活性炭改性及其对模拟废润滑油的净化性能

doi:10.16085/j.issn.1000-6613.2024-0811

化工进展 ›› 2025, Vol. 44 ›› Issue (7): 4022-4031.DOI: 10.16085/j.issn.1000-6613.2024-0811

• 材料科学与技术 • 上一篇

活性炭改性及其对模拟废润滑油的净化性能

徐茹婷¹(), 赵剑¹, 孙康¹, 卢辛成¹(), 蒋剑春¹, 苏忠高², 刘军利¹, 陈子标², 苏子寒²

^1.中国林业科学研究院林产化学工业研究所，江苏省生物质能源与材料重点实验室，国家林业和草原局林产化学工程重点实验室，林木生物质低碳高效利用国家工程研究中心，江苏省林业资源高效加工利用协同创新中心，江苏南京 210042
^2.福建博海材料技术有限公司，福建福州 350000

收稿日期:2024-05-16 修回日期:2024-08-20 出版日期:2025-07-25 发布日期:2025-08-04
通讯作者: 卢辛成
作者简介:徐茹婷（1994—），女，助理研究员，研究方向为炭质吸附材料的制备与应用。E-mail：819275472@qq.com。
基金资助:
国家重点研发计划(2023YFD2201604)

Modification of activated carbon and its purification performance for simulated waste lubricating oil

XU Ruting¹(), ZHAO Jian¹, SUN Kang¹, LU Xincheng¹(), JIANG Jianchun¹, SU Zhonggao², LIU Junli¹, CHEN Zibiao², SU Zihan²

^1.Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Key Laboratory of Biomass Energy and Material, Jiangsu Province, Key Laboratory of Chemical Engineering of Forest Products, National Forestry and Grassland Administration, National Engineering Research Center of Low-Carbon Processing and Utilization of Forest Biomass, Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing 210042, Jiangsu, China
^2.Fujian Bohai Material Technology Co. , Ltd. , Fuzhou 350000, Fujian, China

Received:2024-05-16 Revised:2024-08-20 Online:2025-07-25 Published:2025-08-04
Contact: LU Xincheng

摘要/Abstract

摘要：

以商品活性炭为原料，采用双氧水、硝酸、氨水、乙二胺四乙酸二钠对其进行改性，研究了改性活性炭对模拟废润滑油的净化性能，探讨了活性炭孔结构及表面化学性质对其净化性能的影响机制；进一步研究了活性炭复配聚氨酯制备碳基滤清器对模拟废润滑油的净化性能。结果表明：氨水（NH₃·H₂O）和乙二胺四乙酸二钠（EDTA-Na₂）改性可显著增强活性炭对废润滑油的净化性能，特别是0.03mol/L EDTA-Na₂改性，磨损金属元素吸附量和氧化污染物去除率较未改性活性炭提高了28%和97%，且2次再生后净化性能仍高于未改性活性炭。活性炭对废润滑油的净化性能与其微孔、中孔和表面含氮官能团有关，中孔增加有助于有机污染物和磨损金属元素去除，微孔增加有助于有机污染物去除，表面掺杂吡啶氮增强其净化性能。活性炭与聚氨酯经复配、成型、封装制得碳基滤清器，对废润滑油净化效果显著，具有用于废润滑油再生及汽车发动机滤清器的潜力。

关键词: 活性炭, 改性, 模拟废润滑油, 净化性能, 碳基滤清器

Abstract:

The surface modifications of commercial activated carbon with hydrogen peroxide, nitric acid, ammonia and ethylenediaminetetraacetic acid disodium salt were studied. The effects of pore structure and surface chemical properties of activated carbon on the purification performance of simulated waste lubricating oil were investigated. The purification performance of carbon-based oil filter prepared by activated carbon was further studied. The results showed that the modifications of ammonia (NH₃·H₂O) and ethylenediaminetetraacetic acid disodium salt (EDTA-Na₂) significantly enhanced the purification performance of activated carbon for simulated waste lubricant, especially of 0.03mol/L EDTA-Na₂. The adsorption capacities of wear metal elements and organic pollutants increased by 28% and 97% compared with unmodified activated carbon. The purification performance of the modified activated carbon after secondary regeneration was still higher than that of unmodified activated carbon. The purification performance of activated carbon for simulated waste lubricating oil was related to its micropores, mesopores and surface nitrogen functional groups. The mesopores enhanced the removal of organic pollutants and wear metal elements, the micropores was beneficial to the removal of wear metal elements, and the surface doping of pyridine nitrogen increased the adsorption capacity. Carbon-based oil filter which prepared by combining activated carbon with polyurethane, showed the excellent adsorption property and has potential for waste oil regeneration and used as automotive engine filter.

Key words: activated carbon, modification, simulated waste lubricating oil, purification performance, carbon-based filter

中图分类号:

TQ35

徐茹婷, 赵剑, 孙康, 卢辛成, 蒋剑春, 苏忠高, 刘军利, 陈子标, 苏子寒. 活性炭改性及其对模拟废润滑油的净化性能[J]. 化工进展, 2025, 44(7): 4022-4031.

XU Ruting, ZHAO Jian, SUN Kang, LU Xincheng, JIANG Jianchun, SU Zhonggao, LIU Junli, CHEN Zibiao, SU Zihan. Modification of activated carbon and its purification performance for simulated waste lubricating oil[J]. Chemical Industry and Engineering Progress, 2025, 44(7): 4022-4031.

图/表 16

图1 活性炭的氮气吸-脱附等温线和孔径分布

表1 活性炭的比表面积及孔结构参数

样品	比表面积/m²·g^-1	总孔容/cm³·g^-1	微孔孔容/cm³·g^-1	中孔孔容/cm³·g^-1	平均孔径/nm
AC	1860	1.390	0.489	0.901	3.55
AC-H₂O₂	1004	0.692	0.367	0.325	2.78
AC-HNO₃	1274	0.990	0.455	0.535	3.08
AC-NH₃·H₂O	1873	1.623	0.674	0.949	3.83
AC-EDTA-Na₂	1924	1.664	0.692	0.972	3.37

表2 活性炭的元素分析

样品	C质量分数/%	H质量分数/%	O质量分数/%	N质量分数/%
AC	70.38	1.41	19.34	1.37
AC-H₂O₂	59.41	2.04	32.73	1.21
AC-HNO₃	57.01	1.84	32.99	3.16
AC-NH₃·H₂O	74.37	1.54	19.50	2.44
AC-EDTA-Na₂	73.61	1.70	18.43	2.09

图2 活性炭的FTIR谱图

图3 活性炭的XPS谱图

图4 活性炭的C 1s谱图

图5 活性炭的N 1s谱图

表3 活性炭样品的C 1s和N 1s分峰结果

官能团	峰	结合能/eV	官能团相对含量/%
官能团	峰	结合能/eV	AC	AC-H₂O₂	AC-HNO₃	AC-NH₃·H₂O	AC-EDTA-Na₂
C 1s
C—C/C $̿$ C	A	284.6	75.56	72.00	72.54	78.73	76.31
C—OH	B	286.3	9.47	13.02	11.80	13.25	13.40
C $̿$ O	C	287.4	4.87	3.44	5.16	0.69	1.37
—COOH	D	288.9	9.10	11.54	10.51	7.34	8.92
N 1s
N-6	E	398.9	46.53	10.55	14.60	53.52	56.09
amino-N	F	399.4	10.96	29.50	0.00	0.00	8.24
N-5	G	400.4	19.50	28.51	15.10	17.32	20.96
N-Q	H	401.5	16.13	26.27	17.73	10.42	3.74
—NO _x	I	405.5	6.88	5.17	52.57	18.73	10.97

表3 活性炭样品的C 1s和N 1s分峰结果

官能团	峰	结合能/eV	官能团相对含量/%
官能团	峰	结合能/eV	AC	AC-H₂O₂	AC-HNO₃	AC-NH₃·H₂O	AC-EDTA-Na₂
C 1s
C—C/C $̿$ C	A	284.6	75.56	72.00	72.54	78.73	76.31
C—OH	B	286.3	9.47	13.02	11.80	13.25	13.40
C $̿$ O	C	287.4	4.87	3.44	5.16	0.69	1.37
—COOH	D	288.9	9.10	11.54	10.51	7.34	8.92
N 1s
N-6	E	398.9	46.53	10.55	14.60	53.52	56.09
amino-N	F	399.4	10.96	29.50	0.00	0.00	8.24
N-5	G	400.4	19.50	28.51	15.10	17.32	20.96
N-Q	H	401.5	16.13	26.27	17.73	10.42	3.74
—NO _x	I	405.5	6.88	5.17	52.57	18.73	10.97

图6 活性炭吸附后模拟废润滑油色度变化

表4 活性炭对模拟废润滑油的净化性能

样品	磨损金属元素去除率/%				磨损金属元素总吸附量/mg·g^-1	酸值去除率/%	氧化污染物去除率/%
样品	Fe	Cu	Pb	Al	磨损金属元素总吸附量/mg·g^-1	酸值去除率/%	氧化污染物去除率/%
AC	52±1.73	84±1.52	54±1.15	56±1.00	2.46±0.02	95.34±2.32	27.22±0.96
AC-H₂O₂	14±1.15	72±0.58	22±2.00	20±1.53	1.28±0.02	95.34±0.00	13.55±0.19
AC-HNO₃	44±0.08	92±1.53	54±3.78	46±1.73	2.36±0.07	95.34±2.32	22.44±0.77
AC-NH₃·H₂O	60±2.65	92±2.00	70±1.73	64±1.16	2.86±0.01	>97.67±0.00	32.88±0.39
AC-EDTA-Na₂	72±2.88	90±1.00	68±1.52	64±2.52	2.94±0.06	>97.67±0.00	41.55±0.39

表5 活性炭的孔结构、表面官能团与磨损金属元素吸附容量、氧化污染物去除率的相关性分析

项目	磨损金属元素吸附容量	氧化污染物去除率
比表面积	0.892*	0.895*
总孔容	0.933*	0.950*
微孔孔容	0.895*	0.952*
中孔孔容	0.913*	0.909*
$C$ —OH	0.015	0.199
$C$ $̿$ O	-0.448	-0.621
COOH	0.373	0.250
N-6	0.840	0.902*
amino-N	-0.841	-0.588
N-5	-0.741	-0.439
N-Q	-0.934*	-0.995**
—NO _x	0.172	-0.106

表5 活性炭的孔结构、表面官能团与磨损金属元素吸附容量、氧化污染物去除率的相关性分析

项目	磨损金属元素吸附容量	氧化污染物去除率
比表面积	0.892*	0.895*
总孔容	0.933*	0.950*
微孔孔容	0.895*	0.952*
中孔孔容	0.913*	0.909*
$C$ —OH	0.015	0.199
$C$ $̿$ O	-0.448	-0.621
COOH	0.373	0.250
N-6	0.840	0.902*
amino-N	-0.841	-0.588
N-5	-0.741	-0.439
N-Q	-0.934*	-0.995**
—NO _x	0.172	-0.106

表6 改性试剂浓度对活性炭净化性能的影响

改性试剂浓度	磨损金属元素去除率/%				磨损金属总吸附容量/mg·g^-1	氧化污染物去除率/%
改性试剂浓度	Fe	Cu	Pb	Al	磨损金属总吸附容量/mg·g^-1	氧化污染物去除率/%
5% NH₃·H₂O	62±0.58	92±0.58	68±1.00	64±2.08	2.86±0.02	31.33±1.33
10% NH₃·H₂O	60±2.65	92±2.00	70±1.73	64±1.16	2.86±0.01	32.88±0.39
15% NH₃·H₂O	64±1.53	94±1.15	74±0.58	68±2.65	3.00±0.05	46.22±1.02
0.01mol/L EDTA-Na₂	60±2.00	90±2.31	74±0.58	64±1.53	2.84±0.03	35.11±1.68
0.03mol/L EDTA-Na₂	72±1.15	96±0.00	76±2.52	70±1.53	3.14±0.04	53.55±1.39
0.05mol/LEDTA-Na₂	72±2.88	90±1.00	68±1.52	64±2.52	2.94±0.06	41.55±0.39

表7 再生活性炭对模拟废润滑油的净化性能

样品	磨损金属元素去除率/%				磨损金属元素总吸附容量/mg·g^-1	氧化污染物去除率/%
样品	Fe	Cu	Pb	Al	磨损金属元素总吸附容量/mg·g^-1	氧化污染物去除率/%
AC-EDTA-Na₂-0.03	72±1.15	96±0.00	76±2.52	70±1.53	3.14±0.04	53.55±1.39
一次再生	70±0.58	92±2.08	72±1.00	68±3.00	3.02±0.06	40.00±0.67
二次再生	62±0.58	90±1.00	64±3.21	58±0.00	2.74±0.03	32.89±0.77

图7 碳基滤清器制备及形貌图

图8 碳基芯体微观结构

图9 碳基滤清器与纸质滤清器对废润滑油净化性能

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活性炭改性及其对模拟废润滑油的净化性能

Modification of activated carbon and its purification performance for simulated waste lubricating oil

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