双金属改性多壁碳纳米管联合吸附SO2与NO的实验研究

doi:10.12422/j.issn.1672-6952.2025.03.004

摘要/Abstract

摘要：

采用溶胶凝胶法制备了双金属Cu与Ni掺杂TiO₂改性多壁碳纳米管（MWCNTs/Cu?Ni?TiO₂）新型吸附材料，并对该新型材料进行了脱硫脱硝实验；在n（Cu）/n（Ni）=2的条件下，探究了O₂体积分数、水蒸气体积分数和体积空速等因素对改性多壁碳纳米管联合脱硫脱硝性能的影响，并对材料的吸附性能进行了评价。结果表明，双金属改性的多壁碳纳米管的联合脱硫脱硝性能明显优于单种金属改性的材料，且对SO₂的吸附量明显提升；当模拟烟气的SO₂质量浓度为3 140 mg/m³、NO质量浓度为736 mg/m³时，在水蒸气体积分数为5%、O₂体积分数为8%、体积空速为2 598 h^-1的工况下，双金属改性材料吸附效果最佳，SO₂的最佳吸附量为20.43 mg/g，NO的最佳吸附量为0.86 mg/g。

关键词: 金属改性, 多壁碳纳米管, 脱硫脱硝, 吸附量

Abstract:

A novel adsorption material of bimetallic Cu and Ni?doped TiO₂?modified carbon nanotubes was prepared by sol?gel methodmethod,and experiments on simultaneous desulfurization and denitrification were carried out.The effects of O₂ volume fraction,H₂O volume fraction and volume airspeed on desulfurization and denitrification were studied,Under the condition of a molar ratio of Cu to Ni of 2.The results showed that the adsorption capacity of MWCNTs/Cu?Ni?TiO₂ was significantly better than that of single?metal modified materials. Under the condition of simulating flue gas, the adsorption effect of the bimetallic modified material was the best when the mass concentration of SO₂ was 3 140 mg/m³, the mass concentration of NO was 736 mg/m³, the volume fraction of water vapor was 5%, the fraction of O₂ was 8%, and the volume space velocity was 2 598 h^-1. The optimal adsorption amount of SO₂ was 20.43 mg/g, and the optimal adsorption amount of NO was 0.86 mg/g.

Key words: Metal modification, Multi?walled carbon nanotubes, Desulfurization and denitrification, Adsorption capacity

中图分类号:

O647

庄博涵, 建伟伟, 海秋岩, 刘天强. 双金属改性多壁碳纳米管联合吸附SO₂与NO的实验研究[J]. 辽宁石油化工大学学报, 2025, 45(3): 26-33.

Bohan ZHUANG, Weiwei JIAN, Qiuyan HAI, Tianqiang LIU. Experimental Study on the Combined Adsorption of SO₂ and NO by Bimetallic Modified Multi⁃Walled Carbon Nanotubes[J]. Journal of Liaoning Petrochemical University, 2025, 45(3): 26-33.

图/表 8

图1 联合脱硫脱硝实验装置示意图注：1、2为N2瓶；3为O2瓶；4为SO2和NO混合器；5、6、7、8为质量流量计；9为阀门；10为混合室；11为恒温水浴箱；12为磨口石英塞；13为石英外管；14为石英内管；15为高压汞灯；16为吸附剂；17为环形带孔石英板；18为烟气分析仪；19为数据采集器；20为尾气处理装置。

Fig.1 Diagram of the combined desulfurization and denitrification experimental setup

图2 不同样品的TEM图像(n（Cu）/n（Ni）=2) (n（Cu）/n（Ni）=2，放大图)

Fig.2 TEM images of different samples

图3 MWCNTs/Cu?Ni?TiO2样品的XPS表征（a） XPS宽扫谱图（b） Cu 2p轨道的窄谱扫描（c） Ni 2p轨道的窄谱扫描

Fig.3 XPS characterization of MWCNTs/Cu?Ni?TiO2 samples

表1 联合脱硫脱硝实验工况设计

Table 1 Design of joint desulfurization and denitrification experiment conditions

样品	$φ$ （O₂）/%	$φ$ （水蒸气）/%	体积空速/h^-1
MWCNTs/Cu⁃Ni⁃TiO₂	0、3、6、8、10	5	2 598
MWCNTs/Cu⁃Ni⁃TiO₂	8	0、1、3、5、8	2 598
MWCNTs/Cu⁃Ni⁃TiO₂	8	5	1 559~3 543
MWCNTs/Cu⁃TiO₂	8	5	2 598
MWCNTs/Ni⁃TiO₂	8	5	2 598

表1 联合脱硫脱硝实验工况设计

Table 1 Design of joint desulfurization and denitrification experiment conditions

样品	$φ$ （O₂）/%	$φ$ （水蒸气）/%	体积空速/h^-1
MWCNTs/Cu⁃Ni⁃TiO₂	0、3、6、8、10	5	2 598
MWCNTs/Cu⁃Ni⁃TiO₂	8	0、1、3、5、8	2 598
MWCNTs/Cu⁃Ni⁃TiO₂	8	5	1 559~3 543
MWCNTs/Cu⁃TiO₂	8	5	2 598
MWCNTs/Ni⁃TiO₂	8	5	2 598

图4 不同吸附剂对SO2与NO的吸附量

Fig.4 Adsorption capacity of SO2 and NO by different adsorbents

图5 水蒸气体积分数对MWCNTs/Cu?Ni?TiO2吸附SO2、NO性能的影响

Fig.5 Effect of water vapor volume fraction on the adsorption performance of MWCNTs/Cu?Ni?TiO2 for SO2, NO

图6 O2体积分数对MWCNTs/Cu?Ni?TiO2吸附SO2、NO性能的影响

Fig.6 Effect of O2 volume fraction on the adsorption performance of MWCNTs/Cu?Ni?TiO2 for SO2, NO

图7 O2体积空速对MWCNTs/Cu?Ni?TiO2吸附SO2、NO性能的影响

Fig.7 Effect of volume airspeed on the adsorption performance of MWCNTs/Cu?Ni?TiO2 for SO2, NO

参考文献 30

1	戴宝华，王德亮，曹勇，等. 2022年中国能源行业回顾及2023年展望［J］. 当代石油石化， 2023， 31（1）： 2⁃9.
	DAI B H， WANG D L， CAO Y， et al. China's energy industry： 2022 review and 2023 prospect［J］. Petroleum & Petrochemical Today， 2023， 31（1）： 2⁃9.
2	IIJIMA S. Helical microtubules of graphitic carbon［J］. Nature， 1991， 354（6348）： 56⁃58.
3	SALEH T A. The influence of treatment temperature on the acidity of MWCNT oxidized by HNO₃ or a mixture of HNO₃/H₂SO₄［J］. Applied Surface Science， 2011， 257（17）： 7746⁃7751.
4	LEHMAN J H， TERRONES M， MANSFIELD E， et al. Evaluating the characteristics of multiwall carbon nanotubes［J］. Carbon， 2011， 49（8）： 2581⁃2602.
5	FERNÁNDEZ⁃CATALÁ J， NAVLANI⁃GARCÍA M， VERMA P， et al. Photocatalytically⁃driven H₂ production over Cu/TiO₂ catalysts decorated with multi⁃walled carbon nanotubes［J］. Catalysis Today， 2021， 364： 182⁃189.
6	TOLOMAN D， POPA A， STAN M， et al. Visible⁃light⁃driven photocatalytic degradation of different organic pollutants using Cu doped ZnO⁃MWCNT nanocomposites［J］. Journal of Alloys and Compounds， 2021， 866： 159010.
7	DHODAMANI A G，MORE K V， PATIL S M，et al. Synergistics of Cr（Ⅲ） doping in TiO₂/MWCNTs nanocomposites： Their enhanced physicochemical properties in relation to photovoltaic studies［J］. Solar Energy， 2020， 201： 398⁃408.
8	VATANDOUST L，HABIBI A，NAGHSHARA H，et al.Fabrication of ZnO⁃MWCNT nanocomposite sensor and investigation of its ammonia gas sensing properties at room temperature［J］. Synthetic Metals， 2021， 273： 116710.
9	王雪，建伟伟，陆毅，等.Cu和Sn改性多壁碳纳米管对VOCs气体的吸附［J］.辽宁石油化工大学学报，2021，41（5）： 44⁃49.
	WANG X， JIAN W W， LU Y， et al. Adsorption of VOCs using MWCNTs modified with Cu and Sn［J］. Journal of Liaoning Petrochemical University， 2021， 41（5）： 44⁃49.
10	汤佳玉，孔鹏飞，鞠佳，等. 不同结构碳纳米管吸附胆红素的研究［J］. 辽宁石油化工大学学报， 2021， 41（5）： 38⁃43.
	TANG J Y， KONG P F， JU J， et al. Adsorption of bilirubin by carbon nanotubes with different structures［J］. Journal of Liaoning Petrochemical University， 2021， 41（5）： 38⁃43.
11	DARAEE M， BANIADAM M， RASHIDI A， et al. Doping transition metals into TiO₂⁃CNT nanocatalyst to enhance the selective oxidation of H₂S［J］. ChemistrySelect， 2020， 5（36）： 11242⁃11256.
12	RODRÍGUEZ V， CAMARILLO R， MARTÍNEZ F， et al. CO₂ photocatalytic reduction with CNT/TiO₂ based nanocomposites prepared by high⁃pressure technology［J］. The Journal of Supercritical Fluids， 2020， 163： 104876.
13	ZHANG Y， WIBOWO H， ZHONG L， et al. Cu⁃BTC⁃based composite adsorbents for selective adsorption of CO₂ from syngas［J］. Separation and Purification Technology， 2021， 279： 119644.
14	RAJA S， ALPHIN M S， SIVACHANDIRAN L， et al. TiO₂⁃carbon nanotubes composite supported MnOx⁃CuO catalyst for low⁃temperature NH₃⁃SCR of NO： Investigation of SO₂ and H₂O tolerance［J］. Fuel， 2022， 307： 121886.
15	BAO J J， DAI Y， LIU H， et al. Photocatalytic removal of SO₂ over Mn doped titanium dioxide supported by multi⁃walled carbon nanotubes［J］. International Journal of Hydrogen Energy， 2016， 41（35）： 15688⁃15695.
16	YANG Y C， JIA F R， JIAN W W， et al. Influence of Cr³⁺concentration on SO₂ removal over TiO₂ based multi⁃walled carbon nanotubes［J］. China Petroleum Processing & Petrochemical Technology， 2019， 21（1）： 23⁃35.
17	RAJA S， ALPHIN M S. Systematic effects of Fe doping on the activity of V₂O₅/TiO₂⁃carbon nanotube catalyst for NH₃⁃SCR of NOx［J］. Journal of Nanoparticle Research， 2020， 22（7）： 190.
18	SUN Y， JIAN W W， TONG S Q， et al. Study on photocatalytic desulfurization and denitrification performance of Cu⁃and Cr⁃modified MWCNT［J］. Processes， 2021， 9（10）： 1823.
19	EVERHART B M， MCAULEY B， AL MAYYAHI A， et al. Photocatalytic NOx mitigation under relevant conditions using carbon nanotube⁃modified titania［J］. Chemical Engineering Journal， 2022， 446（Part 1）： 136984.
20	DARVISH S M， ALI A M， SANI S R. Designed air purifier reactor for photocatalytic degradation of CO₂ and NO₂ gases using MWCNT/TiO₂ thin films under visible light irradiation［J］. Materials Chemistry and Physics， 2020， 248： 122872.
21	SEZER N， KOÇ M. Oxidative acid treatment of carbon nanotubes［J］. Surfaces and Interfaces， 2019， 14： 1⁃8.
22	杨彦春. 工业烟气干法脱硫关键技术基础研究［D］. 抚顺：辽宁石油化工大学， 2019.
23	WANG Z Y， GUO R T， SHI X， et al. The enhanced performance of Sb⁃modified Cu/TiO₂ catalyst for selective catalytic reduction of NOx with NH₃［J］. Applied Surface Science， 2019， 475： 334⁃341.
24	LIANG H Y， LIN J H， JIA H N， et al. Hierarchical NiCo⁃LDH@NiOOH core⁃shell heterostructure on carbon fiber cloth as battery⁃like electrode for supercapacitor［J］. Journal of Power Sources， 2018， 378： 248⁃254.
25	TUDU B， NALAJALA N， SAIKIA P， et al. Cu–Ni bimetal integrated TiO₂ thin film for enhanced solar hydrogen generation［J］. Solar RRL， 2020， 4（5）： 1900557.
26	CHEN Z， YIN H B， WANG C Z， et al. New insights on competitive adsorption of NO/SO₂ on TiO₂ anatase for photocatalytic NO oxidation［J］. Environmental Science & Technology， 2021， 55（13）： 9285⁃9292.
27	HENDERSON M A. A surface science perspective on TiO₂ photocatalysis［J］. Surface Science Reports， 2011， 66（6⁃7）： 185⁃297.
28	ZHAO Y， ZHAO L， HAN J， et al. Study on method and mechanism for simultaneous desulfurization and denitrification of flue gas based on the TiO₂ photocatalysis［J］. Science in China Series E： Technological Sciences， 2008， 51（3）： 268⁃276.
29	MA Q X， WANG L， CHU B W， et al. Contrary role of H₂O and O₂ in the kinetics of heterogeneous photochemical reactions of SO₂ on TiO₂［J］. The Journal of Physical Chemistry A， 2019， 123（7）： 1311⁃1318.
30	WANG F M， SHEN B X， ZHU S W， et al. Promotion of Fe and Co doped Mn⁃Ce/TiO₂ catalysts for low temperature NH₃⁃SCR with SO₂ tolerance［J］. Fuel， 2019， 249： 54⁃60.

[1]	王雪, 建伟伟, 陆毅, 张绍鹏, 周小盟, 韩赛钊. Cu和Sn改性多壁碳纳米管对VOCs气体的吸附[J]. 辽宁石油化工大学学报, 2021, 41(5): 44-49.
[2]	张绍鹏，建伟伟，马丹竹，刘超，王雪. 碳基及碳基复合材料吸附剂对VOCs吸附性能研究进展[J]. 辽宁石油化工大学学报, 2021, 41(1): 30-36.
[3]	朱敏，王艳芳，陈树军，付越，李雪健，刘永强. M⁃MOF⁃74吸附分离天然气中CO₂的模拟研究[J]. 辽宁石油化工大学学报, 2019, 39(3): 40-45.
[4]	李强，李晴，吕扬，王焕，秦玉才，宋丽娟，胡绍争. 碱金属改性g-C₃N₄及其对氮气吸附影响的理论研究[J]. 辽宁石油化工大学学报, 2018, 38(06): 37-42.

双金属改性多壁碳纳米管联合吸附SO₂与NO的实验研究

Experimental Study on the Combined Adsorption of SO₂ and NO by Bimetallic Modified Multi⁃Walled Carbon Nanotubes

HTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 30

相关文章 4

编辑推荐

Metrics