the model was validated by variance analysis. The results showed that DL-002 catalyst could catalyze ozonation and remove COD and ammonia nitrogen simultaneously. The effect of ozone dosage on the removal of COD and ammonia nitrogen was more significant. Increasing the ozone dosage or extending the contact time could improve the removal of COD and ammonia nitrogen. The optimized results showed that under the conditions of contact reaction time of 20 min and ozone dosage of 25 mg/L， the COD removal was 10 mg/L and the ammonia nitrogen removal was 0.65 mg/L. The solution of using a proprietary catalyst instead of the existing catalyst in the catalytic ozonation tank to remove COD and ammonia nitrogen simultaneously and achieve the standard discharge was fully feasible.

Key words: heterogeneous, catalytic ozonation, advanced treatment, urban wastewater

摘要：

随着我国城市化进程及工业的加速发展，污染物排放量随之增加，污水处理的相关排放标准愈发严格，城市污水的深度处理已成为研究热点。COD和氨氮是城镇污水中含有的最主要的两种污染物。通过小试及中试探讨了非均相催化臭氧氧化工艺在某污水处理厂深度处理去除COD和氨氮中的应用。通过基于中心组合设计的响应面法，考察了臭氧投加量和接触反应时间的影响及其交互作用。同时建立了以COD和氨氮去除量为响应值的二次响应曲面模型，并用方差分析对模型进行验证。结果表明，DL-002催化剂可催化臭氧氧化同时去除COD和氨氮。臭氧投加量对COD和氨氮去除量的影响更显著，增加臭氧投加量或延长接触反应时间可提高COD和氨氮去除量。优化结果显示，在接触反应时间为20 min、臭氧投加量为25 mg/L的条件下，COD去除量为10 mg/L、氨氮去除量为0.65 mg/L。采用专属催化剂代替催化臭氧氧化池中现有的催化剂，同时去除COD和氨氮并实现达标排放的方案完全可行。

关键词: 非均相, 催化臭氧氧化, 深度处理, 城镇污水

CLC Number:

X703.1

Dan WEI,Jie CHEN,Xun SUN. Study on heterogeneous catalytic ozonation for removal of COD and ammonia nitrogen[J]. Industrial Water Treatment, 2022, 42(12): 136-141.

韦丹,陈捷,孙逊. 非均相催化臭氧氧化同时去除COD和氨氮的研究[J]. 工业水处理, 2022, 42(12): 136-141.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2022-0119

https://www.iwt.cn/EN/Y2022/V42/I12/136

Figures/Tables 12

Fig. 1 Expasion process of a wastewater treatment plant

Table 1 Design inlet and outlet water quality

项目	COD	BOD₅	SS	TN	NH₃-N	TP	pH
进水	≤500	≤150	≤300	≤60	≤30	≤4.0	6.0~9.0
出水	≤30	≤10	≤10	≤15	≤1.5	≤1.5	6.0~9.0

Table 2 Water quality characteristics of flocculation sedimentation effluent

项目	COD	pH	TN	NH₃-N	硝氮
范围	30.5~39.8	7.8~8.1	9.11~12.28	1.24~2.37	6.25~8.81
均值	37.2	8.0	10.54	2.01	7.25

Table 3

项目	DL-002	DL-004
粒径/mm	3~5	3~5
基材	氧化铝	氧化铝
抗压强度/N	≥100	≥100
比表面积/（m²·g^-1）	≥230	≥230
堆密度/（g·cm^-3）	0.68~0.72	0.68~0.72
磨耗率/%	≤1	≤1
吸水率/%	≥30	≥30
活性组分	锰、钴的金属氧化物	锰、铈的金属氧化物

Fig.2 Small-scale test results of catalytic ozonation

Table 4 Experimental factor and level

因素	水平
因素	-1.414	-1	0	1	1.414
A/min	18.96	20	22.5	25	26.04
B/（mg·L^-1）	18.34	20.0	24.0	28.0	29.66

Table 5 Design scheme and results of central composite test

序号	接触反应时间/min	臭氧投加量/（mg·L^-1）	COD去除量/（mg·L^-1）	氨氮去除量/（mg·L^-1）
1	26.04	24.00	10.5	0.65
2	18.96	24.00	9.75	0.58
3	22.50	24.00	9.60	0.57
4	20.00	20.00	9.00	0.39
5	22.50	24.00	9.60	0.57
6	20.00	28.00	10.6	0.68
7	25.00	28.00	10.8	0.71
8	22.50	24.00	9.60	0.62
9	22.50	24.00	9.60	0.57
10	22.50	24.00	9.60	0.57
11	25.00	20.00	9.85	0.49
12	22.50	18.34	8.84	0.41
13	22.50	29.66	11.5	0.75

Table 6 Results of response surface regression analysis of COD removal

方差来源	平方和	自由度	均方差	F值	P值
模型	6.43	5	1.29	45.45	< 0.000 1
A（接触反应时间）	0.56	1	0.56	19.68	0.003 0
B（臭氧的投加量）	4.98	1	4.98	176.03	< 0.000 1
AB	0.11	1	0.11	3.73	0.094 6
A²	0.40	1	0.40	14.31	0.006 9
B²	0.48	1	0.48	17.11	0.004 4
残差	0.20	7	0.028
失拟项	0.20	3	0.066
纯误差	0.000	4	0.000
R²	0.970 1
R $a d j 2$	0.948 8
R $p r e d 2$	0.787 5

Table 6 Results of response surface regression analysis of COD removal

方差来源	平方和	自由度	均方差	F值	P值
模型	6.43	5	1.29	45.45	< 0.000 1
A（接触反应时间）	0.56	1	0.56	19.68	0.003 0
B（臭氧的投加量）	4.98	1	4.98	176.03	< 0.000 1
AB	0.11	1	0.11	3.73	0.094 6
A²	0.40	1	0.40	14.31	0.006 9
B²	0.48	1	0.48	17.11	0.004 4
残差	0.20	7	0.028
失拟项	0.20	3	0.066
纯误差	0.000	4	0.000
R²	0.970 1
R $a d j 2$	0.948 8
R $p r e d 2$	0.787 5

Table 7 Results of response surface regression analysis of ammonia nitrogen removal

方差来源	平方和	自由度	均方差	F值	P值
模型	0.13	5	0.026	45.81	<0.000 1
A（接触反应时间）	6.555×10^-3	1	6.555×10^-3	11.40	0.011 8
B（臭氧的投加量）	0.12	1	0.12	213.34	<0.000 1
AB	1.225×10^-3	1	1.225×10^-3	2.13	0.187 8
A²	6.957×10^-4	1	6.957×10^-4	1.21	0.307 8
B²	3.913×10^-4	1	3.913×10^-4	0.68	0.436 7
残差	4.027×10^-3	7	5.752×10^-4
失拟项	2.027×10^-3	3	6.755×10^-4	1.35	0.376 9
纯误差	2.000×10^-3	4	5.000×10^-4
R²	0.970 3
R $a d j 2$	0.942 9
R $p r e d 2$	0.870 8

Table 7 Results of response surface regression analysis of ammonia nitrogen removal

方差来源	平方和	自由度	均方差	F值	P值
模型	0.13	5	0.026	45.81	<0.000 1
A（接触反应时间）	6.555×10^-3	1	6.555×10^-3	11.40	0.011 8
B（臭氧的投加量）	0.12	1	0.12	213.34	<0.000 1
AB	1.225×10^-3	1	1.225×10^-3	2.13	0.187 8
A²	6.957×10^-4	1	6.957×10^-4	1.21	0.307 8
B²	3.913×10^-4	1	3.913×10^-4	0.68	0.436 7
残差	4.027×10^-3	7	5.752×10^-4
失拟项	2.027×10^-3	3	6.755×10^-4	1.35	0.376 9
纯误差	2.000×10^-3	4	5.000×10^-4
R²	0.970 3
R $a d j 2$	0.942 9
R $p r e d 2$	0.870 8

Fig. 3 Effect of ozone dosage and contact reaction time on COD removal

Fig. 4 Effect of ozone dosage and contact reaction time on ammonia nitrogen removal

Fig. 5 Continuous operation results of catalytic ozonation

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