利用煤焦油中酚类物质Stöber法制备碳纳米球用于CO2吸附

doi:10.16085/j.issn.1000-6613.2022-1851

化工进展 ›› 2023, Vol. 42 ›› Issue (9): 5011-5018.DOI: 10.16085/j.issn.1000-6613.2022-1851

利用煤焦油中酚类物质Stöber法制备碳纳米球用于CO₂吸附

杨莹¹(), 侯豪杰²^,³, 黄瑞²^,³, 崔煜¹, 王兵²^,³(), 刘健⁴, 鲍卫仁²^,³, 常丽萍²^,³, 王建成²^,³, 韩丽娜¹()

^1.太原理工大学材料科学与工程学院，山西太原 030024
^2.太原理工大学省部共建煤基能源清洁高效利用国家重点实验室，山西太原 030024
^3.太原理工大学煤科学与技术教育部重点实验室，山西太原 030024
^4.中国科学院大连化学物理研究所，辽宁大连 116023

收稿日期:2022-10-08 修回日期:2022-11-24 出版日期:2023-09-15 发布日期:2023-09-28
通讯作者: 王兵,韩丽娜
作者简介:杨莹（1998—），女，硕士研究生，研究方向为大气污染物化学和分子筛催化材料。E-mail：yang_ying996@163.com。
基金资助:
国家自然科学基金联合基金(U1710107);晋中市科技重点研发计划(Y201002)

Coal tar phenol-based carbon nanosphere prepared by Stöber method for adsorption of CO₂

YANG Ying¹(), HOU Haojie²^,³, HUANG Rui²^,³, CUI Yu¹, WANG Bing²^,³(), LIU Jian⁴, BAO Weiren²^,³, CHANG Liping²^,³, WANG Jiancheng²^,³, HAN Lina¹()

^1.College of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^2.State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^3.Key Laboratory of Coal Science and Technology, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^4.Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China

Received:2022-10-08 Revised:2022-11-24 Online:2023-09-15 Published:2023-09-28
Contact: WANG Bing, HAN Lina

摘要/Abstract

摘要：

煤焦油的排放和直接利用会造成严重的环境污染，开发高附加值材料的绿色合成方法及应用是煤焦油利用的关键。本文采用Stöber法以间苯二酚和中低温煤焦油为碳源与甲醛聚合制备了多孔碳纳米球CO₂吸附剂，通过扫描电子显微镜、N₂吸附-脱附测试、傅里叶变换红外吸收光谱、X射线衍射等手段对样品进行测试和分析。考察了预聚温度、水热温度和煤焦油添加量对碳纳米球的孔结构和CO₂吸附性能的影响。预聚温度为60℃、水热温度为200℃时，产物具有最优异的比表面积和CO₂吸附性能。C₁-R₁-RT-200吸附剂的比表面积达到787m²/g，CO₂最大吸附量为4.64mmol/g。当煤焦油占总投料质量的50%~76%时，产物的CO₂吸附性能较好，优于纯的间苯二酚模型化合物。所制备的多孔碳纳米球的CO₂吸附等温线可以很好地吻合Langmuir等温线模型，说明多孔碳纳米球对CO₂的吸附为单分子层吸附。

关键词: CO₂捕集, 吸附, 纳米材料, 碳纳米球, St?ber法, 中低温煤焦油

Abstract:

Emission and direct utilization of coal tar caused severe environmental pollution. Thus, developing a green synthesis method and application of high-valued materials is critical to the utilization of coal tar. Herein, we successfully fabricated porous carbon nanosphere as CO₂ adsorbent using resorcinol and medium- and low-temperature coal tar as carbon sources to polymerize with formaldehyde via the Stöber method. The samples were tested and analyzed by scanning electron microscopy, N₂ adsorption-desorption, Fourier transform infrared absorption spectroscopy, and X-ray diffraction. We investigated the effects of pre-polymerization temperature, hydrothermal temperature, and coal tar ratio on the pore structure and adsorption performance of CO₂. When the pre-polymerization and hydrothermal temperatures were 60℃ and 200℃, respectively, the product had the highest specific surface and CO₂ adsorption capacity. The specific surface area of the C₁-R₁-RT-200 adsorbent was 787m²/g with the CO₂ adsorption capacity of 4.64mmol/g. The product had better CO₂ adsorption capacity when the mass fraction of coal tar was 50%—76%, which was much higher than that synthesized using the pure resorcinol model compounds. The CO₂ adsorption isotherm of the prepared porous carbon nanospheres matched well with the Langmuir isotherm model, indicating that the CO₂ adsorption of the porous carbon nanospheres was a monolayer adsorption. Our work could contribute to developing the green synthesis method for coal tar-based CO₂ adsorbents.

Key words: CO₂ capture, adsorption, nanomaterials, carbon nanospheres, St?ber method, medium- and low-temperature coal tar

中图分类号:

TQ526.52

杨莹, 侯豪杰, 黄瑞, 崔煜, 王兵, 刘健, 鲍卫仁, 常丽萍, 王建成, 韩丽娜. 利用煤焦油中酚类物质Stöber法制备碳纳米球用于CO₂吸附[J]. 化工进展, 2023, 42(9): 5011-5018.

YANG Ying, HOU Haojie, HUANG Rui, CUI Yu, WANG Bing, LIU Jian, BAO Weiren, CHANG Liping, WANG Jiancheng, HAN Lina. Coal tar phenol-based carbon nanosphere prepared by Stöber method for adsorption of CO₂[J]. Chemical Industry and Engineering Progress, 2023, 42(9): 5011-5018.

图/表 9

图1 Stöber制备碳纳米球的示意图

图2 预聚合树脂球的红外吸收光谱

图3 碳纳米球的SEM照片（插图为相应SEM图中纳米球的粒径分布图）

图4 C1-R1-RT-200吸附剂的XRD图

图5 不同预聚温度和水热温度制备的吸附剂的N2吸附-脱附曲线及孔径分布图

表1 不同预聚温度和水热温度制备的吸附剂的比表面积及孔结构参数

样品

S_BET

/m²∙g^-1

总孔隙体积

/cm³∙g^-1

微孔隙体积

/cm³∙g^-1

微/总孔隙体积

/cm³∙g^-1

C₁-R₁-60-160

C₁-R₁-RT-200

C₁-R₁-60-200

表2 模型化合物制备系列催化剂的CO2 Langmuir吸附等温方程参数

吸附剂	温度/℃	q_max/mmol·g^-1	K_L/atm^-1	R²
C₁-R₁-RT-160	25	3.75	3.73	0.994
C₁-R₁-60-160	25	3.87	4.52	0.993
C₁-R₁-RT-200	25	3.85	3.48	0.994
C₁-R₁-60-200	25	5.81	3.27	0.992
C₁-R₃-RT-200	25	3.23	1.86	0.995
C₁-R₂-RT-200	25	3.07	2.29	0.994
C₂-R₁-RT-200	25	5.08	2.16	0.988
C₃-R₁-RT-200	25	1.75	1.59	0.990

图6 不同温度制备的吸附剂的CO2吸附性能

图7 不同投料比制备吸附剂的CO2吸附性能

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利用煤焦油中酚类物质Stöber法制备碳纳米球用于CO₂吸附

Coal tar phenol-based carbon nanosphere prepared by Stöber method for adsorption of CO₂

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