Research on the middle-low temperature denitration and anti-poisoning properties of plate V2O5-MoO3/TiO2 SCR catalysts
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摘要: 针对中低温锅炉烟气脱硝技术需求的特点,采用等体积浸渍法,以V2O5为活性组分、MoO3为助剂,制备了高钒高钼含量的V2O5-MoO3/TiO2型粉末和平板式SCR脱硝催化剂,考察了活性组分和助剂含量对催化剂活性以及抗SO2和H2O中毒性能的影响,对反应前后的催化剂进行了微观表征,并针对最优催化剂研究了其在不同烟气工况下催化剂的脱硝性能。结果表明,提升V2O5负载量可以有效提高催化剂的脱硝活性;MoO3助剂的添加也可以提高催化剂的脱硝活性。XPS、XRF、FT-IR等表征结果表明,MoO3的含量会影响催化剂中V4+/V5+的比值,其相对含量的增加有利于催化剂中非化学计量钒物种的形成以及化学吸附氧比例的增加,钼与钒物种间的交互作用是抑制SO2和H2O对催化剂的毒化作用的关键。3V2O5-10MoO3/TiO2平板式催化剂在温度为200℃、空速为3 500 h-1含SO2和H2O烟气条件下,经30 d连续反应,脱硝效率稳定维持在82%左右,该催化剂在中低温下具有优异的抗SO2和H2O中毒性能以及稳定性。Abstract: Considering the technical requirements for middle-low temperature denitration of flue gas, a series of powder and plate type V2O5-MoO3/TiO2 SCR catalysts were prepared using incipient wetness impregnation method with V2O5 as the active component and with MoO3 as the promoter. Experiments were performed to investigate the effects of active component and promoter contents of the catalysts on the activities and the resistance to deactivation by SO2 and H2O. The characterization of the fresh and used catalysts was conducted, and the optimal catalyst was further studied to reveal the denitration performance under different flue gas conditions. The results indicate that the activities of the catalysts are enhanced with the increase of V2O5 loadings. Also, the addition of MoO3 can promote the catalytic activity. The characterization results from XRF, XPS, FT-IR and other analysis suggest that the MoO3 content could affect the V4+/V5+ ratio in the catalyst. The increase in relative MoO3 content is favorable for the formation of non-stoichiometry vanadium species as well as the rise of chemical adsorption oxygen. Therefore, the interactions between molybdenum and vanadium species might be an essential reason for the resistance to the deactivation by SO2 and H2O. The denitrification efficiency of 3V2O5-10MoO3/TiO2 plate catalyst keeps steady around 82% after 30 days test in the presence of SO2 and H2O at temperature of 200℃ and space velocity of 3 500 h-1. The catalyst is identified to have an excellent resistance to the deactivation by SO2 and H2O under middle-low temperatures.
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Key words:
- middle-low temperature denitration /
- plate catalyst /
- V2O5 /
- MoO3 /
- resistance to deactivation
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表 1 催化剂的比表面积和孔结构
Table 1 Specific surface area and pore structure of the catalysts
Sample Catalyst Specific surface area
A/(m2·g-1)Pore volume
v/(cm3·g-1)Average pore diameter
d/nm1 F-3V2O5-10MoO3/TiO2(fresh) 71.43 0.32 17.8 2 F-5V2O5-10MoO3/TiO2(fresh) 50.64 0.25 19.6 3 B-3V2O5-10MoO3/TiO2(fresh) 54.32 0.23 16.7 4 B-5V2O5-10MoO3/TiO2(fresh) 49.04 0.22 18.0 5 F-3V2O5-10MoO3/TiO2(after SCR) 62.09 0.28 18.0 6 F-5V2O5-10MoO3/TiO2(after SCR) 35.78 0.17 19.9 7 B-3V2O5-10MoO3/TiO2(after SCR)* 26.64 0.16 24.4 8 B-5V2O5-10MoO3/TiO2(after SCR) 38.14 0.18 19.3 *duration time of the SO2 and H2O deactivation experiment: NO.5 and NO.6 catalysts were 167 h, NO.7 catalyst was 120 d and NO.8 catalyst was 17 d 表 2 催化剂中各组分含量
Table 2 Each component content of the catalysts
Sample Content w/% V2O5 MoO3 SiO2 Al2O3 SO3 TiO2 1 2.86 8.66 - - - 88.27 2 4.98 8.62 - - - 86.22 3 2.70 8.04 6.59 5.37 - 75.82 4 4.80 7.96 6.38 5.18 - 74.39 5 2.80 8.46 - - 1.64 86.19 6 4.74 8.25 - - 5.43 80.70 7 2.51 7.33 6.21 4.49 8.47 69.06 8 4.34 7.54 6.25 4.93 4.52 71.45 *: annotation: duration time of the SO2 and H2O deactivation experiment: NO.5 and NO.6 catalysts were 167 h, NO.7 catalyst was 120 d and NO.8 catalyst was 17 d -
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