碱金属催化煤热解制备CNT复合材料用于吸附罗丹明B

doi:10.16085/j.issn.1000-6613.2024-0906

化工进展 ›› 2025, Vol. 44 ›› Issue (7): 3985-3996.DOI: 10.16085/j.issn.1000-6613.2024-0906

• 材料科学与技术 • 上一篇

碱金属催化煤热解制备CNT复合材料用于吸附罗丹明B

王影¹(), 汤孟菲¹, 王莹², 张传芳¹, 张国杰¹, 刘俊¹^,³, 赵钰琼¹

^1.太原理工大学化学工程与技术学院，省部共建煤炭清洁高效利用国家重点实验室
^1.山西太原 030024，山西大学电力与建筑学院，山西太原 030006
^2.山西太原 030024，清华大学环境学院
多重烟气污染控制技术与设备国家工程实验室，北京 100084

收稿日期:2024-06-03 修回日期:2024-08-19 出版日期:2025-07-25 发布日期:2025-08-04
通讯作者: 王影
作者简介:王影（1987—），男，博士研究生，讲师，研究方向为煤基碳材料，E-mail: wangying04@tyut.edu.cn。
基金资助:
山西省基础研究计划(202203021222130);山西省基础研究计划(202303021211034);山西省基础研究计划(202303021211032);国家重点研发计划(2022YFC3701900)

Preparation of CNT composites from coal pyrolysis catalyzed by different alkali metals for adsorption of Rhodamine B

WANG Ying¹(), TANG Mengfei¹, WANG Ying², ZHANG Chuanfang¹, ZHANG Guojie¹, LIU Jun¹^,³, ZHAO Yuqiong¹

^1.State Key Laboratory of Clean and Efficient Coal Utilization, College of Chemical Engineering and Technology, Taiyuan University of Science and Technology, Taiyuan 030024, Shanxi, China
^2.School of Electric Power, Civil Engineering and Architecture, Shanxi University, Taiyuan 030006, Shanxi, China
^3.State Engineering Laboratory of Multiple Smoke and Gas Pollution Control Technologies and Equipments, School of Environment, Tsinghua University, Beijing 100084, China

Received:2024-06-03 Revised:2024-08-19 Online:2025-07-25 Published:2025-08-04
Contact: WANG Ying

摘要/Abstract

摘要：

煤热解制备高比表面积和高微孔率碳纳米管（CNT）复合材料过程中，KOH相比于Ba(OH)₂和NaOH催化剂具有更强碱性，能够释放煤中大量碳源和促进CNT的生长和开口状结构形成。为了减少强碱性对CNT结构的崩解，以尿素协同掺杂改善碱性和孔结构，以提高微孔率和CNT表面氮氧官能团的吸附位点。本文以烟煤为碳源，利用不同碱性金属作为催化剂制备碳纳米管复合材料，研究了碱性金属对CNT生长的影响以及碱金属与尿素协同作用对罗丹明B去除的影响，探讨了动力学模型、等温吸附模型和热力学模型。吸附过程符合伪二阶动力学模型和Freundlich等温吸附模型。基于范霍夫方程计算表明该吸附是一个吸热的、自发的、不可逆的过程。最佳复合材料NCNT-K在323K时可达到最大吸附量，为598.09mg/g。

关键词: 碳纳米管, 煤, 吸附, 罗丹明B, 模型

Abstract:

In the process of preparing high specific surface area and high porosity carbon nanotubes (CNTs) composite materials from coal pyrolysis, compared to Ba(OH)₂ and NaOH, KOH has stronger alkalinity which can release a large amount of carbon sources in coal and promote the growth and formation of open structures of CNTs. In order to reduce the disintegration of CNTs structure by strong alkalinity, urea co-doping is used to improve alkalinity and pore structure, so as to increase the microporosity and the adsorption sites of nitrogen and oxygen functional groups on the surface of CNTs. This article used bituminous coal as a carbon source and different alkaline metals as catalysts to prepare carbon nanotube composite materials. The influence of alkaline metals on the growth of CNTs and the synergistic effect of alkaline metals and urea on the removal of Rhodamine B were studied, and the kinetic model, isothermal adsorption model and thermodynamic model were discussed. The adsorption process conformed to the pseudo second-order kinetic model and the Freundlich isotherm adsorption model. The calculation based on the van Hough equation indicated that the adsorption was an endothermic, spontaneous and irreversible process. The results indicated that the optimal composite material NCNT-K could achieve a maximum adsorption capacity of 598.09mg/g at 323K.

Key words: carbon nanotubes, coal, adsorption, Rhodamine B, modeling

中图分类号:

TQ610.9

王影, 汤孟菲, 王莹, 张传芳, 张国杰, 刘俊, 赵钰琼. 碱金属催化煤热解制备CNT复合材料用于吸附罗丹明B[J]. 化工进展, 2025, 44(7): 3985-3996.

WANG Ying, TANG Mengfei, WANG Ying, ZHANG Chuanfang, ZHANG Guojie, LIU Jun, ZHAO Yuqiong. Preparation of CNT composites from coal pyrolysis catalyzed by different alkali metals for adsorption of Rhodamine B[J]. Chemical Industry and Engineering Progress, 2025, 44(7): 3985-3996.

图/表 15

表1 原煤的工业分析和元素分析（质量分数）

工业分析W_ad^①/%				元素分析W_d^②/%
灰分	水分	挥发分	固定碳^③	C	H	N	S
5.53	3.25	30.91	60.33	73.75	4.42	1.45	0.22

图1 复合材料的N2吸附-解吸等温线[(a)]和Na掺杂NLDFT孔径分布[(b)]（内插图为K掺杂NLDFT孔径分布）

表2 复合材料的孔隙结构特征

复合材料	比表面积/m²·g^-1	微孔比表面积/m²·g^-1	孔容/cm³·g^-1	微孔体积/cm³·g^-1	微孔含量/%	平均粒径/nm
CNT-K	1128	1090	0.580	0.443	76.38	2.082
NCNT-K	1439	1384	0.669	0.584	87.29	1.932
CNT-Na	252	198	0.259	0.104	40.15	4.745
NCNT-Na	726	700	0.370	0.292	78.92	2.077
CNT-Ba	18	11	0.037	0.008	21.62	9.294
NCNT-Ba	15	6	0.034	0.007	20.59	16.037

图2 复合材料的XRD分析和Raman分析

图3 复合材料的FTIR光谱分析

图4 复合材料的O 1s谱、N 1s谱和氧、氮峰面积占复合材料总面积的比例

表3 复合材料的XPS分布详细数据

复合材料	C原子分数/%	N原子分数/%	N物种比例/%
复合材料	C原子分数/%	N原子分数/%	N-6		N-5		—NH₂		N-Q		N—O
CNT-K	84.41	1.47	29.17		15.38		22.33		14.25		18.88
NCNT-K	90.47	0.91	42.21		16.92		16.63		11.32		12.92
CNT-Na	80.06	1.52	29.89		30.14		27.35		9.60		3.02
NCNT-Na	87.37	1.47	14.84		26.19		24.70		24.78		9.49
CNT-Ba	87.64	1.79	25.11		27.80		13.86		26.58		6.64
NCNT-Ba	86.10	1.75	19.83		31.40		9.64		17.18		21.95
复合材料	O原子分数/%	O物种比例/%
复合材料	O原子分数/%	C $̿$ O^①		C $̿$ O^②		C—O		COOH		H₂O(ad)
CNT-K	14.12	44.25		43.16		10.82		1.32		0.46
NCNT-K	8.62	55.82		19.72		15.69		7.57		1.20
CNT-Na	18.41	22.47		40.43		30.04		5.76		1.30
NCNT-Na	11.16	13.59		32.24		42.03		8.16		3.97
CNT-Ba	10.57	32.22		34.26		19.16		11.29		3.07
NCNT-Ba	12.15	33.93		35.01		24.95		4.33		1.78

表3 复合材料的XPS分布详细数据

复合材料	C原子分数/%	N原子分数/%	N物种比例/%
复合材料	C原子分数/%	N原子分数/%	N-6		N-5		—NH₂		N-Q		N—O
CNT-K	84.41	1.47	29.17		15.38		22.33		14.25		18.88
NCNT-K	90.47	0.91	42.21		16.92		16.63		11.32		12.92
CNT-Na	80.06	1.52	29.89		30.14		27.35		9.60		3.02
NCNT-Na	87.37	1.47	14.84		26.19		24.70		24.78		9.49
CNT-Ba	87.64	1.79	25.11		27.80		13.86		26.58		6.64
NCNT-Ba	86.10	1.75	19.83		31.40		9.64		17.18		21.95
复合材料	O原子分数/%	O物种比例/%
复合材料	O原子分数/%	C $̿$ O^①		C $̿$ O^②		C—O		COOH		H₂O(ad)
CNT-K	14.12	44.25		43.16		10.82		1.32		0.46
NCNT-K	8.62	55.82		19.72		15.69		7.57		1.20
CNT-Na	18.41	22.47		40.43		30.04		5.76		1.30
NCNT-Na	11.16	13.59		32.24		42.03		8.16		3.97
CNT-Ba	10.57	32.22		34.26		19.16		11.29		3.07
NCNT-Ba	12.15	33.93		35.01		24.95		4.33		1.78

图5 复合材料的SEM分析

图6 接触角

图7 复合材料的时间吸附曲线和NCNT-N的动力学拟合（Rh B浓度=100mg/L，吸附剂浓度=1g/L，pH=7，T=298K）

表4 NCNT-N的动力学拟合详细数据

参数	伪一阶	伪二阶	参数	第一步	第二步	第三步
k/min^-1	0.2531	0.0002	K/mg·g^-0.5∙t^-0.5	49.63	8.04	4.76
q_e/mg·g^-1	137.60	157.81	C	0.90	82.89	103.46
R²	0.8708	0.9320	R²	0.9942	0.9567	0.9041

图8 NCNT-K的粒子扩散模型

图9 在298K、313K、323K温度下NCNT-K的等温吸附模型和1/T与lnK之间的线性关系（Rh B浓度=100mg/L，吸附剂浓度=1g/L，pH=7）

表5 NCNT-K的等温吸附模型详细数据

温度	Langmuir模型			Freundlich模型			q_e/mg·g^-1
温度	q_max/mg·g^-1	K_L/L·mg^-1	R²	n	K_F/mg·g^-1·L^1/ⁿ ·mg^-1/ⁿ	R²	q_e/mg·g^-1
298K	288.15	1.61	0.9675	1.64	17.92	0.9914	275.13
313K	490.17	0.56	0.9707	7.74	269.41	0.9897	454.43
323K	598.26	0.80	0.9723	8.31	364.81	0.9877	598.09

表6 NCNT-K的热力学拟合数据

温度	∆G^⊖/kJ·mol^-1	∆H^⊖/kJ·mol^-1	∆S^⊖/kJ·mol^-1·K^-1
298K	-7.15	+0.11	+4.65
313K	-14.56
323K	-15.84

参考文献 34

[1]	AMALINA Farah, RAZAK Abdul Syukor ABD, KRISHNAN Santhana, et al. A review of eco-sustainable techniques for the removal of Rhodamine B dye utilizing biomass residue adsorbents[J]. Physics and Chemistry of the Earth, Parts A/B/C, 2022, 128: 103267.
[2]	BENI Ali Aghababai, ESMAEILI Akbar. Biosorption, an efficient method for removing heavy metals from industrial effluents: A review[J]. Environmental Technology & Innovation, 2020, 17: 100503.
[3]	Byung-Moon JUN, LEE Hyun-Kyu, PARK Sungbin, et al. Purification of uranium-contaminated radioactive water by adsorption: A review on adsorbent materials[J]. Separation and Purification Technology, 2021, 278: 119675.
[4]	LI Shuangjun, YUAN Xiangzhou, DENG Shuai, et al. A review on biomass-derived CO₂ adsorption capture: Adsorbent, adsorber, adsorption, and advice[J]. Renewable and Sustainable Energy Reviews, 2021, 152: 111708.
[5]	林少华, 武海霞, 高莉苹, 等. 改性碳纳米管及其复合材料在废水处理中的应用现状及展望[J]. 化工进展, 2021, 40(6): 3466-3479.
	LIN Shaohua, WU Haixia, GAO Liping, et al. Current status and future prospects of modified carbon nanotube and its composite materials application for wastewater treatment[J]. Chemical Industry and Engineering Progress, 2021, 40(6): 3466-3479.
[6]	张德懿, 雷龙艳, 尚永花. 氮掺杂对碳材料性能的影响研究进展[J]. 化工进展, 2016, 35(3): 831-836.
	ZHANG Deyi, LEI Longyan, SHANG Yonghua. Effect of the nitrogen doping on the performance of nano-structure carbon materials: A review[J]. Chemical Industry and Engineering Progress, 2016, 35(3): 831-836.
[7]	KUMAR Sumeet, Jayanta DAS. Carbon nanotubes, nanochains and quantum dots synthesized through the chemical treatment of charcoal powder[J]. Journal of Molecular Structure, 2021, 1227: 129419.
[8]	OMAR Sarah, OMAR Mirna, ATTIA Nour F, et al. Rational engineering and fabrication of efficient nanophotocatalysts based on ZnO-SrO-CdS for pharmaceutical pollutants based wastewater degradation[J]. Surfaces and Interfaces, 2024, 45: 103817.
[9]	WANG Gen, GAO Ge, YANG Shengjiong, et al. Magnetic mesoporous carbon nanospheres from renewable plant phenol for efficient hexavalent chromium removal[J]. Microporous and Mesoporous Materials, 2021, 310: 110623.
[10]	ZHANG Xialan, WANG Xin, CHENG Ting, et al. A novel mesoporous carbon nanospheres-based adsorbent material with desirable performances for dyes removal[J]. Journal of Molecular Liquids, 2023, 390: 123091.
[11]	AI Lunhong, ZHANG Chunying, LIAO Fang, et al. Removal of methylene blue from aqueous solution with magnetite loaded multi-wall carbon nanotube: Kinetic, isotherm and mechanism analysis[J]. Journal of Hazardous Materials, 2011, 198: 282-290.
[12]	VARGUES F, BRION M A, ROSA DA COSTA A M, et al. Development of a magnetic activated carbon adsorbent for the removal of common pharmaceuticals in wastewater treatment[J]. International Journal of Environmental Science and Technology, 2021, 18(9): 2805-2818.
[13]	AUNG Myat Thandar, SHIMABUKU Kyle K, Natalia SOARES-QUINETE, et al. Leveraging DOM UV absorbance and fluorescence to accurately predict and monitor short-chain PFAS removal by fixed-bed carbon adsorbers[J]. Water Research, 2022, 213: 118146.
[14]	SHI Wen, WANG Hui, YAN Jinlong, et al. Wheat straw derived biochar with hierarchically porous structure for bisphenol A removal: Preparation, characterization, and adsorption properties[J]. Separation and Purification Technology, 2022, 289: 120796.
[15]	XIAO Ye, AZAIEZ Jalel, HILL Josephine M. Erroneous application of pseudo-second-order adsorption kinetics model: Ignored assumptions and spurious correlations[J]. Industrial & Engineering Chemistry Research, 2018, 57(7): 2705-2709.
[16]	MATOS Beatriz, BATISTA Mary, PIRES João. Efficient adsorption of carbon dioxide and methane on activated carbon prepared from glycerol with potassium acetate[J]. Environmental Chemistry Letters, 2023, 21(3): 1265-1270.
[17]	ELWADOOD Samar N ABD, K Suresh Kumar REDDY, WAHEDI Yasser AL, et al. Hybrid salt-enriched micro-sorbents for atmospheric water sorption[J]. Journal of Water Process Engineering, 2023, 52: 103560.
[18]	HE Zhiqin, LI Yun, QI Benkun. A new and low-cost surface-functionalized corn straw adsorbent for adsorptive removal of sodium dodecylbenzene sulfonate: Adsorbent preparation and adsorption performance[J]. Separation and Purification Technology, 2023, 309: 122999.
[19]	ZHI Fangke, ZHOU Wenjing, CHEN Jingru, et al. Adsorption properties of active biochar: Overlooked role of the structure of biomass[J]. Bioresource Technology, 2023, 387: 129695.
[20]	ZHANG Tiankai, ZHANG Yongfa, WANG Qi, et al. Mechanism of K-catalyzed transformation of solid carbon structure into carbon nanotubes in coal[J]. Fuel Processing Technology, 2020, 204: 106409.
[21]	张天开. Fe/K催化煤热解直接制备碳纳米管机理研究[D]. 太原: 太原理工大学, 2020.
	ZHANG Tiankai. Study on the mechanism of direct preparation of carbon nanotubes from coal pyrolysis catalyzed by Fe/K[D]. Taiyuan: Taiyuan University of Technology, 2020.
[22]	EL-SEESY Ahmed I, WALY Mahmoud S, EL-BATSH Hesham M, et al. Enhancement of the diesel fuel characteristics by using nitrogen-doped multi-walled carbon nanotube additives[J]. Process Safety and Environmental Protection, 2023, 171: 561-577.
[23]	GUO Dawei, WU Jiabo, FENG Dongdong, et al. Mechanism of efficient magnetic biochar for typical aqueous organic contaminant combined-adsorption removal[J]. Fuel Processing Technology, 2023, 247: 107795.
[24]	DAULAY Amru, ASTUTI Widi, SUMARDI Slamet, et al. Synthesis and characteristics of Na-A zeolite from coal fly ash and application for adsorption of cerium(Ⅲ)[J]. Journal of Rare Earths, 2025, 43(1): 171-179.
[25]	CHEN Hsi-Chao, CHIU Hsuan-Yi, HUANG Kuoting. Raman spectroscopy on 3-D acid-functional single-walled carbon nanotubes for flexible transparent-conducting films deposited with vacuum-filtration and dip-coating[J]. Diamond and Related Materials, 2019, 92: 1-8.
[26]	ELLISON Candice, ABDELSAYED Victor, SMITH Mark W. Analysis of char structure and composition from microwave and conventional pyrolysis/gasification of low and middle rank coals[J]. Fuel, 2023, 354: 129301.
[27]	DENIS Pablo A. Heteroatom codoped graphene: The importance of nitrogen[J]. ACS Omega, 2022, 7(50): 45935-45961.
[28]	XU Xiangju, YANG Chen, YANG Zhi, et al. Carbon nanotube growth from alkali metal salt nanoparticles[J]. Carbon, 2014, 80: 490-495.
[29]	JIANG Qinyuan, WANG Fei, LI Run, et al. Synthesis of ultralong carbon nanotubes with ultrahigh yields[J]. Nano Letters, 2023, 23(2): 523-532.
[30]	KANG Jian, DUAN Xiaoguang, WANG Chen, et al. Nitrogen-doped bamboo-like carbon nanotubes with Ni encapsulation for persulfate activation to remove emerging contaminants with excellent catalytic stability[J]. Chemical Engineering Journal, 2018, 332: 398-408.
[31]	WEI Kexin, Tao LYU, WANG Ting, et al. High adsorption of methyl orange by nitrogen-doped activated carbon derived from kraft lignin via self-activation[J]. Surfaces and Interfaces, 2023, 42: 103484.
[32]	HE Haijie, CHAI Kuan, WU Tao, et al. Adsorption of rhodamine B from simulated waste water onto kaolin-bentonite composites[J]. Materials, 2022, 15(12): 4058.
[33]	FODIL M, MAANE S, AVALOS RAMIREZ A, et al. Adsorption of lead from wastewater using olive leaf powder as biosorbent[J]. International Journal of Environmental Science and Technology, 2024, 21(3): 2615-2626.
[34]	GHASEMZADEH Hasan, BABAEI Saeed, TESSON Stéphane, et al. From excess to absolute adsorption isotherm: The effect of the adsorbed density[J]. Chemical Engineering Journal, 2021, 425: 131495.

碱金属催化煤热解制备CNT复合材料用于吸附罗丹明B

Preparation of CNT composites from coal pyrolysis catalyzed by different alkali metals for adsorption of Rhodamine B

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 15

参考文献 34

相关文章 15

编辑推荐

Metrics

本文评价

[1]	吴邦华, 王德武, 王若瑾, 刘燕, 徐荣升, 张少峰. 气固摆动流化床的起始流化特性[J]. 化工进展, 2025, 44(7): 3770-3780.
[2]	陈阳, 罗进, 王典林, 杨祖国, 杨鹏, 陈勇, 钟翔, 唐丽. 不同分子结构表面活性剂复配体系对超稠油乳化降黏影响[J]. 化工进展, 2025, 44(7): 3838-3849.
[3]	高姣姣, 颜诗宇, 杨太顺, 谢尚志, 杨艳娟, 徐晶. 不同晶型Al₂O₃负载Ru催化剂对聚乙烯氢解的影响[J]. 化工进展, 2025, 44(7): 3917-3927.
[4]	梁书玮, 俞杰, 谢钟音, 裴鉴禄, 林中鑫, 陈泽翔. 共价有机框架吸附放射性气态碘的研究进展[J]. 化工进展, 2025, 44(7): 3965-3975.
[5]	范开峰, 余春雨, 周诗岽, 万宇飞, 郭晶晶, 李思. 油品顺序输送界面跟踪技术与混油长度模型研究进展[J]. 化工进展, 2025, 44(7): 3697-3708.
[6]	任鹏锟, 仲兆平, 张小霓, 杨宇轩, 冉真真. 污泥-木屑基活性炭的制备及其对苯系VOCs的吸附性能[J]. 化工进展, 2025, 44(6): 3031-3040.
[7]	周美梅, 何家慧, 向婉婷, 尚佳欣, 魏心语, 孙蜜蜜, 邹伟, 罗平平. 电纺PVA/SiO₂纳米纤维负载A-TiO₂/BiOBr增强可见光催化活性[J]. 化工进展, 2025, 44(6): 3084-3092.
[8]	韩沛, 李金键, 柯天, 张治国, 鲍宗必, 任其龙, 杨启炜. 新型多孔材料吸附分离六氟化硫/氮气研究进展[J]. 化工进展, 2025, 44(6): 3592-3617.
[9]	陈崇明, 李栋, 郁金星, 车凯, 何伟, 陈传敏. 钛基MXene气凝胶对脱硫废水中Hg(Ⅱ)的吸附性能[J]. 化工进展, 2025, 44(6): 3112-3120.
[10]	余子昱, 陈晓飞, 侯春光, 岳殿鹤, 彭跃莲, 安全福. 渗透汽化和真空膜蒸馏在氨基甲酸酯脱水中的比较[J]. 化工进展, 2025, 44(6): 3247-3257.
[11]	李想, 李佳莹, 倪恒, 孙浩然, 曹家伟, 陈宇轩, 刘凤娇. 氢原子转移反应活化能垒预测研究进展[J]. 化工进展, 2025, 44(6): 3336-3344.
[12]	汪柯, 胡登, 王星博, 孙楠楠, 魏伟. Fe _x Co _y Ca₃Al双功能材料用于CO₂捕集-转化一体化制合成气[J]. 化工进展, 2025, 44(5): 2888-2897.
[13]	罗伊雯, 赵亮, 张宇豪, 刘东阳, 高金森, 徐春明. 轻烃分离材料和机理的研究进展[J]. 化工进展, 2025, 44(5): 2938-2954.
[14]	任世鹏, 安元, 娄春, 梅晟东, 刘凯, 陈新建. 融合深度学习算法的炉内燃烧温度场分布在线重建[J]. 化工进展, 2025, 44(4): 1923-1933.
[15]	王光亚, 董美蓉, 周杰恒, 陈翔, 陆继东. 基于火焰图像时序规整的锅炉负荷监测方法[J]. 化工进展, 2025, 44(4): 1934-1944.