Abstract:By impregnating active components Zn, triethylenediamine (TEDA) and Zn-TEDA on the surface of zirconium hydroxide (Zr(OH)4) granules, the NO2 removal performance and mechanism of Zn and/or TEDA modified Zr(OH)4 were investigated. The interaction mechanisms of Zr(OH)4, Zn and TEDA with NO2 and yielded NO were discussed in detail. The results showed that the NO2 purifying ability of Zr(OH)4 was significantly improved by loading 4% Zn and 6% TEDA at the same time. The breakthrough time of the zinc-amine modified Zr(OH)4 could reach 84 min, the adsorption capacity for NO2 breakthrough could reach 24.8 mg·cm?3, and the NO release ratio decreased to 6%. In terms of the interaction mechanism with NO2 and NO, Zr(OH)4 matrix removed NO2 mainly through the reaction between surface terminal hydroxyls and NO2, and producing nitrate and nitrite. Zn mainly acted as the assistant of terminal hydroxyls, providing new surface basic adsorption sites for NO2 or acidic intermediates. TEDA could catalyze the surface hydrolysis of NO2 and led to NO2 transformation into more acidic HNO3 and HNO2, then NO2 can be removed quickly. When both Zn and TEDA were loaded, the matrix, metal and amine could cooperate effectively. The synergistic effect among them had a significant improvement on the NO2 removal performance of the material, NO release was delayed and its production proportion was significantly reduced. This provides guidance on the design and preparation of novel air purification materials for nitrogen oxides removal. Key words:zirconium hydroxide/ zinc/ triethylenediamine/ nitrogen oxides/ removal performance/ removal mechanism/ synergistic effect.
图1NO2脱除性能评价装置 Figure1.Evaluation devices for NO2 removal performance
图3穿透时间和NO2穿透吸附量的实验值与理论计算值的比较 Figure3.Comparison of experimental values of breakthrough time and adsorption capacity of NO2 breakthrough with theoretical values
表1Zn和TEDA负载量对穿透时间的影响 Table1.Effects of Zn and TEDA loading amount on breakthrough time
单一负载金属Zn
单一负载有机胺TEDA
4% Zn +不同负载量TEDA
负载质量分数/%
穿透时间/min
负载质量分数/%
穿透时间/min
负载质量分数/%
穿透时间/min
0
18.5
0
18.5
0
41
1
22
2
30
2
53
2
26
4
38.5
4
68
3
33
6
52
6
84
4
41
8
74
8
75
5
36.5
10
90.5
10
66.5
单一负载金属Zn
单一负载有机胺TEDA
4% Zn +不同负载量TEDA
负载质量分数/%
穿透时间/min
负载质量分数/%
穿透时间/min
负载质量分数/%
穿透时间/min
0
18.5
0
18.5
0
41
1
22
2
30
2
53
2
26
4
38.5
4
68
3
33
6
52
6
84
4
41
8
74
8
75
5
36.5
10
90.5
10
66.5
下载: 导出CSV 表2不同材料的穿透时间、NO2穿透吸附量以及NO释放比例 Table2.Breakthrough time, adsorption capacity of NO2 breakthrough and NO release proportions of different materials
材料
穿透 物质
穿透时间/ min
单位质量 穿透 吸附量/ (mg·g?1)
单位体积 穿透 吸附量/ (mg·cm?3)
NO释放 比例/%
Zr
NO
18.5
2.3
5.5
13
4Zn/Zr
NO
41
4.8
12.1
11
6T/Zr
NO
52
6.4
15.3
10
4Zn6T/Zr
NO
84
10.0
24.8
6
材料
穿透 物质
穿透时间/ min
单位质量 穿透 吸附量/ (mg·g?1)
单位体积 穿透 吸附量/ (mg·cm?3)
NO释放 比例/%
Zr
NO
18.5
2.3
5.5
13
4Zn/Zr
NO
41
4.8
12.1
11
6T/Zr
NO
52
6.4
15.3
10
4Zn6T/Zr
NO
84
10.0
24.8
6
下载: 导出CSV 表3吸附NO2前后不同含氧官能团或表面物种含量的变化 Table3.Change in O-containing functional groups or surface species before and after NO2 adsorption
样品名称
含氧官能团或表面物种相对占比/%
Br—OH/Zr
Br—OH
Te—OH
吸附氧或吸附 氧+${\rm{NO}}_3^ - $ + ${\rm{NO}}_2^ - $
Zr
50.7
31.2
18.1
1.8
Zr-ED
51.0
24.2
24.8
1.8
4Zn/Zr
53.6
32.3
14.2
1.9
4Zn/Zr-ED
53.3
18.0
28.6
1.9
6T/Zr
55.7
30.6
13.7
1.8
6T/Zr-ED
55.9
15.4
28.7
1.9
4Zn6T/Zr
55.6
31.1
13.3
1.8
4Zn6T/Zr-ED
55.1
10.1
34.9
2.0
样品名称
含氧官能团或表面物种相对占比/%
Br—OH/Zr
Br—OH
Te—OH
吸附氧或吸附 氧+${\rm{NO}}_3^ - $ + ${\rm{NO}}_2^ - $
Zr
50.7
31.2
18.1
1.8
Zr-ED
51.0
24.2
24.8
1.8
4Zn/Zr
53.6
32.3
14.2
1.9
4Zn/Zr-ED
53.3
18.0
28.6
1.9
6T/Zr
55.7
30.6
13.7
1.8
6T/Zr-ED
55.9
15.4
28.7
1.9
4Zn6T/Zr
55.6
31.1
13.3
1.8
4Zn6T/Zr-ED
55.1
10.1
34.9
2.0
下载: 导出CSV 表4吸附NO2前后表面含氮物种的相对含量的变化 Table4.Change in N-containing species before and after NO2 adsorption
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State Key Laboratory of NBC Protection for Civilian, Research Institute of Chemical Defense, Beijing 100191, China Received Date: 2019-11-06 Accepted Date: 2020-01-23 Available Online: 2020-10-14 Keywords:zirconium hydroxide/ zinc/ triethylenediamine/ nitrogen oxides/ removal performance/ removal mechanism/ synergistic effect Abstract:By impregnating active components Zn, triethylenediamine (TEDA) and Zn-TEDA on the surface of zirconium hydroxide (Zr(OH)4) granules, the NO2 removal performance and mechanism of Zn and/or TEDA modified Zr(OH)4 were investigated. The interaction mechanisms of Zr(OH)4, Zn and TEDA with NO2 and yielded NO were discussed in detail. The results showed that the NO2 purifying ability of Zr(OH)4 was significantly improved by loading 4% Zn and 6% TEDA at the same time. The breakthrough time of the zinc-amine modified Zr(OH)4 could reach 84 min, the adsorption capacity for NO2 breakthrough could reach 24.8 mg·cm?3, and the NO release ratio decreased to 6%. In terms of the interaction mechanism with NO2 and NO, Zr(OH)4 matrix removed NO2 mainly through the reaction between surface terminal hydroxyls and NO2, and producing nitrate and nitrite. Zn mainly acted as the assistant of terminal hydroxyls, providing new surface basic adsorption sites for NO2 or acidic intermediates. TEDA could catalyze the surface hydrolysis of NO2 and led to NO2 transformation into more acidic HNO3 and HNO2, then NO2 can be removed quickly. When both Zn and TEDA were loaded, the matrix, metal and amine could cooperate effectively. The synergistic effect among them had a significant improvement on the NO2 removal performance of the material, NO release was delayed and its production proportion was significantly reduced. This provides guidance on the design and preparation of novel air purification materials for nitrogen oxides removal.
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