碳材料吸附脱除二氧化硫性能的影响因素

doi:10.16085/j.issn.1000-6613.2021-2205

化工进展 ›› 2022, Vol. 41 ›› Issue (9): 4963-4972.DOI: 10.16085/j.issn.1000-6613.2021-2205

碳材料吸附脱除二氧化硫性能的影响因素

李兴¹^,²^,³(), 黄宏宇²^,³, 大坂侑吾⁴, 呼和涛力¹^,⁵, 肖林发²^,³, 李军²^,³()

^1.南京工业大学机械与动力工程学院，江苏南京 211816
^2.中国科学院广州能源研究所，广东广州 510640
^3.南方海洋科学与工程广东省实验室(广州)，广东广州 511458
^4.日本金泽大学，金泽 9201192
^5.常州大学城乡矿山研究院，江苏常州 213164

收稿日期:2021-10-28 修回日期:2022-01-11 出版日期:2022-09-25 发布日期:2022-09-27
通讯作者: 李军
作者简介:李兴（1988—），男，硕士，助理研究员，研究方向为脱硫材料。E-mail：lixing1@ms.giec.ac.cn。
基金资助:
南方海洋科学与工程广东省实验室（广州）人才团队引进重大专项(GML2019ZD0108);广东省重点领域研发计划(2020B0202010004);中国科学院前沿科学重点研究项目(QYZDY-SSW-JSC038)

Study on the influencing factors of the adsorption performance of carbon materials for the sulfur dioxide removal

LI Xing¹^,²^,³(), HUANG Hongyu²^,³, OSAKA Yugo⁴, HUHE Taoli¹^,⁵, XIAO Linfa²^,³, LI Jun²^,³()

^1.School of Mechanical and Power Engineering, Nanjing Tech University, Nanjing 211816, Jiangsu, China
^2.Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
^3.Southern Marine Science and Engineering Guangdong Laboratory (Guangzhou), Guangzhou 511458, Guangdong, China
^4.Kanazawa University, Kanazawa 9201192, Japan
^5.Institute of Urban and Rural Mining, Changzhou University, Changzhou 213164, Jiangsu, China

Received:2021-10-28 Revised:2022-01-11 Online:2022-09-25 Published:2022-09-27
Contact: LI Jun

摘要/Abstract

摘要：

选用了7种不同物理化学特性的碳材料，分别为活性炭-1（比表面积1779m²/g）、活性炭-2（比表面积970m²/g）、多孔纳米炭-1（平均孔径14nm）、多孔纳米炭-2（平均孔径85nm）、多孔纳米炭-3（平均孔径4.7nm，掺氮）、多孔纳米炭-4（平均孔径4.1nm，不掺氮）和纳米碳纤维。在对比这7种不同的碳材料的物理化学特性与其脱硫性能的基础上，研究材料的物理化学特性、脱硫温度、反应空速等因素对碳材料吸附脱除SO₂性能的影响。结果表明，碳材料吸附脱除SO₂的性能受材料的比表面积、孔隙结构、表面官能团、脱硫温度和反应空速的综合影响。不同的碳材料中，材料的孔隙结构和表面官能团对材料的脱硫性能影响很大，以微孔结构为主的碳材料SO₂去除率较高，以介孔结构为主的碳材料脱硫容量较高；随着脱硫温度升高，碳材料的吸附脱硫性能降低；随着反应空速降低，碳材料的吸附脱硫性能升高。本研究中，多孔纳米炭NCP-10的吸附脱除SO₂性能最好，能在室温下保持100%的SO₂去除率持续1h，且在室温下1h内累积的脱硫容量最高可达108mg(SO₂)/g(材料)。

关键词: 环境, 碳材料, 吸附剂, 二氧化硫脱除, 固定床, 脱硫性能

Abstract:

Carbon materials can be used as excellent adsorption desulfurization materials. Their sulfur dioxide (SO₂) capture performance is affected by physicochemical characteristics and desulfurization conditions. In this study, seven types of carbon materials were selected: activated carbon-1 (specific surface area was 1779m²/g, AC-1700), activated carbon-2 (specific surface area was 970m²/g, AC-900), porous nano-carbon-1 (average pore size was 14nm, NCP-10), porous nano-carbon-2 (average pore size was 85nm, NCP-100), porous nano-carbon-3 (average pore size was 4.7nm, nitrating, CMK-3N), porous nano-carbon-4 (average pore size was 4.1nm without nitrating, CMK-3) and carbon nanofibers (NCF). Based on the comparison of the physicochemical characteristic of these seven different carbon materials and their desulfurization performance, the effects of physicochemica properties, desulfurization temperature, reaction space velocity and so on on the SO₂ capture performance of carbon materials were studied. It provided guidance for the research and development of carbon materials and their composites with suitable physical and chemical properties and high desulfurization performance. The results showed that the SO₂ capture performance of carbon materials was comprehensive affected by the specific surface area, pore structure, surface functional groups, desulfurization temperature and reaction space velocity. The pore structure and surface functional groups of different carbon materials had great influence on the desulfurization performance of the carbon materials. The activated carbon AC-1700 and AC-900 with microporous structure had a higher SO₂ removal rate. The porous nano-carbon NCP-10, NCP-100, CMK-3N and CMK-3 with mesoporous structure had a higher desulfurization capacity. Oxygen functional groups and nitrogen functional groups can improve the adsorption performance of carbon materials for SO₂ capture. The process of SO₂ removal by carbon materials was mainly physical adsorption. The SO₂ capture performance of carbon materials decreased with increasing desulfurization temperature. Above 100℃, the SO₂ capture performance of carbon materials would be ineffective. The reaction space velocity had a great influence on the SO₂ capture performance of carbon materials. With the decrease of reaction space velocity, the SO₂ capture performance of carbon materials increased. When the reaction space velocity was low enough, carbon materials can effectively remove SO₂ pollution. In this study, porous nano-carbon NCP-10 had the best SO₂ capture performance, which can maintain 100% SO₂ removal rate at room temperature for 1 hour, and the 1 hour cumulative desulfurization capacity was up to $108 m g S O 2$ /g_material at room temperature while maintaining a SO₂ removal rate of higher than 90%.

Key words: environment, carbon materials, adsorbents, sulfur dioxide removal, fixed-bed, desulfurization performance

中图分类号:

X511

李兴, 黄宏宇, 大坂侑吾, 呼和涛力, 肖林发, 李军. 碳材料吸附脱除二氧化硫性能的影响因素[J]. 化工进展, 2022, 41(9): 4963-4972.

LI Xing, HUANG Hongyu, OSAKA Yugo, HUHE Taoli, XIAO Linfa, LI Jun. Study on the influencing factors of the adsorption performance of carbon materials for the sulfur dioxide removal[J]. Chemical Industry and Engineering Progress, 2022, 41(9): 4963-4972.

图/表 16

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碳材料	ω_C/%	ω_N/%	ω_H/%
AC-1700	90.7	0.01	0.78
AC-900	86.5	0.3	1.95
NCP-10	93.8	0	0.82
NCP-100	89	0.01	0.62
CMK-3N	70.2	14.9	1.72
CMK-3	85.3	0	1.2
NCF	91.6	0.14	0.43

碳材料	ω_C/%	ω_N/%	ω_H/%
AC-1700	90.7	0.01	0.78
AC-900	86.5	0.3	1.95
NCP-10	93.8	0	0.82
NCP-100	89	0.01	0.62
CMK-3N	70.2	14.9	1.72
CMK-3	85.3	0	1.2
NCF	91.6	0.14	0.43

样品	微孔比表面积/m²·g^-1	总比表面积/m²·g^-1	微孔容/cm³·g^-1	总孔容/cm³·g^-1	平均孔径/nm	总碱量/μmol·g^-1
AC-1700	1559	1779	0.748	0.836	2.11	102
AC-900	559	970	0.268	0.662	2.73	57
NCP-10	31.1	455	0.020	0.799	14.1	116
NCP-100	15.3	155	0.008	0.812	85.3	72
CMK-3N	91.8	557	0.046	0.752	4.69	201
CMK-3	0	690	0	0.818	4.11	95
NCF	0	13.2	0	0.053	4.98	63

样品	微孔比表面积/m²·g^-1	总比表面积/m²·g^-1	微孔容/cm³·g^-1	总孔容/cm³·g^-1	平均孔径/nm	总碱量/μmol·g^-1
AC-1700	1559	1779	0.748	0.836	2.11	102
AC-900	559	970	0.268	0.662	2.73	57
NCP-10	31.1	455	0.020	0.799	14.1	116
NCP-100	15.3	155	0.008	0.812	85.3	72
CMK-3N	91.8	557	0.046	0.752	4.69	201
CMK-3	0	690	0	0.818	4.11	95
NCF	0	13.2	0	0.053	4.98	63

材料	官能团及其质量分数/%
材料	C=O（530.0~531.1eV）	C—O—H或C—O—C（531.0~532.1eV）	C—O—C=O（532.1~533.1eV）	—COOH（533.3~534.1eV）
AC-1700	2.87	2.56	2.95	1.34
AC-900	4.11	1.41	2.60	0.54
NCP-10	0.89	0.43	0.55	0.11
NCP-100	0.77	0.42	0.46	0.09
CMK-3N	2.44	1.56	2.44	0.27
CMK-3	1.05	0.82	0.99	0.13
NCF	1.32	1.20	1.15	0.12

碳材料吸附脱除二氧化硫性能的影响因素

Study on the influencing factors of the adsorption performance of carbon materials for the sulfur dioxide removal

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图/表 16

参考文献 20

相关文章 15

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样品	反应质量/g	反应空速/h^-1	0.1% SO₂ + 5% O₂ + N₂		0.1% SO₂ + 6% CO₂ + 10% O₂ + N₂
样品	反应质量/g	反应空速/h^-1	前1h内SO₂平均去除率/%	前1h累计脱硫容量/mg（SO₂）·g^-1（材料）	前1h内SO₂平均去除率/%	前1h累计脱硫容量/mg（SO₂）·g^-1（材料）
AC-1700	0.36	3410	100	47.7	100	47.7
AC-900	0.56	3395	94.7	29.0	90.2	27.6
NCP-10	0.20	3420	97.1	87.9	95.4	81.9
NCP-100	0.21	3415	81.9	66.9	34.9	28.5
CMK-3N	0.27	3400	93.2	59.2	86.2	54.8
CMK-3	0.33	3395	74.2	38.6	68.1	35.4
NCF	0.30	3410	22.4	12.8	18.0	10.3

脱硫温度/℃	AC-1700		NCP-10
脱硫温度/℃	前30min内SO₂平均去除率/%	前30min累计脱硫容量/mg（SO₂）·g^-1（材料）	前30min内SO₂平均去除率/%	前30min累计脱硫容量/mg（SO₂）·g^-1（材料）
25	97.7	44.1	99.0	56.6
40	89.2	40.3	97.8	55.9
60	63.3	28.6	91.1	52.1
80	57.2	25.9	66.8	38.2
100	46.2	20.9	29.8	17.1

反应空速/h^-1	反应质量/g	脱硫温度/℃	前1h内SO₂平均去除率/%	前1h累计脱硫容量/mg（SO₂）·g^-1（材料）
7905	0.101	25	81.5	138.5
5400	0.150	25	94.5	108.1
3420	0.201	25	96.7	82.5
3076	0.251	25	98.2	67.1
2802	0.283	25	99.1	60.1
2635	0.301	25	100	57.0

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