污泥-木屑基活性炭的制备及其对苯系VOCs的吸附性能

doi:10.16085/j.issn.1000-6613.2024-1144

摘要/Abstract

摘要：

将市政污泥与木屑共热解，采用不同活化剂（KOH、K₂CO₃）和不同活化方法（球磨活化、浸渍活化）将其活化改性，制备出一系列污泥-木屑基活性炭，并通过吸附实验研究苯系VOCs在所制备炭材料上的吸附行为。研究发现，所制备的4种污泥-木屑基活性炭均含有丰富的微孔和介孔结构，其中KOH球磨改性共热解炭（H-SBBC）拥有最高的比表面积（1640.21m²/g）和孔容（1.0384cm³/g），其表面呈现更利于气态污染物吸附的蜂窝状三维孔道结构。动态吸附实验结果显示，H-SBBC对甲苯和对二甲苯的饱和吸附容量最高，分别为270.80mg/g和312.86mg/g，其良好的吸附性能来源于发达的孔洞结构和丰富的表面官能团。静态吸附实验结果显示，甲苯和对二甲苯在H-SBBC上的吸附过程符合L-F模型，吸附过程以物理吸附为主，其中H-SBBC与对二甲苯的亲和力更高。H-SBBC在循环6次后，对甲苯和对二甲苯的吸附容量仍保持在85%以上，拥有良好的再生性能，具有较高的工业应用潜力。

关键词: 污泥, 挥发性有机化合物, 共热解, 活化, 吸附

Abstract:

Co-pyrolysis of municipal sludge and sawdust was conducted, followed by activation modification using different activators (KOH, K₂CO₃) and various activation methods (ball milling activation, impregnation activation). A series of sludge-sawdust-based activated carbons were prepared, and the adsorption behavior of benzene-series VOCs on these prepared carbon materials was studied through adsorption experiments. The study found that all four types of sludge-sawdust-based activated carbons contained abundant microporous and mesoporous structures. Among them, KOH-ball- milling-modified co-pyrolysis carbon (H-SBBC) possessed the highest specific surface area (1640.21m²/g) and pore volume (1.0384cm³/g), with a surface exhibiting a honeycomb-like three-dimensional pore structure conducive to the adsorption of gaseous pollutants. The results of dynamic adsorption experiments showed that H-SBBC had the highest saturated adsorption capacities for toluene and p-xylene, being 270.80mg/g and 312.86mg/g, respectively. Its excellent adsorption performance stemmed from its developed pore structure and abundant surface functional groups. The static adsorption experiments indicated that the adsorption processes of toluene and p-xylene on H-SBBC conformed to the Langmuir-Freundlich (L-F) model, primarily involving physical adsorption, with H-SBBC showing higher affinity towards p-xylene. After six cycles, the adsorption capacities of H-SBBC for toluene and p-xylene remained above 85%, demonstrating good regeneration performance and high potential for industrial applications.

Key words: sludge, volatile organic compounds, co-pyrolysis, activation, adsorption

中图分类号:

X705

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.

REN Pengkun, ZHONG Zhaoping, ZHANG Xiaoni, YANG Yuxuan, RAN Zhenzhen. Preparation of sludge-sawdust-based activated carbon and its adsorption performance for benzene series VOCs[J]. Chemical Industry and Engineering Progress, 2025, 44(6): 3031-3040.

图/表 14

参考文献 32

[1]	CHAMBERS D M, REESE C M, THORNBURG L G, et al. Distinguishing petroleum (crude oil and fuel) from smoke exposure within populations based on the relative blood levels of benzene, toluene, ethylbenzene, and xylenes (BTEX), styrene and 2,‍5-dimethylfuran by pattern recognition using artificial neural networks[J]. Environmental Science & Technology, 2018, 52(1): 308-316.
[2]	HE Jiakai, ZHAO Yuanyuan, ZHOU Yun, et al. Preparation of high-performance activated carbons from hemicellulose pre-extracted residues of poplar and their application in VOCs removal[J]. BioResources, 2023, 18(2): 2874-2896.
[3]	LIU Shuang, WU Shubin, CHENG Hao, et al. Sodium lignosulfonate derived hierarchical porous carbon spheres for VOC removal and supercapacitors[J]. Industrial Crops and Products, 2022, 179: 114657.
[4]	ZHANG Xueyang, MIAO Xudong, XIANG Wei, et al. Ball milling biochar with ammonia hydroxide or hydrogen peroxide enhances its adsorption of phenyl volatile organic compounds (VOCs)[J]. Journal of Hazardous Materials, 2021, 403: 123540.
[5]	QI Guangdou, PAN Zhifei, ZHANG Xueyang, et al. Effect of ball milling with hydrogen peroxide or ammonia hydroxide on sorption performance of volatile organic compounds by biochar from different pyrolysis temperatures[J]. Chemical Engineering Journal, 2022, 450: 138027.
[6]	Karin BJÖRKLUND, LI Loretta Y. Adsorption of organic stormwater pollutants onto activated carbon from sewage sludge[J]. Journal of Environmental Management, 2017, 197: 490-497.
[7]	ZHAO Lei, SUN Zhongfang, PAN Xiaowen, et al. Sewage sludge derived biochar for environmental improvement: Advances, challenges, and solutions[J]. Water Research X, 2023, 18: 100167.
[8]	HAN Lei, LI Jinling, QU Chengtun, et al. Recent progress in sludge co-pyrolysis technology[J]. Sustainability, 2022, 14(13): 7574.
[9]	FENG Dongdong, GUO Dawei, ZHANG Yu, et al. Functionalized construction of biochar with hierarchical pore structures and surface O-/N-containing groups for phenol adsorption[J]. Chemical Engineering Journal, 2021, 410: 127707.
[10]	OUZZINE M, ROMERO-ANAYA A J, LILLO-RÓDENAS M A, et al. Spherical activated carbons for the adsorption of a real multicomponent VOC mixture[J]. Carbon, 2019, 148: 214-223.
[11]	GUO Qianqian, JING Wen, HOU Yaqin, et al. On the nature of oxygen groups for NH₃-SCR of NO over carbon at low temperatures[J]. Chemical Engineering Journal, 2015, 270: 41-49.
[12]	HUANG Weihao, LEE Duu-Jong, HUANG Chihpin. Modification on biochars for applications: A research update[J]. Bioresource Technology, 2021, 319: 124100.
[13]	ZHOU Ke, MA Weiwu, ZENG Zheng, et al. Waste biomass-derived oxygen and nitrogen co-doped porous carbon/MgO composites as superior acetone adsorbent: Experimental and DFT study on the adsorption behavior[J]. Chemical Engineering Journal, 2020, 387: 124173.
[14]	XIAO Xin, CHEN Baoliang, ZHU Lizhong. Transformation, morphology, and dissolution of silicon and carbon in rice straw-derived biochars under different pyrolytic temperatures[J]. Environmental Science & Technology, 2014, 48(6): 3411-3419.
[15]	JIN Baichuan, LI Jie, WANG Yuhui, et al. Nitrogen doping and porous tuning carbon derived from waste biomass boosting for toluene capture: Experimental study and density functional theory simulation[J]. Chemical Engineering Journal Advances, 2022, 10: 100276.
[16]	WANG Xingdong, CHI Qiaoqiao, LIU Xuejiao, et al. Influence of pyrolysis temperature on characteristics and environmental risk of heavy metals in pyrolyzed biochar made from hydrothermally treated sewage sludge[J]. Chemosphere, 2019, 216: 698-706.
[17]	CHEN Baoliang, ZHOU Dandan, ZHU Lizhong. Transitional adsorption and partition of nonpolar and polar aromatic contaminants by biochars of pine needles with different pyrolytic temperatures[J]. Environmental Science & Technology, 2008, 42(14): 5137-5143.
[18]	WANG Fei, REN Xinhao, SUN Hongwen, et al. Sorption of polychlorinated biphenyls onto biochars derived from corn straw and the effect of propranolol[J]. Bioresource Technology, 2016, 219: 458-465.
[19]	LIU Huijuan, YU Yansong, SHAO Qi, et al. Porous polymeric resin for adsorbing low concentration of VOCs: Unveiling adsorption mechanism and effect of VOCs’ molecular properties[J]. Separation and Purification Technology, 2019, 228: 115755.
[20]	LU Shengyong, HUANG Xinlei, TANG Minghui, et al. Synthesis of N-doped hierarchical porous carbon with excellent toluene adsorption properties and its activation mechanism[J]. Environmental Pollution, 2021, 284: 117113.
[21]	张智, 马修卫, 李津津, 等. 中高温环境下VOCs在活性炭上的吸附性能研究 [J]. 化工学报, 2019, 70(12): 4811-4820.
	ZHANG Zhi, MA Xiuwei, Li Jinjin, et al. Study on adsorption capacity of VOCs on activated carbon at medium-high temperature [J]. CIESC Journal, 2019, 70(12): 4811-4820.
[22]	YANG Yuxuan, SUN Chen, HUANG Qunxing, et al. Hierarchical porous structure formation mechanism in food waste component derived N-doped biochar: Application in VOCs removal[J]. Chemosphere, 2022, 291: 132702.
[23]	SHEN Yafei, ZHANG Niyu. Facile synthesis of porous carbons from silica-rich rice husk char for volatile organic compounds (VOCs) sorption[J]. Bioresource Technology, 2019, 282: 294-300.
[24]	PI Xinxin, QU Zhibin, SUN Fei, et al. Catalytic activation preparation of nitrogen-doped hierarchical porous bio-char for efficient adsorption of dichloromethane and toluene[J]. Journal of Analytical and Applied Pyrolysis, 2021, 156: 105150.
[25]	CHENG Tangying, BIAN Ye, LI Jinjin, et al. Nitrogen-doped porous biochar for selective adsorption of toluene under humid conditions[J]. Fuel, 2023, 334: 126452.
[26]	MOSLEH Mojgan Hadi, RAJABI Hamid. NaOH-benzoic acid modified biochar for enhanced removal of aromatic VOCs[J]. Separation and Purification Technology, 2024, 330: 125453.
[27]	BEDANE Alemayehu H, GUO Tianxiang, Mladen EIĆ, et al. Adsorption of volatile organic compounds on peanut shell activated carbon[J]. The Canadian Journal of Chemical Engineering, 2019, 97(1): 238-246.
[28]	MA Xiuwei, Hao LYU, YANG Linjun, et al. Removal characteristics of organic pollutants by the adsorbent injection coupled with bag filtering system[J]. Journal of Hazardous Materials, 2021, 405: 124193.
[29]	CHENG Tangying, LI Jinjin, MA Xiuwei, et al. Alkylation modified pistachio shell-based biochar to promote the adsorption of VOCs in high humidity environment[J]. Environmental Pollution, 2022, 295: 118714.
[30]	LI Jinjin, YIN Yin, CHENG Tangying, et al. Superior pore size for enhancing the competitive adsorption of VOCs under high humid conditions: An experiment and molecular simulation study[J]. Journal of Environmental Chemical Engineering, 2023, 11(5): 111091.
[31]	岳旭, 王胜, 高杨, 等. VOCs在吸附剂上吸附性能的热力学研究[J]. 燃料化学学报, 2020, 48: 752-760.
	YUE Xu, WANG Sheng, GAO Yang, et al. Thermodynamics analysis on the adsorption behaviors of VOCs on various adsorbents [J]. Journal of Fuel Chemistry and Technology, 2020, 48: 752-760.
[32]	LUO Junying, LIU Baogen, SHI Rui, et al. The effects of nitrogen functional groups and narrow micropore sizes on CO₂ adsorption onto N-doped biomass-based porous carbon under different pressure[J]. Microporous and Mesoporous Materials, 2021, 327: 111404.

样品	工业分析/%			元素分析/%
样品	灰分	挥发分	固定碳	C	H	O	N	S
市政污泥	58.58	38.42	3.00	15.22	3.61	17.22	2.17	3.20
松木屑	0.58	85.28	14.14	46.43	5.53	44.81	0.66	1.99

样品	工业分析/%			元素分析/%
样品	灰分	挥发分	固定碳	C	H	O	N	S
市政污泥	58.58	38.42	3.00	15.22	3.61	17.22	2.17	3.20
松木屑	0.58	85.28	14.14	46.43	5.53	44.81	0.66	1.99

样品	比表面积/m²·g^-1	微孔面积/m²·g^-1	孔容/cm³·g^-1	微孔孔容/cm³·g^-1	微孔率/%	平均孔径/nm
H-SBBC	1640.21	1542.63	1.0384	0.6695	64.47	2.5325
C-SBBC	1514.95	1427.85	0.9082	0.6073	66.87	2.3981
H-SBZC	1496.59	1421.43	1.0258	0.6152	59.97	2.7419
C-SBZC	1403.50	1320.07	0.8637	0.5677	65.73	2.4614
AC	759.41	664.77	0.6035	0.3194	52.92	3.1786

样品	比表面积/m²·g^-1	微孔面积/m²·g^-1	孔容/cm³·g^-1	微孔孔容/cm³·g^-1	微孔率/%	平均孔径/nm
H-SBBC	1640.21	1542.63	1.0384	0.6695	64.47	2.5325
C-SBBC	1514.95	1427.85	0.9082	0.6073	66.87	2.3981
H-SBZC	1496.59	1421.43	1.0258	0.6152	59.97	2.7419
C-SBZC	1403.50	1320.07	0.8637	0.5677	65.73	2.4614
AC	759.41	664.77	0.6035	0.3194	52.92	3.1786

吸附质	吸附剂	比表面积/m²·g^-1	孔容/cm³·g^-1	吸附温度/K	吸附容量/mg·g^-1	参考文献
甲苯	H-SBBC	1640.21	1.04	293	270.80	本文
	骨头生物炭	1405.06	0.97	298	288.12	[22]
	富硅稻壳生物炭	1818.45	0.90	293	264.00	[23]
	木屑生物炭	1606.70	1.13	298	308.00	[24]
	开心果壳生物炭	1832.03	0.80	298	223.00	[25]
对二甲苯	H-SBBC	1640.21	1.04	293	312.86	本文
	球磨秸秆生物炭	405.61	0.19	298	130.21	[4]
	硬木活性炭	101.58	0.1802	—	131.24	[26]
	花生壳活性炭	1025.00	1.07	293	296.80	[27]