氮掺杂木质素基活性炭的制备、表征及其吸附性能研究

doi:10.3969/j.issn.0253-2417.2023.01.016

摘要/Abstract

摘要：

以碱木质素(AL)作为原料，KOH为活化剂，壳聚糖(CS)为氮源制备氮掺杂木质素基活性炭(N-LAC)，采用SEM、XPS和N₂吸附-脱附等温线等方法对活性炭的结构进行表征，并考察了N-LAC对甲基橙(MO)和亚甲基蓝(MB)的吸附性能。研究结果表明：N-LAC主要由微孔构成，掺氮增大了木质素基活性炭(LAC)的表面孔隙，在制备条件为KOH与AL质量比2∶1、CS添加量(以碱木质素质量计)30%、活化温度800 ℃、活化时间2 h时，N-LAC的比表面积为1 457.79 m²/g，总孔容为0.789 cm³/g，微孔孔容为0.612 cm³/g，平均孔径为2.165 nm。N-LAC中氮元素主要以吡咯型氮(N-5)和吡啶型氮(N-6)形式存在，氮的掺杂会降低活性炭的石墨化程度。N-LAC吸附MO和MB的吸附动力学结果表明：N-LAC吸附MO符合粒内扩散模型，以表面吸附为主；N-LAC吸附MB符合准二级动力学模型。

关键词: 木质素, KOH, 活性炭, 壳聚糖, 吸附

Abstract:

The introduction of nitrogen functional groups on carbon materials can effectively improve carbon materials for dye adsorption performance.We used alkali lignin(AL) as raw material, KOH as an activator, chitosan(CS) for nitrogen source to prepare nitrogen-doped lignin-based activated carbon(N-LAC), the performance of activated carbon was characterized by SEM, XPS and N₂ adsorption-desorption experiments. Experimental results show that N-LAC is dominated by micropore, and nitrogen addition increases the surface porosity of activated carbon. When the preparation conditions are KOH to alkali lignin ratio of 2∶1, account for 30% of chitosan(alkali lignin mass fraction ratio), activation temperature of 800 ℃, and activation time of 2 h, specific surface area is 1 457.79 m²/g, total pore volume is 0.789 cm³/g, micropore volume is 0.612 cm³/g, and average pore size is 2.165 nm. Nitrogen is mainly in the forms of pyrrole nitrogen(N-5) and pyridine nitrogen(N-6), and the doping of nitrogen will reduce the graphitization degree of activated carbon. The N-LAC was applied to the adsorption experiments of methyl orange(MO) and methylene blue(MB), and the adsorption kinetics showed that, N-LAC adsorbed MO according to the intra-particle diffusion model, mainly based on surface adsorption; N-LAC adsorbed MB according to the quasi-second-order kinetic model.

Key words: lignin, KOH, activated carbon, chitosan, adsorption

中图分类号:

TQ35

叶结旺, 周志丹, 金贞福. 氮掺杂木质素基活性炭的制备、表征及其吸附性能研究[J]. 林产化学与工业, 2023, 43(1): 127-132.

Jiewang YE, Zhidan ZHOU, Zhenfu JIN. Preparation, Characterization and Adsorption Properties of Nitrogen-doped Lignin-based Activated Carbon[J]. Chemistry and Industry of Forest Products, 2023, 43(1): 127-132.

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样品 sample	活化温度/℃ temperature	活化时间/h time	比表面积/(m²·g^-1) S_BET	总孔容积/(cm³·g^-1) V_tot	微孔容积/(cm³·g^-1) V_mic	平均孔径/nm average pore size
1	600	2	817.80	0.442	0.395	2.163
2	700	2	1 384.32	0.768	0.615	2.219
3	800	2	1 457.79	0.789	0.612	2.165
4	700	1	1 056.34	0.390	0.433	2.235
5	700	3	1 192.61	0.698	0.509	2.340

初始质量浓度/(mg·L^-1) initial mass concentration	准一级动力学模型 pseudo first-order adsorption kinetics			准二级动力学模型 pseudo second-order adsorption kinetics			Elovich模型 Elovich model			粒内扩散模型 Weber and Morris intra-particle diffusion
初始质量浓度/(mg·L^-1) initial mass concentration	q_e	K_f	R²	q_e	K_s	R²	A	K_e	R²	K_id	C	R²
300	158.47	0.000 23	0.87	140.85	0.007 4	0.85	146.53	0.44	0.91	0.21	146.65	0.97
400	190.25	0.000 39	0.77	111.11	0.016 0	0.78	192.64	0.95	0.90	0.43	193.01	0.88
500	190.31	0.004 00	0.88	149.25	0.011 0	0.92	214.57	1.02	0.80	0.50	241.75	0.92

N-LAC投加量/g N-LAC dosage	准一级动力学模型 pseudo first-order adsorption kinetics			准二级动力学模型 pseudo second-order adsorption kinetics			Elovich模型 Elovich model			粒内扩散模型 Weber and Morris intra-particle diffusion
N-LAC投加量/g N-LAC dosage	q_e	K_f	R²	q_e	K_s	R²	A	K_e	R²	K_id	C	R²
0.05	53.14	0.001 64	0.90	666.67	0.001 1	0.90	490.80	0.956	0.79	0.48	490.90	0.95
0.10	140.67	0.000 32	0.91	303.03	0.002 7	0.91	245.60	0.473	0.74	0.24	245.62	0.92
0.15	55.46	0.000 50	0.94	222.79	0.003 3	0.96	164.39	0.340	0.53	0.14	164.30	0.85

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