杂多酸改性V-Mo/Ti-W催化剂的宽温SCR脱硝性能

doi:10.16085/j.issn.1000-6613.2021-1888

摘要/Abstract

摘要：

采用等体积浸渍法制备了一系列Keggin型杂多酸改性的V-Mo/Ti-W催化剂，并通过X射线衍射（XRD）、BET比表面分析（BET）、NH₃程序升温脱附（NH₃-TPD）、H₂程序升温还原（H₂-TPR）、X射线光电子能谱（XPS）和傅里叶变换红外光谱（FTIR）等表征方法对催化剂物化性质进行了表征分析。各项表征分析结果表明，杂多酸改性后的HPAs-V-Mo/Ti-W催化剂相比于改性前的催化剂，平均孔径尺寸更大，可抑制硫酸氢铵沉积，以提高催化剂抗硫性能；与V-Mo/Ti-W样品相比，改性后的催化剂具有更强的NH₃吸附能力、更好的还原性能和更多的化学吸附氧物种，从而表现出更优异的脱硝性能和N₂选择性。杂多酸改性后的催化剂在200~380℃温度范围内、150000h^-1高空速、高浓度SO₂和H₂O存在的模拟烟气中表现出高 NH₃-SCR活性、优异的抗SO₂性能，并保持几乎100%的N₂选择性，可作为燃煤电厂深度调峰的宽温催化剂，具备良好的工业应用价值。

关键词: 杂多酸, 选择催化还原, 催化剂

Abstract:

A series of Keggin heteropoly acid-modified V-Mo/Ti-W catalysts were prepared by incipient-wetness impregnation method and their physicochemical properties were investigated by using XRD, BET, NH₃-TPD, H₂-TPR, XPS and FTIR. The analysis indicated that heteropoly acid could inhibit the deposition of ammonium bisulfate by increasing the average pore diameter of the catalyst to improve its resistance to sulfur. Compared with V-Mo/Ti-W catalyst, the HPAs-modified V-Mo/Ti-W catalysts showed higher NH₃ adsorption capacity, better reduction performance and more chemisorbed oxygen species, which provided better DeNO _x performance and N₂ selectivity. The HPAs-modified V-Mo/Ti-W catalysts exhibited high NH₃-SCR activity and excellent SO₂resistance performance in a wide temperature range and almost 100% N₂ selectivity in simulated atmosphere with high concentrations of SO₂and H₂O and under 150000h^-1 gas space velocity. Hence, the HPAs-modified V-Mo/Ti-W catalysts can be used as promising wide-temperature catalysts for deep peak shaving in coal-fired power plants.

Key words: heteropoly acids, selective catalytic reduction (SCR), catalyst

中图分类号:

X511

周佳丽, 马子然, 赵俊平, 马静, 赵春林, 李歌, 王红妍, 王宝冬. 杂多酸改性V-Mo/Ti-W催化剂的宽温SCR脱硝性能[J]. 化工进展, 2022, 41(7): 3615-3623.

ZHOU Jiali, MA Ziran, ZHAO Junping, MA Jing, ZHAO Chunlin, LI Ge, WANG Hongyan, WANG Baodong. HPAs-modified V-Mo/Ti-W catalysts for the selective catalytic reduction of NO _x over a wide temperature range[J]. Chemical Industry and Engineering Progress, 2022, 41(7): 3615-3623.

图/表 10

图1 杂多酸改性的催化剂及V-Mo/Ti-W催化剂的脱硝性能测试（[NO]=[NH3]=300μL/L, [O2]=3%（体积分数）, [SO2]=500μL/L[(a)、(b)]、500~2000μL/L(c), H2O=8%（体积分数）, GHSV=150000h-1）

图2 杂多酸改性的催化剂及V-Mo/Ti-W的XRD谱图

图3 杂多酸改性催化剂及V-Mo/Ti-W的FTIR谱图

表1 Keggin型杂多酸各键反对称伸缩振动频率υas

键	波数/cm^-1
键	W系	Mo系
P—O_a	约1079	约1064
Si—O_a	约950
M $? ???????$ O_d	约983	约964
M—O_b—M	890~850
M—O_c—M	800~760

表1 Keggin型杂多酸各键反对称伸缩振动频率υas

键	波数/cm^-1
键	W系	Mo系
P—O_a	约1079	约1064
Si—O_a	约950
M $? ???????$ O_d	约983	约964
M—O_b—M	890~850
M—O_c—M	800~760

表2 杂多酸改性的催化剂及V-Mo/Ti-W的比表面积和孔结构

样品	BET比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔径/nm
V-Mo/Ti-W	82.7	0.35	13.0
HPMo-V/Ti-W	83.2	0.42	16.0
HPW-V-Mo/Ti	78.4	0.34	14.0
HSiW-V-Mo/Ti	78.9	0.35	14.2
Ti-W粉	94.0	0.39	14.7
TiO₂粉	89.5	0.42	13.2

图4 杂多酸改性的催化剂及V-Mo/Ti-W的XPS谱图

表3 杂多酸改性的催化剂及V-Mo/Ti-W表面不同O和V元素原子比

样品	O_α/（O_α+O_β）	V⁴⁺/（V⁴⁺+V⁵⁺）
V-Mo/Ti-W	13.90	0.28
HPMo-V/Ti-W	27.01	0.32
HPW-V-Mo/Ti	25.00	0.32
HSiW-V- Mo/Ti	21.88	0.31

图5 杂多酸改性的催化剂及V-Mo/Ti-W的H2-TPR谱图

图6 杂多酸改性的催化剂及V-Mo/Ti-W的NH3-TPD谱图

表4 杂多酸改性的催化剂及V-Mo/Ti-W不同温度下的NH3脱附量

样品	NH₃脱附量 /μmol·g^-1	低温		中温		高温
样品	NH₃脱附量 /μmol·g^-1	温度/℃	NH₃脱附量/μmol·g^-1	温度/℃	NH₃脱附量/μmol·g^-1	温度/℃	NH₃脱附量/μmol·g^-1
V-Mo/Ti-W	318.4	174	86.9	285	231.5
HPMo-V/Ti-W	342.7	163	72.4	237	167.4	353	103.0
HPW-V-Mo/Ti	320.5	160	68.5	207	106.5	288	145.5
HSiW-V-Mo/Ti	337.5	160	63.8	222	117	336	156.7

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