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

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

Abstract

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

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

CLC Number:

TQ35

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.

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.

Figures/Tables 16

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

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

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

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

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

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

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

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

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

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