Catalytic performance of Ag(x)/ZSM-5 catalysts for selective catalytic reduction of nitric oxide by methane
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摘要: 采用浸渍法制备Ag（x）/ZSM-5（x=3、6、9）催化剂。采用XRD、SEM、NH3-TPD、Py-FTIR、XPS和NO-TPD等手段对催化剂的理化性质进行表征，在常压固定床微型反应器中评价催化剂甲烷选择性催化还原（CH4-SCR）NO催化性能，考察Ag负载量对Ag（x）/ZSM-5催化剂CH4-SCR脱硝性能的影响。结果表明，ZSM-5分子筛负载Ag，催化剂的酸性和酸量发生变化，改善了催化剂对NO的吸附脱附性能。随着Ag负载量增加，形成较大的Ag晶粒，有利于甲烷活化，Ag（x）/ZSM-5催化剂CH4-SCR脱硝活性提高。Ag（9）/ZSM-5催化剂CH4-SCR脱硝性能较好，在350℃时NO转化率为41.87%。Abstract: Ag(x)/ZSM-5 (x=3, 6, 9) catalysts for selective catalytic reduction of nitric oxide by methane (CH4-SCR) were prepared by impregnation method. The physicochemical properties of the catalysts were characterized by XRD, SEM, NH3-TPD, Py-FTIR, XPS and NO-TPD. The catalytic performance for selective catalytic reduction of nitric oxide by methane was evaluated in a fixed-bed micro-reactor under atmospheric pressure and the influence of Ag loading were investigated.The results show that the impregnation of Ag has changed the acidity and amount of acid of the catalyst and improved the adsorption and desorption performance of NO on ZSM-5 molecular sieve. With the increase of Ag loading, Ag particle size increases and results in higher methane activation as well as the denitration activity of CH4-SCR over Ag(x)/ZSM-5 catalyst. Ag(9)/ZSM-5 has better denitration activity and the NO conversion is 41.87% at 350℃.
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Key words:
- methane /
- NO /
- Ag /
- ZSM-5 /
- selective reduction
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图 1 Ag(x)/ZSM-5 (x=0、3、6、9)催化剂的活性评价
Figure 1 Activity evaluation of the Ag(x)/ZSM-5 (x=0, 3, 6, 9) catalysts
图 2 Ag(x)/ZSM-5(x=0、3、6、9)催化剂的XRD谱图
Figure 2 XRD patterns of the Ag(x)/ ZSM-5 (x=0, 3, 6, 9) catalysts
图 3 Ag(x)/ZSM-5催化剂的SEM照片和Ag(9)/ZSM-5的TEM照片
Figure 3 SEM images of the Ag(x)/ZSM-5 catalysts and TEM images of the Ag(9)/ZSM-5 catalysts
(a): ZSM-5; (b): Ag(6)/ZSM-5; (c): Ag(9)/ZSM-5; (d): Ag(9)/ZSM-5
图 4 Ag(x)/ZSM-5(x=0、3、6、9)催化剂的NH3-TPD谱图
Figure 4 NH3-TPD profiles of the Ag(x)/ ZSM-5 (x=0, 3, 6, 9) catalysts
图 5 不同温度下Ag(x)/ZSM-5(x=0、3、6、9)催化剂的吡啶红外吸附光谱谱图
Figure 5 Py-FTIR spectra of the Ag(x)/ZSM-5 (x=0, 3, 6, 9) catalysts at different temperatures
图 6 Ag(x)/ZSM-5(x=3、6、9)催化剂的Ag 3d态的光电子能谱图
Figure 6 XPS spectra of Ag 3d state of the Ag(x)/ ZSM-5 Ag(x)/ZSM-5 (x=3, 6, 9) catalysts
图 7 Ag(x)/ZSM-5(x=0、3、6、9)催化剂的NO-TPD谱图
Figure 7 NO-TPD profiles of the Ag(x)/ ZSM-5 (x=0, 3, 6, 9) catalysts
表 1 Ag(x)/ZSM-5(x=0、3、6、9)催化剂中元素含量
Table 1 Elemental contents of the Ag(x)/ZSM-5 Ag(x)/ ZSM-5 (x=0, 3, 6, 9) catalysts
Catalyst Elemental composition w/% O Na Al Si Ag* ZSM-5 63.42 0.59 0.94 35.05 - Ag(3)/ZSM-5 55.34 0.24 1.01 41.03 2.44 Ag(6)/ZSM-5 57.44 0.11 1.44 36.17 5.08 Ag(9)/ZSM-5 59.97 0.07 0.69 32.47 7.30 *: base on carrier 
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表 2 Ag(x)/ZSM-5(x=0、3、6、9)催化剂样品的NH3-TPD测试
Table 2 NH3-TPD results of the Ag(x)/ZSM-5 (x=0, 3, 6, 9) catalysts
Catalyst Weak acid Medium acid Strong acid peak t/℃ percentage/% peak t/℃ percentage/% peak t/℃ percentage/% ZSM-5 191 57.6 280 22.1 395 20.3 Ag(3)/ZSM-5 228 53.8 303 29.0 465 17.3 Ag(6)/ZSM-5 228 51.3 300 33.7 465 15.0 Ag(9)/ZSM-5 225 50.2 295 38.3 450 11.4
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表 3 Ag(x)/ZSM-5 Ag(x)/ZSM-5(x=3、6、9)催化剂的XPS表征
Table 3 XPS results of the Ag(x)/ZSM-5 (x=3, 6, 9) catalysts
Catalyst Binding energy of Ag 3d5/2 E/eV SAg0/% Binding energy of Ag 3d3/2 E/eV SAg0/% Ag+ Ag0 Ag+ Ag0 Ag(3)/ZSM-5 367.2 368.8 69 373.3 374.8 71 Ag(6)/ZSM-5 367.6 368.8 73 373.5 374.8 76 Ag(9)/ZSM-5 367.9 368.8 81 373.9 374.8 81
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表 4 Ag(x)/ZSM-5(x=3、6、9)催化剂的NO-TPD测试
Table 4 NO-TPD results of the Ag(x)/ZSM-5 (x=3, 6, 9) catalysts
Catalyst α β γ η peak t/℃ percentage/% peak t/℃ percentage/% peak t/℃ percentage/% peak t/℃ percentage/% Ag(3)/ZSM-5 96 8.4 185 17.6 262 44.4 315 29.6 Ag(6)/ZSM-5 113 9.9 212 21.7 283 42.9 327 25.5 Ag(9)/ZSM-5 105 19.0 200 25.3 269 35.0 319 20.7
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