Hydrotalcite-derived CuMgFe-LDO catalyst for simultaneous abatement of nitrogen oxides and methanol

doi:10.11949/0438-1157.20240155

Abstract

Abstract:

The simultaneous abatement of NO _x and volatile organic compounds (VOCs) by NH₃-SCR catalysts has attracted lots of attention. However, the presence of VOCs can have negative impact on deNO _x efficiency especially at low temperatures. In this study, hydrotalcite-derived composite oxide (Cu) MgFe-LDO catalysts were selected to explore the simultaneous removal of NO _x and methanol, focusing on the introduction of Cu and the influence of CuO _x and FeO _x interaction on the synergistic reaction, and the prepared catalysts were characterized and tested. The results showed that the deNO _x activity of Cu-containing catalysts was higher than that of MgFe-LDO catalysts, and the optimal catalyst Cu_0.5MgFe-LDO exhibits the best catalytic activity for both NH₃-SCR and methanol oxidation in the temperature window of 230—300℃.The appropriate introduction of Cu strengthens the interaction between Cu and Fe species, which is conducive to the redox cycle, resulting in more oxygen defects and reactive oxygen species. Excessive Cu doping will destroy the catalyst structure and reduce the surface acidity. The introduction of Cu can slow down the inhibitory effect of methanol on the SCR reaction. These results can provide useful guidance for the practical application of SCR catalysts for synergistic removal of VOCs.

Key words: LDHs, CuMgFe-LDO, methanol oxidation, NH₃-SCR, simultaneous removal

摘要：

NH₃-SCR催化剂同时去除NO _x 和挥发性有机物（VOCs）引起了人们的广泛关注，然而，VOCs的存在会对脱硝反应产生负面影响，尤其在低温条件下。本研究选定水滑石衍生复合氧化物（Cu）MgFe-LDO催化剂探索协同脱除NO _x 和甲醇性能，着重考察Cu的引入以及CuO _x 和FeO _x 相互作用对协同反应的影响，并对所制备的催化剂进行表征测试。结果表明，含Cu催化剂的脱硝活性均高于MgFe-LDO催化剂，最佳催化剂Cu_0.5MgFe-LDO在230~300℃温窗内具有较好的脱硝活性和甲醇氧化性能。适量引入Cu加强了Cu、Fe物种间的相互作用，有利于氧化还原循环，从而产生更多的氧缺陷及活性氧，过量Cu掺杂会破坏催化剂结构，降低表面酸性，引入Cu可以减缓甲醇对SCR反应的抑制作用。这些结果可为实际应用SCR催化剂协同去除VOCs提供指导。

关键词: 类水滑石, CuMgFe-LDO, 甲醇氧化, NH₃-SCR, 协同脱除

CLC Number:

TQ 032.4

Xinxin XU, Yunli JI, Xianfeng WU, Xia AN, Xu WU. Hydrotalcite-derived CuMgFe-LDO catalyst for simultaneous abatement of nitrogen oxides and methanol[J]. CIESC Journal, 2024, 75(5): 1890-1902.

徐欣欣, 冀芸丽, 武鲜凤, 安霞, 吴旭. 水滑石衍生CuMgFe-LDO催化剂协同净化氮氧化物和甲醇[J]. 化工学报, 2024, 75(5): 1890-1902.

Figures/Tables 15

Fig.1 XRD patterns and FT-IR spectra of series precursors， and SEM images of MgFe-LDH, Cu0.5MgFe-LDH, Cu1MgFe-LDH, Cu2.5MgFe-LDH

Fig.2 NO x conversion, methanol conversion,N2 selectivity,CO2 selectivity over different catalysts [reaction conditions: 500 mg/L NO x, 500 mg/L NH3, 750 mg/L methanol, 5% O2 and N2 as balance, GHSV=30000 ml/(g·h)]

Fig.3 XRD patterns of MgFe-LDO,Cu1MgFe-LDO,Cu0.5MgFe-LDO,Cu2.5MgFe-LDO

Fig.4 N2 adsorption-desorption isotherms and pore size distribution of catalysts

Table 1 The specific surface area， pore diameter and pore volume of catalysts

催化剂	比表面积/ (m²/g)	孔径/nm	孔容/(cm³/g)
MgFe-LDO	62.6	8.8	0.2
Cu_0.5MgFe-LDO	38.1	16.4	0.2
Cu₁MgFe-LDO	31.8	11.8	0.1
Cu_2.5MgFe-LDO	19.7	22.6	0.1

Fig.5 NH3-TPD profiles of catalysts

Table 2 NH3 desorption results of catalysts

催化剂	NH₃相对吸附量	NH₃脱附比例/%
催化剂	NH₃相对吸附量	弱酸	强酸
MgFe-LDO	1.0	100	－
Cu_0.5MgFe-LDO	0.7	30	70
Cu₁MgFe-LDO	0.6	34	66
Cu_2.5MgFe-LDO	0.2	96	4

Fig.6 H2-TPR profiles of catalysts

Fig.7 O2-TPD profiles of catalysts

Table 3 Analysis of O2-TPD data for various catalysts

催化剂	表面元素物种/%			总氧物种脱附量
催化剂	O_ɑ	O_β	O_γ	总氧物种脱附量
Mg₃Fe₁-LDO	28.8	1.8	69.4	1
Cu_0.5MgFe-LDO	37.7	60.5	1.8	0.8
Cu₁Mg₂Fe₁-LDO	43.1	49.5	7.4	0.6
Cu_2.5Mg_0.5Fe₁-LDO	32.7	67.3	—	0.5

Fig.8 XPS spectra of catalysts

Table 4 XPS analysis of different catalysts

催化剂	相对浓度比/%
催化剂	Cu⁺/(Cu⁺+Cu²⁺)	Fe³⁺/(Fe³⁺+Fe²⁺)	O_β/(O_α+O_β)
MgFe-LDO	—	40	58
Cu_0.5MgFe-LDO	51	61	71
Cu₁MgFe-LDO	56	59	51
Cu_2.5MgFe-LDO	65	58	50

Fig.9 Effects of methanol on NO x conversion and N2 selectivity [reaction condition: 500 mg/L NO, 500 mg/L NH3, 750 mg/L methanol, 5% O2 and N2 as balance, GHSV=30000 ml/(g·h)]

Fig.10 Effects of SCR gas components on methanol conversion and CO2 selectivity [reaction condition: 500 mg/L NO, 500 mg/L NH3,750 mg/L methanol, 5% O2 and N2 as balance, GHSV = 30000 ml/(g·h)]

Fig.11 In situ DRIFTs spectra of synergistic reaction process (reaction condition: 500 mg/L NO x, 500 mg/L NH3, 750 mg/L methanol, 5% O2 and N2)

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