Ir基催化剂用于CO选择性催化还原NO的研究进展

doi:10.16085/j.issn.1000-6613.2018-1749

摘要/Abstract

摘要：

针对具有烟温低、氧含量高和CO浓度大等特征的固定源烟气（钢铁烧结/球团烟气和焦化烟气等）脱硝领域，CO选择性催化还原NO _x （CO-SCR）技术具有良好的发展前景。Ir基贵金属催化剂因其在CO-SCR反应体系中表现出了良好的抗氧能力和较高的催化活性成为催化脱硝领域研究的热点之一。本文重点总结了单一载体、复合载体与复合活性组分三类Ir基催化剂在CO-SCR脱除NO _x 中的催化性能，同时从制备条件和反应条件两大方面归纳了其对Ir基催化剂的CO-SCR脱硝性能的影响，简要阐述了Ir基催化剂表面反应机理，并对未来研究工作进行了展望，指出采用多种手段对催化剂进行改性，并通过降低Ir负载量、反应温度窗口以及提升其催化活性等方式来降低成本，为实现Ir基催化剂CO-SCR工业化应用提供借鉴。

关键词: 选择催化还原, 一氧化碳, 铱, 催化剂

Abstract:

The CO selective catalytic reduction of NO _x (CO-SCR) technique has attracted considerable attentions in reduction denitration for flue gas from stationary source such as steel sintering/pellet emissions and coking flue gas, and the most outstanding characteristics of these emissions are low temperature, high oxygen content and high CO concentration. Ir-based catalysts, one class of precious metal catalysts, have become one of the hotspots in catalytic reduction denitration due to their excellent antioxidant capacity and high catalytic activity in the CO-SCR reaction system. This review was devoted to the catalytic performance of three types of Ir-based catalysts in CO-SCR removal of NO _x , including single carrier, composite carrier and composite active component. The effects of the preparation conditions and reaction conditions on the CO-SCR denitration performance of the Ir-based catalysts were also summarized. Finally, the reaction mechanism of NO _x on the surface of the Ir-based catalysts was briefly described. The paper points out that the catalyst can be modified by various methods, and the cost can be reduced by reducing the Ir loading and the reaction temperature window or improving the catalytic activity, which provides reference for the industrial application of the Ir-based catalyst CO-SCR.

Key words: selective catalytic reduction(SCR), carbon monoxide, iridium, catalyst

中图分类号:

O643.36

孟婧轩, 高凤雨, 唐晓龙, 易红宏, 周远松. Ir基催化剂用于CO选择性催化还原NO的研究进展[J]. 化工进展, 2019, 38(06): 2746-2755.

Jingxuan MENG, Fengyu GAO, Xiaolong TANG, Honghong YI, Yuansong ZHOU. Review of the Ir-based catalyst in selective catalytic reduction of NO with CO[J]. Chemical Industry and Engineering Progress, 2019, 38(06): 2746-2755.

图/表 7

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催化剂	反应条件	温度/℃	NO转化率/%	CO转化率/%	参考文献
Ce_0.67Sn_0.33O₂	[NO]=5%,[CO]=10%,He 平衡气, GHSV=12000h^-1	325	70	—	[31]
Cu/Ce/Al(20∶1，Ce和Al体积比)	[NO]=5%,[CO]=10%, He平衡气, GHSV=12000h^-1	350	100	—	[32]
CuO-V₂O₅/γ-Al₂O₃	[NO]=5%,[CO]=10%, Ar平衡气, GHSV=24000h^-1	350	100	—	[10]
CuO/Ni _x O _y /γ-Al₂O₃	[NO]=5%,[CO]=10%, He平衡气, GHSV=24000h^-1	350	100	—	[33]
Cu/CeMn-10∶1	[NO]=5%,[CO]=5%, He平衡气, GHSV=24000h^-1	225	98	48	[34]
Co_2.9Cu_0.1O₄	[NO]=5%,[CO]=5%,[O₂]=2.5%,[H₂O]=2.5%, Ar平衡气, GHSV=5000h^-1	200	70	100	[6]

催化剂	反应条件	温度/℃	NO转化率/%	CO转化率/%	参考文献
Ce_0.67Sn_0.33O₂	[NO]=5%,[CO]=10%,He 平衡气, GHSV=12000h^-1	325	70	—	[31]
Cu/Ce/Al(20∶1，Ce和Al体积比)	[NO]=5%,[CO]=10%, He平衡气, GHSV=12000h^-1	350	100	—	[32]
CuO-V₂O₅/γ-Al₂O₃	[NO]=5%,[CO]=10%, Ar平衡气, GHSV=24000h^-1	350	100	—	[10]
CuO/Ni _x O _y /γ-Al₂O₃	[NO]=5%,[CO]=10%, He平衡气, GHSV=24000h^-1	350	100	—	[33]
Cu/CeMn-10∶1	[NO]=5%,[CO]=5%, He平衡气, GHSV=24000h^-1	225	98	48	[34]
Co_2.9Cu_0.1O₄	[NO]=5%,[CO]=5%,[O₂]=2.5%,[H₂O]=2.5%, Ar平衡气, GHSV=5000h^-1	200	70	100	[6]

催化剂	反应条件	温度 /℃	NO转化率/%	CO转化率/%	参考文献
3% Pt/TiO₂-SG	[NO]=0.5%,[CO]=1.5%,[O₂]=1.5%, He平衡气	300	73	—	[17]
Pt/WO₃/ZrO₂	[NO]=0.5%,[CO]=1.5%,[O₂]=2%, N₂平衡气	380	16	—	[15]
Pd/Ce_0.6Zr_0.4O₂	[NO]= 0.023%,[CO]= 0.0685%,[O₂]=10.5%, N₂平衡气	350	96	100	[20]
Rh/Na-Beta zeolite	[NO]=0.05%,[CO]=1.5%,[O₂]=9%,[H₂O]=6%, N₂平衡气	350	45	79	[21]
LaCu-ZSM-5/cordierite	[NO]=0.05%,[CO]=0.1%,[O₂]=6.8%,[SO₂]=100μL/L, [H₂O]=10.5%, He平衡气	250	50	100	[35]
Ba/Ir/WO₃-SiO₂	[NO]=0.05%,[CO]=0.3%,[O₂]=5%,[SO₂]=1μL/L, [H₂O]=6%,He平衡气, GHSV=60000h^-1	260	100	—	[36]

催化剂	反应条件	温度 /℃	NO转化率/%	CO转化率/%	参考文献
3% Pt/TiO₂-SG	[NO]=0.5%,[CO]=1.5%,[O₂]=1.5%, He平衡气	300	73	—	[17]
Pt/WO₃/ZrO₂	[NO]=0.5%,[CO]=1.5%,[O₂]=2%, N₂平衡气	380	16	—	[15]
Pd/Ce_0.6Zr_0.4O₂	[NO]= 0.023%,[CO]= 0.0685%,[O₂]=10.5%, N₂平衡气	350	96	100	[20]
Rh/Na-Beta zeolite	[NO]=0.05%,[CO]=1.5%,[O₂]=9%,[H₂O]=6%, N₂平衡气	350	45	79	[21]
LaCu-ZSM-5/cordierite	[NO]=0.05%,[CO]=0.1%,[O₂]=6.8%,[SO₂]=100μL/L, [H₂O]=10.5%, He平衡气	250	50	100	[35]
Ba/Ir/WO₃-SiO₂	[NO]=0.05%,[CO]=0.3%,[O₂]=5%,[SO₂]=1μL/L, [H₂O]=6%,He平衡气, GHSV=60000h^-1	260	100	—	[36]

催化剂	反应条件	温度/℃	NO 转化率/%	CO转化率/%	参考文献
Ir/SiO₂	[NO]=0.1%,[CO]=0.75%,[O₂]=1%,He平衡气,GHSV=40000h^-1	365	80	—	[37]
Ir/Al₂O₃	[NO]=0.1%,[CO]=0.75%,[O₂]=1%,He平衡气,GHSV=40000h^-1	400	50	—	[37]
Ir/SiO₂	[NO]=0.1%,[CO]=0.6%,[O₂]=5%,[SO₂]=20μL/L,[H₂O]=6%,He平衡气, GHSV=75000h^-1	350	62	90	[28]
Ir/WO₃	[NO]=0.1%,[CO]=1%,[O₂]=2%,He平衡气	250	79.5	—	[38]
Ir/WO₃-SiO₂	[NO]=0.05%,[CO]=0.3%,[O₂]=5%,[SO₂]=1μL/L,[H₂O]=6%,He平衡气, GHSV=75000h^-1	300	70	55	[39]
Ir/WO₃-SiO₂	[NO]=0.05%,[CO]=0.5%,[O₂]=10%,[H₂O]=1%,He平衡气,GHSV=34000h^-1	260	86	—	[40]
Nb₂O₅/Ir/SiO₂	[NO]=0.05%,[CO]=0.3%,[O₂]=5%,[H₂O]=6%,He平衡气,GHSV=75000h^-1	280	80	—	[44]
Ba/Ir/SiO₂	[NO]=0.05%,[CO]=0.3%,[O₂]=5%,[SO₂]=1μL/L,[H₂O]=6%,He平衡气, GHSV=75000h^-1	280	65	60	[45]
Ba-Ir/WO₃-SiO₂	[NO]=0.05%,[CO]=0.3%,[O₂]=5%,[SO₂]=1μL/L,[H₂O]=6%,He平衡气, GHSV=75000h^-1	280	94	90	[42]
Ba/Ir/WO₃-SiO₂	[NO]=0.05%,[CO]=0.3%,[O₂]=5%,[SO₂]=1μL/L,[H₂O]=6%,He平衡气, GHSV=60000h^-1	260	100	—	[36]