Cu/Ce负载对赤泥脱除中低温烟气中NO的促进作用

李扬; 徐博; 杨赫; 靳立军; 胡浩权

doi:10.1016/S1872-5813(23)60388-3

Cu/Ce负载对赤泥脱除中低温烟气中NO的促进作用

doi: 10.1016/S1872-5813(23)60388-3

大连理工大学化工学院煤化工研究设计所精细化工国家重点实验室辽宁大连 116024

基金项目: 国家重点研发计划(2018YFB0605104),国家自然科学基金(22278066)和中央高校基本科研业务费(DUT2021TB03)资助

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通讯作者:
E-mail: hhu@dlut.edu.cn，Tel: 0411-84986157

中图分类号: X511
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出版历程
- 收稿日期: 2023-05-04
- 修回日期: 2023-06-24
- 录用日期: 2023-06-25
- 网络出版日期: 2023-10-31

Promotion of Cu/Ce Supported Red Mud for NO Removal from Low and Medium Flue Gas

State Key Laboratory of Fine Chemicals, Institute of Coal Chemical Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China

Funds: The project was supported by National Key R&D Program of China (2018YFB0605104), National Natural Science Foundation of China (22278066) and The Fundamental Research Funds for the Central Universities (DUT2021TB03)

摘要

摘要: 赤泥是制铝工业的固体废弃物，具有一定的环境危害，但研究表明其可作为NO_x选择性催化还原(SCR)催化剂的替代品。通过对赤泥酸洗处理能够改善赤泥的碱性和表面性质，提高其对NO_x的转化率。本文采用对酸洗赤泥催化剂进行Cu、Ce、Cu/Ce浸渍负载，并研究了金属改性赤泥对烟气中NO_x的催化转化性能。研究结果表明，Cu负载催化剂中的Cu⁺与Cu^{2 +}，有效促进了赤泥对低温烟气(200–300 ℃)中的NO转化率，Cu的负载量达到6%时，赤泥的最高NO转化率达到了90.7%；而Ce负载催化剂中的Ce^{3 +}与Ce^{4 +}，有效促进了赤泥对中温烟气(200–400 ℃)中的NO转化率，Ce的负载量达到8%时，赤泥的最高NO转化率达到了94.0%；Cu/Ce负载催化剂表现出比单金属负载催化剂更好的低温NO转化率，最佳的负载Cu:Ce比例为1∶1，双金属负载催化剂表现出比Cu负载催化剂更好的中温(300–400 ℃)中的NO转化率，最高达到了95.5%。其原因可能是，在Cu/Ce协同作用下，Cu⁺以及Cu^{2 +}的还原过程分别从229 ℃、302 ℃降至201 ℃以及247 ℃，同时使发生Fe₂O₃→FeO的还原过程的温度降低，促使ACRM-Cu1Ce1具有更强的低温氧化还原能力，同时，双金属负载使催化剂具有更高的弱酸性峰，也使催化剂的强、弱酸性峰都向低温偏移，并使负载后的赤泥具有了较高的Fe离子平均氧化态以及较高的Cu⁺含量，促进了赤泥催化剂对低温NO的转化率。
- 赤泥 /
- SCR /
- Cu /
- Ce /
- 负载
Abstract: Red mud is a solid waste in aluminum industry and has been proven to be an efficient alternative to NO_x selective catalytic reduction (SCR) catalysts. Acid washing treatment to red mud can improve its alkalinity and surface properties, and increase the conversion rate of NO_x. In this paper, Cu, Ce, and Cu/Ce was supported on acid washed red mud and NO_x catalytic conversion performance on metal modified red mud catalysts was studied. The research results indicate that the Cu⁺ and Cu^{2 +} in the Cu-loaded catalyst effectively promoted the NO conversion of red mud to low-temperature flue gas (200−300 ℃), and the highest NO conversion of red mud reached 90.7% at a loading of 6% of Cu; while the Ce^{3 +} and Ce^{4 +} in the Ce-loaded catalyst promoted the NO conversion of red mud to medium-temperature flue gas (200−400 ℃), and the highest NO conversion of red mud reached 94.7% at a loading of 8% of Ce. The Ce^{3 +} and Ce^{4 +} in the Ce-loaded catalyst effectively promoted the NO conversion of red mud to medium-temperature flue gas (200−400 ℃), and the maximum NO conversion of red mud reached 94.0% with a Ce loading of 8%; the Cu/Ce-loaded catalyst showed a better low-temperature NO conversion than that of the single-metal-loaded catalyst, and the optimal loading ratio of Cu:Ce was 1∶1, and the bimetallic-loaded catalyst showed better low-temperature NO conversion than that of the Cu-loaded catalyst. The optimum loading Cu:Ce ratio was 1∶1, and the bimetallic-loaded catalysts showed better NO conversion at medium temperatures (300−400 ℃) than the Cu-loaded catalysts, with a maximum of 95.5%. The reason may be that, under the synergistic effect of Cu/Ce, the reduction process of Cu⁺ as well as Cu^{2 +} was reduced from 229 ℃ and 302 ℃ to 201 ℃ and 247 ℃, respectively, and at the same time, the temperature at which the Fe₂O₃→FeO reduction process occurred was lowered, which contributed to the stronger low-temperature redox ability of ACRM-Cu1Ce1, and at the same time, the bimetallic loading enabled the catalyst to have higher weak acidity peaks, which also shifted both the strong and weak acidic peaks of the catalyst to low temperature, and gave the loaded red mud a higher average oxidation state of Fe ions as well as a higher Cu⁺ content, which promoted the conversion of the red mud catalyst to low-temperature NO.
- red mud /
- scr /
- cu /
- ce /
- supporting

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图 1 实验装置流程示意图

Figure 1 Schematic diagram of experimental apparatus

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图 2 Cu负载量对催化剂的NO转化率的影响(BFG)

Figure 2 The effect of Cu supporting on the NO conversion rate of catalysts catalyst (BFG)

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图 3 Ce负载量对催化剂的NO转化率的影响(BFG)

Figure 3 The effect of Ce supporting on the NO conversion rate of catalysts catalyst (BFG)

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图 4 Cu/Ce负载比例对催化剂的NO转化率的影响(BFG)

Figure 4 The effect of Cu/Ce supporting ratio on the NO conversion rate of catalysts(BFG)

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图 5 不同催化剂的NO转化率(BFG)

Figure 5 NO conversion rate of different catalysts (BFG)

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图 6 负载金属催化剂的等温吸附曲线与孔径分布(a)、(b)、(c)分别是Cu负载、Ce负载以及Cu/Ce负载催化剂的等温吸附曲线；(d)、(e)、(f)分别是对应催化剂的孔径分布

Figure 6 Isothermal adsorption curves and pore size distribution of the loaded catalysts (a), (b) and (c) are the isothermal adsorption curves of Cu loaded, Ce loaded and Cu/Ce loaded catalysts, respectively; (d), (e) and (f) are the pore size distribution of the corresponding catalysts

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图 7 负载催化剂的XRD图谱

Figure 7 XRD of supported catalyst

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图 8 负载催化剂的H₂-TPR图

Figure 8 H₂-TPR diagram of supported catalyst

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图 9 负载催化剂的NH₃-TPD图

Figure 9 NH₃-TPR diagram of supported catalyst

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图 10 负载催化剂的Fe 2p谱图

Figure 10 Fe 2p spectrum of supported catalyst (a) ACRM;(b) ACRM-Cu6;(c) ACRM-Ce8;(d) ACRM-Cu1Ce1

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图 11 金属负载催化剂的Cu 2p谱图

Figure 11 Cu 2p spectrum of supported catalyst (a) ACRM-Cu6;(b) ACRM-Cu1Ce1

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图 12 金属负载催化剂的Ce 3d谱图

Figure 12 Ce 3d spectrum of supported catalyst (a) ACRM-Ce8;(b) ACRM-Cu1Ce1

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图 13 负载催化剂的O 1s谱图

Figure 13 O 1s spectrum of supported catalyst (a) ACRM;(b) ACRM-Cu6;(c) ACRM-Ce8;(d) ACRM-Cu1Ce1

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表 1 赤泥的组成分析

Table 1 Analysis of the composition of red mud

Sample	Fe₂O₃	Al₂O₃	SiO₂	TiO₂	Na₂O	Others
RM	42.0	21.3	22.5	3.7	6.9	3.6

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表 2 催化剂的比表面积与孔径分布

Table 2 Surface area and pore size distribution of catalysts

Sample	S_BET m²·g⁻¹	V_t cm³·g⁻¹	D_ave nm
ACRM-Cu1	51	0.155	9.3
ACRM-Cu2	53	0.168	9.8
ACRM-Cu4	45	0.149	9.7
ACRM-Cu6	44	0.156	10.3
ACRM-Cu8	42	0.149	14.2
ACRM-Ce1	50	0.172	9.8
ACRM-Ce2	54	0.162	9.6
ACRM-Ce4	49	0.148	9.4
ACRM-Ce6	49	0.147	9.6
ACRM-Ce8	50	0.137	9.2
ACRM-Cu3Ce1	42	0.146	10.7
ACRM-Cu2Ce1	41	0.154	11.5
ACRM-Cu1Ce1	43	0.137	10.1
ACRM-Cu1Ce2	45	0.139	10.0
ACRM-Cu1Ce3	48	0.143	9.4

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