氢气辅助HC-SCR脱硝性能和作用机制的研究进展

doi:10.16085/j.issn.1000-6613.2023-1735

摘要/Abstract

摘要：

柴油发动机尾气是氮氧化物（NO _x ）主要来源之一，烃类化合物（HC）选择催化还原氮氧化物（HC-SCR）技术是一种常见的脱除氮氧化物方法，但是在HC-SCR催化还原NO _x 中，Ag基氧化物催化剂的低温脱硝活性较差，活性温度窗口较窄。在HC-SCR反应气氛中添加少量氢气（H₂）能显著提升Ag/γ-Al₂O₃等催化剂的低温脱硝活性，拓宽活性温度窗口。本文以贫燃柴油发动机尾气脱硝为背景，归纳了H₂对活性中心Ag物种种类、烃类化合物和氧气的活化以及活性含氮中间体转化的影响，总结了H₂在提升HC-SCR催化剂抗硫和抗水性能起到的作用，列举了近年来新型催化剂在H₂辅助HC-SCR（H₂-HC-SCR）脱硝体系中的应用。相关研究表明H₂促进HC-SCR中具有催化活性的Ag物种的生成，促进O₂活化为活性氧物种，加速烃类化合物转化为异氰酸盐、烯醇物种等关键中间体，并减少可毒化活性中心硝酸盐物种的含量，从而提高HC-SCR脱硝活性。H₂辅助HC-SCR脱硝技术有望在机动车尾气脱硝中发挥重要作用，推动HC-SCR脱硝技术的发展。

关键词: 选择催化还原, 氢气, 活化, 低温脱硝活性, 催化剂

Abstract:

Diesel engine exhaust is one of the sources of nitrogen oxides (NO _x ). Hydrocarbon (HC) selective catalytic reduction (HC-SCR) of nitrogen oxides is a common technique for NO _x reduction. However, the NO _x reduction activity of Ag-based oxide catalysts is not sufficiently high in low temperature region and the active temperature window is narrow. The addition of small amounts of hydrogen (H₂) in HC-SCR reaction atmosphere can significantly increase the low-temperature denitrification activity and broaden the active temperature window of catalysts such as Ag/γ-Al₂O₃. Based on the background of lean-burn diesel engine exhaust denitration, the aim of this review is to summarize the effects of H₂ on the types of active Ag species, the activation of hydrocarbons and oxygen, and the conversion of active nitrogen-containing intermediates. The role of H₂ in improving the sulfur and water resistance of HC-SCR catalysts is summarized, and the application of new catalysts in H₂-assisted HC-SCR (H₂-HC-SCR) reaction in recent years is introduced as well. Relevant studies have shown that H₂ promotes the formation of the active Ag species in HC-SCR and the activation of O₂ into reactive oxygen species. H₂ also accelerates the conversion of hydrocarbons into key intermediates such as isocyanate and enolic surface species and reduces the content of nitrate species which would poison the catalytic active sites. Blending H₂ into the feed of the HC-SCR eventually improves the denitrification activity of HC-SCR. H₂-assisted HC-SCR denitration technology is expected to play an important role in the denitration of motor vehicle exhaust, and to promote the development of HC-SCR of nitrogen oxides technology.

Key words: selective catalytic reduction (SCR), hydrogen, activation, low-temperature denitrification activity, catalyst

中图分类号:

O643.31

周强, 殷成阳, 刘百军, 赵震. 氢气辅助HC-SCR脱硝性能和作用机制的研究进展[J]. 化工进展, 2024, 43(11): 6140-6154.

ZHOU Qiang, YIN Chengyang, LIU Baijun, ZHAO Zhen. Research progress on the performance and mechanism of H₂-assisted HC-SCR denitration[J]. Chemical Industry and Engineering Progress, 2024, 43(11): 6140-6154.

图/表 14

表1 不同柴油发动机负荷下的实际尾气物质组成（体积分数）[35]

发动机操作条件

O₂/%

CO/%

CO₂/%

H₂/%

HC/%

NO _x /%

H₂O^①/%

发动机尾气温度/℃

发动机负荷25% 发动机转速1500r/min 平均指示缸内压力0.3MPa

发动机负荷50% 发动机转速1500r/min 平均指示缸内压力0.43MPa

发动机负荷75% 发动机转速1500r/min

平均指示缸内压力0.59MPa

图1 Ag/γ-Al2O3和Co/γ-Al2O3催化剂上C3H6-SCR氧化还原机理的多种可能反应路径[42]

图2 C3H6-SCR反应中Ag/γ-Al2O3催化剂不同Ag活性中心上NO转化机理[44]

图3 HC-SCR中引入H2对Ag/γ-Al2O3催化剂上活性中心结构和反应动力学的影响[54]

图4 Ag/γ-Al2O3催化剂上H2促进HC-SCR的反应机理[55]

图5 H2促进Ag-MFI催化剂C3H8-SCR脱硝的机理[60]

图6 H2促进Ag/γ-Al2O3催化剂C2H5OH-SCR的机理[64]

图7 H2促进硝酸盐物种转化为NO2中间体的反应机理[19]

图8 Ag（质量分数2.5%）-Zn（质量分数2.5%）Mg/γ-Al2O3催化剂上H2-C3H6-SCR反应机理[18]

表2 H2对Ag基催化剂HC-SCR脱硝活性的影响

序号	催化剂种类	基本反应条件	[H₂]^①/%	X_NOmax^②/%-T_NOmax^③/℃	T₅₀^④/℃	∆T₅₀^⑤/℃	参考文献
1	2%Ag/γ-Al₂O₃	0.1%NO/0.15%C₃H₆/10% O₂/Ar	0	约92-400	约350	约50	[15]
1	2%Ag/γ-Al₂O₃	0.1%NO/0.15%C₃H₆/10% O₂/Ar	0.1	约95-400	约300	约50	[15]
2	1%Ag/γ-Al₂O₃ （未水热老化）	0.05%NO/0.1333%C₃H₆/8% O₂/0.05%CO/5 %H₂O/N₂	0	约92-450	约410	约170	[16]
2	1%Ag/γ-Al₂O₃ （未水热老化）	0.05%NO/0.1333%C₃H₆/8% O₂/0.05%CO/5 %H₂O/N₂	1	约100-300	约240	约170	[16]
3	2%Ag/γ-Al₂O₃-WO _x	0.05%NO/0.0625%C₃H₈/0.02%CO/2% O₂/N₂	0	约80-450	约410	约260	[84]
3	2%Ag/γ-Al₂O₃-WO _x	0.05%NO/0.0625%C₃H₈/0.02%CO/2% O₂/N₂	0.066	约65-170	约150	约260	[84]
4	2%Ag/CeZr_0.4	0.07%NO/0.07%C₃H₆/3% O₂/Ar	0	约72-350	约225	约50	[8]
4	2%Ag/CeZr_0.4	0.07%NO/0.07%C₃H₆/3% O₂/Ar	0.5	约86-400	约175	约50	[8]
5	2%Ag-Ce_0.4ZrO_2-_δ	0.1% NO/0.1% C₃H₆/10% O₂/He	0	约70-320	约220	约40	[80]
5	2%Ag-Ce_0.4ZrO_2-_δ	0.1% NO/0.1% C₃H₆/10% O₂/He	10	约82-500	约180	约40	[80]

图9 Pt/Ce0.5Zr0.5O2-δ 催化剂上C3H6/H2-SCR机理[85]

表3 H2对贵金属催化剂HC-SCR脱硝活性的影响

序号	催化剂种类	反应条件	[H₂]/%	T_max^①/℃	(X_NO_x_toN2)_max^②/%	参考文献
1	0.5%Pt/γ-Al₂O₃	0.1%NO/0.1% C₃H₆/2% O₂/Ar	0	约220	约25	[7]
1	0.5%Pt/γ-Al₂O₃	0.1%NO/0.1% C₃H₆/2% O₂/Ar	0.5	约110	约72	[7]
2	0.5%Ir/γ-Al₂O₃	0.1%NO/0.1% C₃H₆/2% O₂/Ar	0	约325	约20	[7]
2	0.5%Ir/γ-Al₂O₃	0.1%NO/0.1% C₃H₆/2% O₂/Ar	0.5	约280	约60	[7]
3	0.07g Au(1.6%)/γ-Al₂O₃+0.30g γ-Al₂O₃	0.037%NO/0.04%C₃H₆/8% O₂/He	0	400	约30	[86]
3	0.07g Au(1.6%)/γ-Al₂O₃+0.30g γ-Al₂O₃	0.037%NO/0.04%C₃H₆/8% O₂/He	0.21	400	约43	[86]
4	0.5%Au/γ-Al₂O₃	0.0385%NO _x (~96% NO)/0.04%C₃H₆/8% O₂/He	0	约400	约39	[87]
4	0.5%Au/γ-Al₂O₃	0.0385%NO _x (~96% NO)/0.04%C₃H₆/8% O₂/He	0.21	约390	约57	[87]

表4 H2-HC-SCR催化剂的活性对比

催化剂	反应条件	烃类化合物种类	温度/℃	(X_NO $x$ _toN $2$ )_max/%		参考文献
催化剂	反应条件	烃类化合物种类	温度/℃	不添加H₂	添加H₂	参考文献
γ-Al₂O₃	R#1	C₃H₈	500	15	35	[62]
2%Ag/γ-Al₂O₃	R#1	C₃H₈	300	0	36	[62]
2%Ag/TiO₂	R#1	C₃H₈	500	3	3	[62]
2%Ag/Ga₂O₃	R#1	C₃H₈	500	34	12	[62]
2%Co/γ-Al₂O₃	R#1	C₃H₈	350	12	10	[62]
0.5%Pt/γ-Al₂O₃（Engelhard公司生产）	R#1	C₃H₈	325	8	6	[62]
0.5%Pt/γ-Al₂O₃（初湿浸渍法）	R#2	C₃H₆	约110	约0	约72	[7]
0.5%Pd/γ-Al₂O₃	R#2	C₃H₆	200	约12	约16	[7]
0.5%Ir/γ-Al₂O₃	R#2	C₃H₆	约280	约0	约61	[7]

表4 H2-HC-SCR催化剂的活性对比

催化剂	反应条件	烃类化合物种类	温度/℃	(X_NO $x$ _toN $2$ )_max/%		参考文献
催化剂	反应条件	烃类化合物种类	温度/℃	不添加H₂	添加H₂	参考文献
γ-Al₂O₃	R#1	C₃H₈	500	15	35	[62]
2%Ag/γ-Al₂O₃	R#1	C₃H₈	300	0	36	[62]
2%Ag/TiO₂	R#1	C₃H₈	500	3	3	[62]
2%Ag/Ga₂O₃	R#1	C₃H₈	500	34	12	[62]
2%Co/γ-Al₂O₃	R#1	C₃H₈	350	12	10	[62]
0.5%Pt/γ-Al₂O₃（Engelhard公司生产）	R#1	C₃H₈	325	8	6	[62]
0.5%Pt/γ-Al₂O₃（初湿浸渍法）	R#2	C₃H₆	约110	约0	约72	[7]
0.5%Pd/γ-Al₂O₃	R#2	C₃H₆	200	约12	约16	[7]
0.5%Ir/γ-Al₂O₃	R#2	C₃H₆	约280	约0	约61	[7]

图10 Ag/γ-Al2O3和Pd/γ-Al2O3催化剂在不同还原气氛下的脱硝活性[16](基本反应条件：[NO]=0.05%，[O2]=8%，[CO]=0.05%，[H2O]=5%；H2–SCR：[H2]=1%；C3H6–SCR：[C3H6]=0.1333%；H2-C3H6–SCR：[H2]=1%，[C3H6]=0.1333%)

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