Pr掺杂对V2O5-MoO3/TiO2催化剂NH3-SCR反应活性的影响

doi:10.7503/cjcu20140895

摘要/Abstract

摘要：

采用溶胶-凝胶法制备了不同Pr掺杂量的Pr₆O₁₁-TiO₂载体, 并以浸渍法制备了V₂O₅-MoO₃/Pr₆O₁₁-TiO₂催化剂. 活性评价结果表明, 该催化剂在220~400 ℃范围内具有良好的脱硝效率和N₂选择性以及较强的抗SO₂和H₂O性能. 表征结果表明, 掺杂Pr可以提高V₂O₅-MoO₃/TiO₂催化剂的比表面积、表面化学吸附氧物种浓度、桥式硝酸盐物种和Brönsted酸位数量, 从而提高了催化剂上NO_x的选择性催化还原(NH₃-SCR)活性.

关键词: Pr掺杂, V2O5-MoO3/TiO2催化剂, 选择性催化还原, 氨气

Abstract:

V₂O₅-MoO₃/Pr₆O₁₁-TiO₂ catalysts were prepared by means of an impregnation method and TiO₂ supports doped with different amounts of Pr were synthesized via a sol-gel method. The evaluation of selective catalytic reduction(SCR) activity indicated the catalysts with high activity and N₂ selectivity in a temperature range of 220—400 ℃. And the Pr-doped catalyst also exhibited good resistance to SO₂ and H₂O. The catalysts were characterized by means of X-ray diffraction(XRD), N₂ adsorption-desorption(BET), X-ray photo-electron spectrometer(XPS) and in situ diffuse reflectance infrared Fourier transform spectroscopy(in situ DRIFTS). The results showed that the specific surface areas of Pr-doped V₂O₅-MoO₃/TiO₂ catalysts were larger than that of the V₂O₅-MoO₃/TiO₂ catalyst. Furthermore, the addition of Pr on V₂O₅-MoO₃/TiO₂ catalyst could give more NH₃ adsorption species, chemisorbed oxygen species, bridged nitrate species and the numbers of Brönsted acid sites, resulting in an enhance in the catalytic activity for NH₃-SCR of NO_x.

Key words: Pr-Doping, V2O5-MoO3/TiO2 catalyst, Selective catalytic reduction(SCR), NH3

中图分类号:

O643

TrendMD:

晁晶迪, 何洪, 宋丽云, 房玉娇, 梁全明, 张桂臻, 邱文革, 张然. Pr掺杂对V₂O₅-MoO₃/TiO₂催化剂NH₃-SCR反应活性的影响. 高等学校化学学报, 2015, 36(3): 523.

CHAO Jingdi, HE Hong, SONG Liyun, FANG Yujiao, LIANG Quanming, ZHANG Guizhen, QIU Wenge, ZHANG Ran. Promotional Effect of Pr-Doping on the NH₃-SCR Activity over the V₂O₅-MoO₃/TiO₂ Catalyst^†. Chem. J. Chinese Universities, 2015, 36(3): 523.

图/表 9

Fig.1 XRD patterns of V2O5-MoO3/Pr6O11-TiO2 catalysts a. 3V6MoTi; b. 3V6Mo2PrTi; c. 3V6Mo4PrTi; d. 3V6Mo8PrTi.

Table 1 SBET, pore volume and average crystallite size of the Pr6O11-TiO2 supports and V2O5-MoO3/Pr6O11-TiO2 catalysts

Sample	Content of Pr(%)	S_BET/(m²·g^-1)	Pore volume/(cm³·g^-1)	Crystallite size/nm
TiO₂		34.8	0.06	29.8
2Pr-TiO₂	2	76.0	0.12	11.6
4Pr-TiO₂	4	123.2	0.19	12.0
8Pr-TiO₂	8	101.5	0.16	11.7
3V6MoTi		15.7	0.03	33.6
3V6Mo2PrTi	2	64.5	0.10	12.2
3V6Mo4PrTi	4	85.0	0.14	12.7
3V6Mo8PrTi	8	87.6	0.16	12.6

Fig.2 Conversion of NOx(A), selectivity of N2 and production of N2O(B) over the V2O5-MoO3/Pr6O11-TiO2 catalysts Test condition: 760 mg/m3 NH3, 1340 mg/m3 NO, 8%O2, He balance, space velocity: 3×104 h-1.

Table 2 XPS data of the catalysts*

Sample	A(V⁴⁺)/A(V₂_p)	A(O_α)/A(O₁_s)
3V6MoTi	0.12	0.15
3V6Mo4PrTi	0.11	0.20

Fig.3 XPS spectra of Ti2p(A), V2p(B), Mo3d(C) and O1s(D) over the 3V6MoTi(a) and 3V6Mo4PrTi(b) catalysts

Fig.4 XPS spectra of Pr3d over the 3V6Mo2PrTi(a),3V6Mo4PrTi(b) and 3V6Mo8PrTi(c) catalyst

Fig.5 In situ DRIFTS spectra of NH3 adsorption over the 3V6MoTi(A) and 3V6Mo4PrTi(B) catalysts Temperature/℃: a. 40; b. 100; c. 150; d. 200; e. 250; f. 300.

Fig.6 In situ DRIFTS spectra of NO+O2 co-adsorption over the 3V6MoTi(A) and 3V6Mo4PrTi(B) catalysts

Fig.7 Effects of SO2 and H2O on the NOx conversion over 3V6MoTi(a) and 3V6Mo4PrTi(b) catalysts at 260 ℃ Reaction condition: NH3(760 mg/m3), NO(1340 mg/m3), O2(8%), SO2(1430 mg/m3), H2O(5%), N2 balance, space velocity: 3×104 h-1.

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Pr掺杂对V₂O₅-MoO₃/TiO₂催化剂NH₃-SCR反应活性的影响

Promotional Effect of Pr-Doping on the NH₃-SCR Activity over the V₂O₅-MoO₃/TiO₂ Catalyst^†

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