热处理温度对粘胶基活性碳纤维结构及催化脱硫性能的影响

doi:10.19964/j.issn.1006-4990.2025-0145

摘要/Abstract

摘要：

“双碳”背景下，传统的石灰石-石膏法烟气脱硫技术的主导地位面临巨大的挑战。炭法脱硫能将SO₂催化氧化转化为产物硫酸，实现硫资源回收，是一种具有广阔应用前景的新型脱硫技术。通过对粘胶基活性碳纤维（ACF）高温热处理前后的物理结构和表面化学结构变化进行研究，探讨热处理ACF的结构变化对催化氧化SO₂性能的影响。在高浓度模拟烟气SO₂、O₂、H₂O体积分数分别为0.2%、10%、20%，脱硫温度为80 ℃，体积空速为600 h^-1条件下，未经热处理的ACF-O的穿透硫容仅为21 mg/g，1 000 ℃高温热处理1 h后其穿透硫容达到153 mg/g，是ACF-O的7倍以上。结果表明，1 000 ℃高温热处理有利于粘胶基ACF表面酸性含氧官能团的分解和含氮官能团向石墨氮的转化，使热改性ACF的表面碱性提高、边缘结构缺陷增多、内部电子传导能力增强、比表面积增大，进而促进SO₂和O₂的吸附、活化和催化氧化，在烟气含水的体系下最终形成产物硫酸。

关键词: 非金属催化, 烟气脱硫, SO₂, 粘胶基活性碳纤维

Abstract:

Under the “dual-carbon” background，the dominant position of traditional limestone-gypsum flue gas desulfurization（FGD） technology faces significant challenges.Carbon-based desulfurization，which catalytically oxidizes SO₂ into sulfuric acid for sulfur resource recovery，represents a promising new desulfurization technology.By investigating the structural evolution of viscose-based activated carbon fiber（ACF） before and after high-temperature heat treatment，focusing on physical and surface chemical structure changes，the effect of these modifications on SO₂ catalytic oxidation performance was explored.Under simulated high-concentration flue gas conditions（0.2% SO₂，10% O₂，20% H₂O） at 80 ℃ with a volume space velocity of 600 h⁻¹，untreated ACF-O exhibited a breakthrough sulfur capacity of merely 21 mg/g ACF.After 1 hour heat treatment at 1 000 ℃，this capacity was increased to 153 mg/g ACF-more than 7 times that of ACF-O.The results demonstrated that 1 000 ℃ heat treatment facilitated the decomposition of acidic oxygen-containing functional groups and the conversion of nitrogen-containing groups into graphitic nitrogen on ACF surfaces.These structural modifications enhanced the heat-treated ACF's surface alkalinity，increased edge defects，improved electron transfer capability，and expanded specific surface area.Consequently，these improvements promoted the adsorption，activation，and catalytic oxidation of SO₂ and O₂，ultimately forming sulfuric acid in humid flue gas systems.

Key words: nonmetallic catalysis, flue gas desulfurization, SO?, ACF

中图分类号:

TQ127.1

马天丽, 李明松, 吕莉, 唐盛伟, 张涛, 唐文翔. 热处理温度对粘胶基活性碳纤维结构及催化脱硫性能的影响[J]. 无机盐工业, 2026, 58(3): 112-118.

MA Tianli, LI Mingsong, LÜ Li, TANG Shengwei, ZHANG Tao, TANG Wenxiang. Effect of heat treatment temperature on structure of viscose-based activated carbon fibers and their catalytic desulfurization performance[J]. Inorganic Chemicals Industry, 2026, 58(3): 112-118.

图/表 12

图1

图2

图3

图4

表1

表 2

图5

图6

图7

图8

图9

表 3

参考文献 27

[1]	LI Xueke， HAN Jinru， LIU Yan，et al.Summary of research progress on industrial flue gas desulfurization technology［J］.Separation and Purification Technology，2022，281：119849.
[2]	华雯，吕瑞亮.湿法烟气脱硫技术应用现状及发展方向［J］.无机盐工业，2022，54（12）：10-18.
	HUA Wen， Ruiliang LÜ.Application status and development direction of wet flue gas desulfurization technology［J］.Inorganic Chemicals Industry，2022，54（12）：10-18.
[3]	杜家芝，曹顺安.湿法烟气脱硫技术的现状与进展［J］.应用化工，2019，48（6）：1495-1500.
	DU Jiazhi， CAO Shun’an.Research status and progress of wet flue gas desulfurization technology［J］.Applied Chemical Industry，2019，48（6）：1495-1500.
[4]	ZHENG Jiahao， ZHANG Shule， ZENG Yiqing，et al.Synergistic effect of oxygen-containing and nitrogen-containing groups on promoting low-temperature denitration over non-metallic carbon-based catalyst［J］.Molecular Catalysis，2024，554：113824.
[5]	李婉君，黄帮福，杨征宇，等.活性炭改性及其脱硫脱硝性能研究与展望［J］.硅酸盐通报，2022，41（4）：1318-1327.
	LI Wanjun， HUANG Bangfu， YANG Zhengyu，et al.Research and prospect on modification of activated carbon and its desulfurization and denitrification performance［J］.Bulletin of the Chinese Ceramic Society，2022，41（4）：1318-1327.
[6]	KONG Dexing， LIAN Liqun， WANG Yan，et al.A review on carbon-based and coordination polymer-based materials for adsorption of SO2 from flue gas［J］.Chemical Engineering Journal，2024，500：157089.
[7]	LIU Zhenshu， LI Wenkai， HUNG M J.Simultaneous removal of sulfur dioxide and polycyclic aromatic hydrocarbons from incineration flue gas using activated carbon fibers［J］.Journal of the Air & Waste Management Association，2014，64（9）：1038-1044.
[8]	王志强，张俊杰，刘相成，等.改性活性炭对低浓度二氧化硫吸附动力学模型研究［J］.无机盐工业，2022，54（9）：69-76.
	WANG Zhiqiang， ZHANG Junjie， LIU Xiangcheng，et al.Study on adsorption kinetics model of modified activated carbon on SO₂ with low-concentration［J］.Inorganic Chemicals Industry，2022，54（9）：69-76.
[9]	GAUR V， SHARMA A， VERMA N.Removal of SO₂ by activated carbon fibre impregnated with transition metals［J］.The Canadian Journal of Chemical Engineering，2007，85（2）：188-198.
[10]	ABDULRASHEED A A， JALIL A A， TRIWAHYONO S，et al.Surface modification of activated carbon for adsorption of SO₂ and NO _x ：A review of existing and emerging technologies［J］.Renewable and Sustainable Energy Reviews，2018，94：1067-1085.
[11]	YE Yanli， XIE Junlin， FANG De，et al.Effect of acid treatment on surfaces of activated carbon supported catalysts for NO and SO₂ removal［J］.Fullerenes，Nanotubes and Carbon Nanostructures，2022，30（2）：297-305.
[12]	LIN Jian， CHOOWANG R， ZHAO Guangjie.Fabrication and characterization of activated carbon fibers from oil palm trunk［J］.Polymers，2020，12（12）：2775.
[13]	GERVEN D J V.SO₃ als reaktionsmedium：Synthese und charakterisierung neuer sulfatderivate ［D］.Köln：Universität zu Köln，2020.
[14]	LI Liqing， YAO Xiaolong， LI Hailong，et al.Thermal stability of oxygen-containing functional groups on activated carbon surfaces in a thermal oxidative environment［J］.Journal of Chemical Engineering of Japan，2014，47（1）：21-27.
[15]	DÜNGEN P， SCHLÖGL R， HEUMANN S.Non-linear thermogra-vimetric mass spectrometry of carbon materials providing direct speciation separation of oxygen functional groups［J］.Carbon，2018，130：614-622.
[16]	XU Siyu， CHEN Jiefeng， PENG Haoyi，et al.Effect of biomass type and pyrolysis temperature on nitrogen in biochar，and the comparison with hydrochar［J］.Fuel，2021，291：120128.
[17]	YANG Gaixiu， ZHENG Xuhong， WANG Kexin，et al.The effect of pyrolysis temperature on the N conversion of biochar derived from the residue of Chlorella vulgaris after lipid extraction［J］.Journal of Analytical and Applied Pyrolysis，2023，169：105810.
[18]	FUJIMOTO Y.Formation，structure，electronic，and transport properties of nitrogen defects in graphene and carbon nanotu- bes［J］.Micromachines，2024，15（9）：1172.
[19]	LI Dan， CHEN Wenhua， WU Jianping，et al.The preparation of waste biomass-derived N-doped carbons and their application in acid gas removal：Focus on N functional groups［J］.Journal of Materials Chemistry A，2020，8（47）：24977-24995.
[20]	VALI I P， ANUSHA B S， PRUTHVIJA M，et al.Bamboo and conut shell based activated carbon：A Raman spectroscopic study［J］.Materials Chemistry and Physics，2024，318：129240.
[21]	SHOKRANI HAVIGH R， MAHMOUDI CHENARI H.A comprehensive study on the effect of carbonization temperature on the physical and chemical properties of carbon fibers［J］.Scientific Reports，2022，12：10704.
[22]	LEE T H， PARK S， CHOI T H，et al.Detailed characterization of an annealed reduced graphene oxide catalyst for selective peroxide formation activity［J］.ACS Applied Materials & Interfaces，2020，12（41）：46439-46445.
[23]	BOUKHVALOV D W， OSIPOV V Y， SHAMES A I，et al.Charge transfer and weak bonding between molecular oxygen and graphene zigzag edges at low temperatures［J］.Carbon，2016，107：800-810.
[24]	LI Tianbai， YARMOFF J A.Defect-induced oxygen adsorption on graphene films［J］.Surface Science，2018，675：70-77.
[25]	BREITENBACH S， DUCHOSLAV J， MARDARE A I，et al.Comparative behavior of viscose-based supercapacitor electrodes activated by KOH，H₂O，and CO₂ ［J］.Nanomaterials，2022，12（4）：677.
[26]	LI Chao， LI Dianqiang， JIANG Yuchen，et al.Biomass-derived volatiles for activation of the biochar of same origin［J］.Fuel，2023，332：126034.
[27]	SAMOJEDEN B， GRZYBEK T.The influence of nitrogen groups introduced onto activated carbons by high-or low-temperature NH₃ treatment on SO₂ sorption capacity［J］.Adsorption Science & Technology，2017，35（5/6）：572-581.

E/eV	含氧官能团	相对含量/%
E/eV	含氧官能团	ACF-O	ACF-500	ACF-800	ACF-1000
530.0	无机氧	4.8	4.7	4.7	2.9
531.4	C=O	21.1	16.7	8.7	3.0
532.8	C—O	42.0	52.7	71.2	84.6
534.5	—COO—	26.7	21.5	10.9	2.3
536.3	CO₂/O₂	5.8	4.5	3.2	7.2

E/eV	含氮官能团	相对含量/%
E/eV	含氮官能团	ACF-O	ACF-500	ACF-800	ACF-1000
398.4	N-6	20.9	26.3	25.1	21.1
400.1	N-5	39.7	33.5	27.2	27.5
401.5	N-4	27.0	29.9	34.4	40.9
403.3	N—O	14.4	12.3	13.0	11.1

ACF材料	比表面积/ （m²·g^-1）	微孔体积/ （cm³·g^-1）	比孔容/ （cm³·g^-1）
ACF-O	1 417	0.57	0.62
ACF-500	1 460	0.58	0.63
ACF-800	1 477	0.63	0.68
ACF-1000	1 689	0.75	0.83

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会