氮自掺杂蓝藻生物质基活性炭的制备及其CO2吸附性能

doi:10.16085/j.issn.1000-6613.2024-0925

摘要/Abstract

摘要：

碳捕集、利用与封存（carbon capture, utilization and storage，CCUS）是解决二氧化碳过度排放的有效方法。本文以蓝藻（cyanobacteria，CB）为前体，氯化锌（zinc chloride，ZnCl₂）为活化剂，通过热解活化法制备N自掺杂CB基活性炭（AC-X），用于CO₂的高效吸附。探讨了活化温度对AC-X比表面积、孔结构、氮（N）原子分数及含N官能团种类的影响，研究了AC-X在0℃和25℃下对CO₂的吸附能力。结果表明，在锌炭比为1.5、活化温度为700℃时，AC-7有最佳的孔隙结构，比表面积为1112.28m²/g，孔体积和微孔体积可达0.82cm³/g和0.52cm³/g。0℃时AC-7对CO₂的吸附效果最佳，为140.45mg/g；当CO₂吸附温度为25℃时，活化温度为600℃所得的AC-6对CO₂的吸附效果最佳，为95.74mg/g，优于AC-7（90.17mg/g）。25℃时AC-6表现出更好的CO₂吸附能力，这得益于AC-6高吡咯N和吡啶N原子分数。通过相关性研究表明，比表面积、微孔体积以及吡咯N和吡啶N的原子分数共同决定了AC-X的CO₂吸附性能。本研究不仅为CB生物质资源化利用提供了一种有效方法，而且设计的N自掺杂CB基活性炭可高效捕集CO₂，助力双碳目标的实现。

关键词: 蓝藻, 活性炭, 二氧化碳捕集, 吸附, 生物质

Abstract:

Carbon capture, utilization, and storage (CCUS) technology is an effective solution to address excessive carbon dioxide (CO₂) emissions. Cyanobacteria (CB) is a widely distributed, accessible, and nitrogen (N)-enriched biomass resource. In this work, nitrogen (N) self-doped activated carbons (AC-X) were prepared via pyrolysis of CB with the aid of zinc chloride (ZnCl₂). The effects of specific surface area, pore structure, N content, types of N-containing functional groups, and adsorption temperatures on the adsorption capacity of AC-X for CO₂ were investigated. The results showed that AC-7 possessed a large specific surface area (1112.28m²/g), the highest pore volume (0.82cm³/g) and micropore volume (0.52cm³/g) when the mass ratio of ZnCl₂/activated carbon was 1.5 and the activation temperature was 700℃. The optimal CO₂ sorption capacity of AC-7 at 0℃ was 140.45mg/g. At 25℃, the CO₂ sorption capacity of AC-6 was 95.74mg/g, superior to that of AC-7 (90.17mg/g), which was beneficial from the high content of pyrrole N and pyridine N in AC-6. The correlation study showed that the specific surface area, the micropore volume, and the content of pyrrole N and pyridine N collectively determined the CO₂ adsorption performance of AC-X. This study not only provided an effective method for the resource utilization of CB biomass but also provided N self-doped CB-based activated carbons which could efficiently capture CO₂.

Key words: cyanobacteria, activated carbon, CO₂capture, adsorption, biomass

中图分类号:

秘一芳, 王保国, 王文强, 孙国金, 曹志海. 氮自掺杂蓝藻生物质基活性炭的制备及其CO₂吸附性能[J]. 化工进展, 2025, 44(7): 4223-4232.

MI Yifang, WANG Baoguo, WANG Wenqiang, SUN Guojin, CAO Zhihai. Preparation of nitrogen self-doped cyanobacterial biomass-based activated carbon for CO₂ adsorption[J]. Chemical Industry and Engineering Progress, 2025, 44(7): 4223-4232.

图/表 12

参考文献 35

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样品	比表面积/m²·g^-1	微孔面积/m²·g^-1	总孔体积/cm³·g^-1	微孔体积/cm³·g^-1	平均孔径/nm
AC-5	726.71	693.86	0.43	0.33	2.38
AC-6	1158.39	865.71	0.82	0.43	2.84
AC-7	1112.28	979.32	0.82	0.52	2.97
AC-8	1019.25	853.35	0.65	0.42	2.55

样品	比表面积/m²·g^-1	微孔面积/m²·g^-1	总孔体积/cm³·g^-1	微孔体积/cm³·g^-1	平均孔径/nm
AC-5	726.71	693.86	0.43	0.33	2.38
AC-6	1158.39	865.71	0.82	0.43	2.84
AC-7	1112.28	979.32	0.82	0.52	2.97
AC-8	1019.25	853.35	0.65	0.42	2.55

样品	温度 /℃	Langmuir			Freundlich			q_e/mg·g^-1
样品	温度 /℃	q₀/mg·g^-1	K_l/kPa^-1	R²	n	K_f/mg·g^-1·kPa ⁿ	R²	q_e/mg·g^-1
AC-5	0	147.21	0.0331	0.9913	2.146	13.77	0.9973	116.97
AC-6		196.05	0.0215	0.9930	1.878	11.89	0.9991	138.29
AC-7		193.38	0.0236	0.9915	1.938	13.03	0.9992	140.45
AC-8		189.26	0.0190	0.9934	1.814	10.07	0.9995	128.00
AC-5	25	115.44	0.0199	0.9968	1.801	6.22	0.9978	78.79
AC-6		155.31	0.0150	0.9967	1.669	6.05	0.9991	95.74
AC-7		144.66	0.0155	0.9967	1.686	5.88	0.9990	90.17
AC-8		149.64	0.0139	0.9965	1.639	5.37	0.9994	89.49

样品	温度 /℃	Langmuir			Freundlich			q_e/mg·g^-1
样品	温度 /℃	q₀/mg·g^-1	K_l/kPa^-1	R²	n	K_f/mg·g^-1·kPa ⁿ	R²	q_e/mg·g^-1
AC-5	0	147.21	0.0331	0.9913	2.146	13.77	0.9973	116.97
AC-6		196.05	0.0215	0.9930	1.878	11.89	0.9991	138.29
AC-7		193.38	0.0236	0.9915	1.938	13.03	0.9992	140.45
AC-8		189.26	0.0190	0.9934	1.814	10.07	0.9995	128.00
AC-5	25	115.44	0.0199	0.9968	1.801	6.22	0.9978	78.79
AC-6		155.31	0.0150	0.9967	1.669	6.05	0.9991	95.74
AC-7		144.66	0.0155	0.9967	1.686	5.88	0.9990	90.17
AC-8		149.64	0.0139	0.9965	1.639	5.37	0.9994	89.49

活性炭	比表面积/m²·g^-1	总孔体积/cm³·g^-1	总N原子分数/%	CO₂吸附量/mg·g^-1		吸附下降/%	参考文献
活性炭	比表面积/m²·g^-1	总孔体积/cm³·g^-1	总N原子分数/%	0℃	25℃	吸附下降/%	参考文献
AC-5	726.71	0.43	5.60	116.97	78.79	32.64	本研究
AC-6	1158.39	0.82	10.80	138.29	95.74	30.77	本研究
AC-7	1112.28	0.82	11.35	140.45	90.17	35.80	本研究
AC-8	1019.25	0.65	9.96	128.00	89.49	30.08	本研究
非洲棕榈壳	501.00	0.24	—	129.80	—	—	[28]
核桃壳	700.00	0.53	—	—	69.52		[29]
葡萄枝	767.00	0.37	—	179.08	69.52	61.18	[30]
柏木屑	1134.00	0.95	2.58	120.12	76.12	36.63	[31]
稻草杆	781.40	—	1.36	139.48	87.12	37.54	[17]
芦竹	1863.00	1.00	6.50	158.40	92.40	41.67	[32]

氮自掺杂蓝藻生物质基活性炭的制备及其CO₂吸附性能

Preparation of nitrogen self-doped cyanobacterial biomass-based activated carbon for CO₂ adsorption

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