Mn掺杂多孔炭基复合功能材料制备及低温脱硝性能研究

刘一玮; 李本行; 魏子章; 刘肖瑶; 何旭; 梁高磊; 马小东

doi:10.13205/j.hjgc.202410014

Mn掺杂多孔炭基复合功能材料制备及低温脱硝性能研究

doi: 10.13205/j.hjgc.202410014

1. 河北工业大学能源与环境工程学院, 天津 300401;
2. 天津市生态环境科学研究院, 天津 300191

基金项目:

国家自然科学基金项目(22106037,21876042,22106036)

河北省重点研发计划项目(B2019202200,21374204D,22374206D)

国家重点研发计划课题(2020YFC1808603)

详细信息

作者简介:
刘一玮(1998-),女,硕士研究生,主要研究方向为烟气脱硝技术。liuyiwei2021@stu.hebut.edu.cn

通讯作者:
马小东(1972-),男,博士,教授,主要研究方向为环境功能材料研发及应用。maxd@hebut.edu.cn

计量
- 文章访问数: 15
- HTML全文浏览量: 2
- PDF下载量: 0
- 被引次数: 0
出版历程
- 收稿日期: 2024-01-25
- 网络出版日期: 2024-11-30

PREPARATION AND LOW-TEMPERATURE DENITRIFICATION PROPERTIES OF Mn-DOPED POROUS CAROBON MATRIX COMPOSITE FUNCTIONAL MATERIALS

1. School of Energy and Environmental Engineering, Hebei University of Technology, Tianjin 300401, China;
2. Tianjin Academy of Eco-Environmental Sciences, Tianjin 300191, China

摘要

摘要: 双碳背景下,以生物质为原料制备生物炭代替煤基炭,用于钢铁行业烧结烟气低温脱硝成为研究热点。以生物质为原料,通过单因素实验考察硝酸氧化、Mn掺杂量、粘结剂添加、活化条件对材料性能的影响,制备得到机械强度达标、脱硝效率高和催化稳定性好的Mn掺杂多孔炭基复合功能材料,并通过一系列表征初步探究材料组成、结构与低温脱硝活性之间的构效关系。结果表明,以硝酸氧化后的玉米秸秆生物炭为载体,掺杂活性组分Mn,添加混合粘结剂辅以水蒸气活化得到综合性能最佳的复合功能材料,在低温(120 ℃)脱硝活性测试中NO的稳态去除率达66.4%,是煤基活性炭的7倍左右,在模拟湿烟气工况下脱硝活性也显著高于煤基活性炭。研究成果为钢铁行业烧结烟气低温SCR脱硝提供了一种新的思路。
- Mn掺杂 /
- 多孔生物炭 /
- NH₃选择性催化还原 /
- 低温脱硝 /
- 烧结烟气
Abstract: Under the background of "Dual Carbon Goal", the preparation of biochar using biomass as the raw material instead of coal-based carbon for low-temperature denitrification of sintering flue gas in iron and steel industry has become a research hotspot. In this paper, using biomass as raw material, the effects of nitric acid oxidation, Mn doping amount, binder addition and activation conditions on material properties were investigated through single-factor experiments, and Mn-doped porous carbon matrix composite functional materials with the required mechanical strength, high denitrification efficiency and good catalytic stability were prepared. Moreover, the structure-activity relationship between material composition, structure and low-temperature denitrification activity was initially explored through a series of characterization. The results showed that the composite functional material with the best comprehensive properties was obtained by doping the active component Mn with the addition of mixed binder and water vapor activation. The steady-state removal rate of NO at low temperature (120 ℃) was 66.4%, which was about 7 times that of the coal-based activated carbon. The denitrification activity was also significantly higher than that of coal-based activated carbon under simulated wet flue gas conditions. The research results provide a new idea for the low-temperature SCR denitrification of sintering flue gas in iron and steel industry.
- Mn-doping /
- porous biochar /
- NH₃-selective catalytic reduction /
- low temperature denitrification /
- sintering flue gas

HTML全文

参考文献(28)

[1]	GUO Z, LIN B, HUANG Y, et al. Design of bimetallic catalyst with dual-functional Cu-Ce sites for synergistic NO_<em>x and toluene abatement[J]. Applied Catalysis B: Environmental, 2024, 342: 123430.
[2]	SONG I, LEE H, JEON S W, et al. Simple physical mixing of zeolite prevents sulfur deactivation of vanadia catalysts for NO_<em>x removal[J]. Nature Communications, 2021, 12(1): 901.
[3]	MA Y, ZHANG D, SUN H, et al. Fe-Ce mixed oxides supported on carbon nanotubes for simultaneous removal of NO and HgO in flue gas[J]. Industrial & Engineering Chemistry Research, 2018, 57(9): 3187-3194.
[4]	解强, 张香兰, 梁鼎成, 等. 煤基活性炭定向制备:原理·方法·应用[J]. 煤炭科学技术, 2021, 49(1): 28.
[5]	张福新, 白锋堂. 中长期煤炭消费碳排放与二氧化碳排放值预测[J]. 中国煤炭, 2022, 48(4): 36-40.
[6]	周茂军, 张代华. 宝钢烧结烟气超低排放技术集成与实践[J]. 钢铁, 2020, 55(2): 144-151.
[7]	JIANG L J, LIU Q C, ZHAO Q, et al. Promotional effect of Ce on the SCR of NO with NH₃ at low temperature over MnO_<em>x supported by nitric acid-modified activated carbon[J]. Research on Chemical Intermediates, 2018, 44(3): 1729-1744.
[8]	陈薇, 肖高, 郭杰, 等. 煤基活性炭表面改性对稀土负载型CeO₂/AC低温脱硝性能的影响[J]. 环境工程学报, 2018, 12(7): 9.
[9]	YANG J, REN S, ZHANG T S, et al. Iron doped effects on active sites formation over activated carbon supported Mn-Ce oxide catalysts for low-temperature SCR of NO[J]. Chemical Engineering Journal, 2020, 379: 122398.
[10]	吴海苗, 王晓波, 归柯庭. 以活性炭为载体的负载型催化剂的SCR脱硝性能[J]. 东南大学学报:自然科学版, 2013, 43(4): 5.
[11]	HE G, GAO M, PENG Y, et al. Superior oxidative dehydrogenation performance toward NH₃ determines the excellent low-temperature NH₃-SCR activity of Mn-based catalysts[J]. Environmental Science & Technology, 2021, 55, 10: 6995-7003.
[12]	李芬, 李梁, 杨莹, 等. 稻草活性炭的成型及其对H₂S的吸附性能[J]. 环境工程学报, 2017, 11(4): 2350-2354.
[13]	蒋恩臣, 卢爽, 张伟, 等. 粘结剂对生物质炭基尿素微观结构和性能影响的研究[J]. 可再生能源, 2017, 35(10): 1437-1442.
[14]	山西新华化工有限责任公司, 中国科学院山西煤炭化学研究所. 脱硫脱硝用煤质颗粒活性炭试验方法第5部分:脱硝率[Z]. 中华人民共和国国家质量监督检验检疫总局, 中国国家标准化管理委员会. 2013: 8.
[15]	LI X, SUN F, QU Z, et al. Insight into synergistic effects of oxygen and nitrogen dual-dopants in carbon catalysts on selective catalytic reduction of NO_<em>x with NH₃: a combined computational and experimental verification[J]. Chemical Engineering Journal, 2023, 454: 140098.
[16]	侯彩霞, 孔碧华, 樊丽华, 等. 硝酸改性无灰煤基多孔炭电极材料的制备[J]. 功能材料. 2018, 49(5): 5137-5144.
[17]	SUN F, YANG C, QU Z, et al. Inexpensive activated coke electrocatalyst for high-efficiency hydrogen peroxide production: coupling effects of amorphous carbon cluster and oxygen dopant[J]. Applied Catalysis B: Environmental, 2021, 286: 119860.
[18]	HUANG F, LI D, WANG L, et al. Rational introduction of nitridizing agent to hydrothermal carbonization for enhancing CO₂ capture performance of tobacco stalk-based porous carbons[J]. Journal of Analytical and Applied Pyrolysis, 2021, 157: 105047.
[19]	WANG Y, PENG W, WANG J, et al. Sulfamethoxazole degradation by regulating active sites on distilled spirits lees-derived biochar in a continuous flow fixed bed peroxymonosulfate reactor[J]. Applied Catalysis B: Environmental, 2022, 310: 121342.
[20]	XIE Z, LYU Z, WANG J, et al. Ultrafine-Mn₂O₃@N-doped porous carbon hybrids derived from Mn-MOFs: dual-reaction centre catalyst with singlet oxygen-dominant oxidation process[J]. Chemical Engineering Journal, 2022, 429: 132299.
[21]	GE Z, CHEN X, ZHANG X, et al. Porous MnO/pitch carbon composite as an anode material for low-cost and high-performance lithium-ion battery[J]. Chemical Engineering Science, 2024, 285: 119625.
[22]	WANG L, HUANG B, SU Y, et al. Manganese oxides supported on multi-walled carbon nanotubes for selective catalytic reduction of NO with NH₃: catalytic activity and characterization[J]. Chemical Engineering Journal, 2012, 192: 232-241.
[23]	EFIMOV M N, MURATOV D G, KLYUEV A L, et al. Ultrasonic treatment duration: a nuanced parameter in synthesis affecting structural properties and ORR performance of KOH-activated carbon[J]. Diamond and Related Materials, 2024, 142: 110804.
[24]	DONOHUE M D, ARANOVICH G L. Classification of Gibbs adsorption isotherms[J]. Advances in Colloid and Interface Science, 1998, 76/77: 137-152.
[25]	邵远超, 田华宇, 王国睿, 等. 低灰分刺竹炭制备及性能表征[J]. 林业工程学报, 2023, 8(1): 80-87.
[26]	LI H X, JIN L Y, ZHANG A C, et al. Investigation of Co-doped Mn oxide catalyst for NH₃-SCR activity and SO₂/H₂O resistance[J]. Journal of Fuel Chemistry and Technology, 2022, 50(11): 1404-1416.
[27]	FENG X, LIU S, YUE K, et al. Insight into the promotional effect of Mn-modified nitrogenous biochar on the NH₃-SCR denitrification activity at low temperatures[J]. Energy, 2023, 285: 129323.
[28]	XIA Y, YANG Y, CHEN Z, et al. Boosting the low-temperature NH₃-SCR performance via metals co-doping with inequality Mn/Ce ratios in the carbon-based catalyst prepared by Cr-containing leather waste[J]. Molecular Catalysis, 2023, 551: 113615.