Treatment of coal chemical wastewater by Mn-Ti-Mg/Al2O3 catalyzed ozonation process

doi:10.19965/j.cnki.iwt.2022-0440

Abstract

Abstract:

Metallic composite catalyst Mn-Ti-Mg/Al₂O₃was prepared by impregnation method and characterized by SEM-EDS，XPS，BET to display the appearance and investigate the atomic composition，existence of metal elements，specific surface area and the average pore size. In addition，the pH_zpc of composite catalyst was analyzed. The composite catalyst was used for catalytic ozonation treatment of the coal chemical wastewater and the catalytic activity was evaluated. The effects of catalyst dosage，O₃ flow rate and initial pH of solution on its catalytic performance were investigated，and its stability was also studied. The results showed that the Mn-Ti-Mg/Al₂O₃ composite catalyst had a good effect on catalytic ozonation treatment of coal chemical wastewater. The increase of catalyst dosage and ozone flow rate was conducive to improving the removal rate of COD in coal chemical wastewater，and the wastewater was easier to be treated under alkaline conditions. The pH of wastewater declined after the catalyzed ozonation process，which caused the metal cation leaching and deactivation of composite catalyst. Under the conditions of temperature 22 ℃，initial pH of the solution 7.8，catalyst dosage mass concentration 10 g/L，ozone flow rate 1.0 mg/min，and reaction time 40 min，Mn-Ti-Mg/Al₂O₃ was used to catalyze ozonation treatment of coal chemical wastewater，the COD，BOD₅，NH₃-N and other indicators of the treated wastewater met the Emission Standard of Pollutants for Coking Chemical Industry（GB 16171—2012）. GC-MS analysis results showed that the organic pollutants of coal chemical wastewater were mainly phenols，alkanes and other substances，and Mn-Ti-Mg/Al₂O₃catalyzed ozonation process could cause well degradation of organic pollutants in the wastewater.

Key words: metal load, Al₂O₃, catalysis, ozone, coal chemical wastewater

摘要：

以浸渍法制备金属复合催化剂Mn-Ti-Mg/Al₂O₃，采用SEM-EDS、XPS、BET对复合催化剂的表观形貌、原子组成、金属元素的存在状态、比表面积和平均孔径进行表征，并测定了其pH_zpc。之后将其作为多相催化剂用于催化臭氧氧化处理煤化工废水，对其催化效果进行研究，考察了催化剂投加量、O₃流速、溶液初始pH对其催化效能的影响，并对其稳定性进行了研究。结果表明，Mn-Ti-Mg/Al₂O₃复合催化剂对于催化臭氧氧化处理煤化工废水效果较好，催化剂投加量和臭氧流速的增加有利于提高煤化工废水COD的去除率，废水在碱性条件下更易被处理。经过催化臭氧氧化处理之后，废水的pH显著降低，导致催化剂中金属活性成分溶出，催化剂活性降低。在温度22 ℃、溶液初始pH 7.8、催化剂投加质量浓度10 g/L、臭氧流速1.0 mg/min、反应时间40 min条件下，采用Mn-Ti-Mg/Al₂O₃催化臭氧氧化处理煤化工废水，处理后废水的COD、BOD₅、NH₃-N等指标满足炼焦化学工业污染物排放标准（GB 16171—2012）。GC-MS分析结果表明，煤化工废水中有机污染物主要包括酚类、烷烃类等物质，催化臭氧氧化过程使废水中的有机污染物得到良好的降解。

关键词: 金属负载, Al₂O₃, 催化, 臭氧, 煤化工废水

CLC Number:

X703.1

Han QIAO, Yifan MENG, Size YU, Yixin YANG. Treatment of coal chemical wastewater by Mn-Ti-Mg/Al₂O₃ catalyzed ozonation process[J]. Industrial Water Treatment, 2023, 43(3): 114-123.

乔函, 孟一帆, 余思泽, 杨忆新. Mn-Ti-Mg/Al₂O₃催化臭氧氧化处理煤化工废水[J]. 工业水处理, 2023, 43(3): 114-123.

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https://www.iwt.cn/EN/Y2023/V43/I3/114

Figures/Tables 15

References 21

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催化剂	原子分数/%
催化剂	Al	O	Mn	Mg	Ti
Mn/Al₂O₃	40.01	58.00	1.09	—	—
Mg/Al₂O₃	41.20	57.67	—	1.13	—
Ti/Al₂O₃	38.19	58.50	—	—	3.31
Mn-Ti-Mg/Al₂O₃	40.18	57.80	0.23	0.74	1.05

催化剂	原子分数/%
催化剂	Al	O	Mn	Mg	Ti
Mn/Al₂O₃	40.01	58.00	1.09	—	—
Mg/Al₂O₃	41.20	57.67	—	1.13	—
Ti/Al₂O₃	38.19	58.50	—	—	3.31
Mn-Ti-Mg/Al₂O₃	40.18	57.80	0.23	0.74	1.05

样品	比表面积/（m²·g^-1）	孔体积/（cm³·g^-1）	平均孔径/nm	pH_zpc
Al₂O₃	327.22	0.49	5.72	7.3
Mn/Al₂O₃	287.97	0.54	6.18	5.3
Mg/Al₂O₃	222.09	0.45	6.81	5.2
Ti/Al₂O₃	267.73	0.48	6.13	5.0
Mn-Ti-Mg/Al₂O₃	292.45	0.59	6.77	6.6

样品	比表面积/（m²·g^-1）	孔体积/（cm³·g^-1）	平均孔径/nm	pH_zpc
Al₂O₃	327.22	0.49	5.72	7.3
Mn/Al₂O₃	287.97	0.54	6.18	5.3
Mg/Al₂O₃	222.09	0.45	6.81	5.2
Ti/Al₂O₃	267.73	0.48	6.13	5.0
Mn-Ti-Mg/Al₂O₃	292.45	0.59	6.77	6.6

	原子分数/%
	Al	O	Mn	Mg	Ti
使用前	40.18	57.80	0.23	0.74	1.05
使用后	39.22	59.36	0.09	0.36	0.97

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Treatment of coal chemical wastewater by Mn-Ti-Mg/Al₂O₃ catalyzed ozonation process

Mn-Ti-Mg/Al₂O₃催化臭氧氧化处理煤化工废水

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项目	原水样	处理后水样
COD/（mg·L^-1）	156.0	53.6
BOD₅/（mg·L^-1）	23.8	—
UV₂₅₄/cm^-1	1.25	0.13
TOC/（mg·L^-1）	40.12	20.07
NH₃-N/（mg·L^-1）	5.7	2.3
pH	7.8	3.4

编号	分子式	有机物名称	有机物类别
1	C₆H₆O	苯酚	酚类
2	C₇H₈O	2-甲基苯酚	酚类
3	C₇H₈O	4-甲基苯酚	酚类
4	C₈H₁₀O	3-乙基苯酚	酚类
5	C₁₄H₂₂O	2，4-双（1，1-二甲基乙基）-苯酚	酚类
6	C₁₀H₂₂	癸烷	烷烃类
7	C₁₃H₂₈	2-甲基十二烷	烷烃类
8	C₁₅H₃₂	十五烷	烷烃类
9	C₁₈H₃₈	2，6，10-三甲基十五烷	烷烃类
10	C₁₆H₃₄	十六烷	烷烃类
11	C₁₇H₃₆	2-甲基十六烷	烷烃类
12	C₂₀H₄₂	2，6，10，14-四甲基十六烷	烷烃类
13	C₁₇H₃₆	十七烷	烷烃类
14	C₁₉H₄₀	2，6-二甲基十七烷	烷烃类
15	C₁₈H₃₈	十八烷	烷烃类
16	C₂₀H₄₂	二十烷	烷烃类
17	C₆H₈O₃	3，4-二甲基-2，5-呋喃二酮	酮类
18	C₇H₁₀O	2，3-二甲基-2-环戊烯酮	酮类
19	C₉H₆O₃	4-甲基-1，3-异苯并呋喃二酮	酮类
20	C₁₀H₁₀O₄	邻苯二甲酸二甲酯	酯类
21	C₃₀H₆₃O₄P	磷酸三癸基酯	酯类
22	C₁₆H₂₂O₄	邻苯二甲酸二异丁酯	酯类
23	C₈H₁₆O₂	辛酸	酸类
24	C₂₀H₃₄O	香叶基香叶醇	醇类
25	C₁₆H₁₃N	N-苯基-1-萘胺	胺类
26	C₈H₉N	N-苯亚甲基甲胺	胺类
27	C₁₀H₁₄N₂O₃S	4-（吗啉磺酰）苯胺	胺类
28	C₁₉H₂₃NO	N-苄基-N-乙基-对异丙基苯甲酰胺	胺类

编号	分子式	有机物名称	有机物类别
1	C₁₄H₂₂O	2，5-双（1，1-二甲基乙基）苯酚	酚类
2	C₁₀H₂₀	1-甲基-2-丙基环己烷	烷烃类
3	C₁₃H₂₈	2-甲基十二烷	烷烃类
4	C₁₈H₃₈	2，6，10-三甲基十五烷	烷烃类
5	C₁₉H₄₀	2，6，10，14-四甲基十五烷	烷烃类
6	C₁₂H₁₄O₄	邻苯二甲酸异丁酯	酯类
7	C₁₆H₂₂O₄	丁基仲-丁基邻苯二甲酸酯	酯类
8	C₂₄H₃₈O₄	邻苯二甲酸二异辛酯	酯类
9	C₁₉H₃₈O₂	14-甲基十五烷酸异丙酯	酯类
10	C₁₉H₂₃NO	N-苄基-N-乙基对异丙基苯甲酰胺	胺类

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