热解自活化法制备竹箨活性炭及其砷吸附性能

姚尧; 刘志佳; 陈瑶; 何林韩; 高建民

doi:10.12171/j.1000-1522.20230162

热解自活化法制备竹箨活性炭及其砷吸附性能

姚尧^{1, 2,},
刘志佳³,
陈瑶^{1, 2, ,},
何林韩^{1, 2},
高建民^{1, 2}

1.
北京林业大学木质材料科学与应用教育部重点实验室，北京 100083
2.
木材科学与工程北京市重点实验室，北京 100083
3.
国家林业和草原局/北京市共建竹藤科学与技术重点实验室，国际竹藤中心，北京 100102

基金项目: 国家自然科学基金项目（31971742）。

详细信息

作者简介:
姚尧。主要研究方向：生物质基吸附材料。Email：yaoyao4196@foxmail.com　地址：100083北京市海淀区清华东路35号北京林业大学材料科学与技术学院

责任作者:
陈瑶，博士，副教授。主要研究方向：碳材料及功能性改良、生物质资源综合利用。Email：ychen@bjfu.edu.cn　地址：同上。

中图分类号: S644.2；TQ424.1；X523
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出版历程
- 收稿日期: 2023-06-27
- 修回日期: 2023-09-14
- 录用日期: 2023-09-17
- 网络出版日期: 2023-09-21
- 刊出日期: 2023-10-30

Preparation of activated carbon from bamboo shoot shell by pyrolysis self-activation method and its arsenic adsorption performance

Yao Yao^{1, 2,},
Liu Zhijia³,
Chen Yao^{1, 2, ,},
He Linhan^{1, 2},
Gao Jianmin^{1, 2}

1.
Key Laboratory of Wood Material Science and Application of Ministry of Education, Beijing Forestry University, Beijing 100083, China
2.
Key Laboratory of Wood Science and Engineering, Beijing Forestry University, Beijing 100083, China
3.
Key Laboratory of National Forestry and Grassland Administration, Beijing for Bamboo & Rattan Science and Technology, International Center for Bamboo and Rattan, Beijing 100102, China

摘要

摘要:
目的
利用竹材加工剩余物竹箨探索一种高效除砷活性炭材料。
方法
以竹箨为原材料，以微波加热为热源，利用高温热解自活化技术在不同的活化温度和时间下制备竹箨活性炭，通过表征竹箨活性炭的微观形貌、比表面积、孔隙结构、石墨化程度、表面元素和官能团，揭示活化时间和温度等对其微观结构的影响，探讨竹箨活性炭的砷吸附性能，比较不同制备方法下活性炭的比表面积和砷吸附容量的差异。
结果
活化温度1 050 ℃、活化时间30 min时，竹箨活性炭孔隙结构排列整齐致密，比表面积达到1 251.7 m²/g，孔容为0.697 cm³/g，微孔比表面积比率和微孔孔容比率分别为60.9%和64.0%，平均孔径为0.448 nm，主要由微孔和少量介孔组成，孔径远大于砷酸根离子（AsO₄ ³⁻）和亚砷酸分子（H₃AsO₃）的空间构型尺寸，有利于对As（Ⅲ）和As（Ⅴ）的吸附。反映石墨化程度的R 值为1.340，表面具有丰富的含氧官能团，对As（Ⅲ）的最大吸附量为3.87 mg/g，对As（Ⅴ）的最大吸附量为3.17 mg/g。对比文献中不同活性炭的比表面积和砷吸附容量，竹箨活性炭表现出一定优势。
结论
适当提高活化温度、延长活化时间有利于表面微孔的形成，从而提高砷吸附容量；但过高的活化温度和过长的活化时间会导致孔隙结构坍塌，减小比表面积和微孔比率，降低砷吸附容量。本研究为高效治理水体砷污染活性炭材料的制备提供了一种简单环保的方法，具有良好的除砷性能。
- 热解自活化 /
- 竹箨活性炭 /
- 砷吸附性能 /
- 微观形貌 /
- 孔隙结构
Abstract:
Objective
This paper aims to explore an efficient arsenic removal activated carbon material using bamboo shoot shell residue from bamboo processing.
Method
Bamboo shoot shell was used as the raw material, while microwave heating was employed as the heat source. Activated carbon from bamboo shoot shell was prepared through catalytic pyrolysis self-activation technique at different activation temperatures and times. The microstructure, specific surface area, pore structure, graphitization degree, surface elements, and functional groups of the activated carbon were characterized to reveal the influence of activation time and temperature on its microstructure. The arsenic adsorption performance of the activated carbon was investigated, and the differences in specific surface area and arsenic adsorption capacity were compared among different preparation methods.
Result
At an activation temperature of 1 050 ℃ and activation time of 30 min, the activated carbon exhibited an orderly and dense pore structure. The specific surface area reached 1 251.7 m²/g, with a pore volume of 0.697 cm³/g. The ratio of micropore specific surface area and the ratio of pore volume were 60.9% and 64.0%, respectively. The average pore diameter was 0.448 nm, primarily composed of micropores and a small amount of mesopores. The pore size was much larger than the spatial configuration dimensions of arsenate ions (AsO₄ ³⁻) and arsenous acid molecules (H₃AsO₃), which facilitated the adsorption of As(Ⅲ) and As(V). The graphitization degree (R) was 1.340, and the surface contained abundant oxygen-containing functional groups. The maximum adsorption capacity for As(Ⅲ) was 3.87 mg/g, while for As(V), it was 3.17 mg/g. Compared with the specific surface area and arsenic adsorption capacity of activated carbon in previous literature, the bamboo strip activated carbon demonstrated certain advantages.
Conclusion
Properly increasing the activation temperature and extending the activation time are beneficial for the formation of surface micropores, thereby enhancing the arsenic adsorption capacity. However, excessively high activation temperature and prolonged activation time can cause the collapse of pore structure, resulting in reduced specific surface area, micropore ratio, and reduce arsenic adsorption capacity. This research provides a simple and environmentally friendly method for the preparation of efficient arsenic removal activated carbon materials, offering promising arsenic treatment performance in water bodies.
- pyrolysis self-activation /
- activated carbon from bamboo shoot shell /
- arsenic adsorption performance /
- microstructure /
- pore structure

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图 1 不同工艺条件下竹箨活性炭的SEM图

a. 950 ℃, 15 min; b. 950 ℃, 30 min; c. 950 ℃, 45 min; d. 950 ℃, 60 min; e. 1 000 ℃, 15 min; f. 1 000 ℃, 30 min; g. 1 000 ℃, 45 min; h. 1 000 ℃, 60 min; i. 1 050 ℃, 15 min; j. 1050 ℃, 30 min; k. 1 050 ℃, 45 min; l. 1 050 ℃, 60 min; m. 1 100 ℃, 15 min; n. 1 100 ℃, 30 min; o. 1 100 ℃, 45 min; p. 1 100 ℃, 60 min.

Figure 1. SEM images of activated carbon from bamboo shoot shell under different process conditions

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图 2 不同加热温度对竹箨活性炭比表面积（a）和孔容（b）的影响

Figure 2. Effects of different heating temperatures on the specific surface area (a) and pore volume (b) of activated carbon frombamboo shoot shell

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图 3 不同加热温度下竹箨活性炭的N₂吸附–脱附等温线（a）和孔径分布（b）图

Figure 3. N₂ adsorption-desorption isotherms (a) and pore size distribution (b) of activated carbon from bamboo shoot shell at different heating temperatures

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图 4 不同加热时间对竹箨活性炭比表面积（a）和孔容（b）的影响

Figure 4. Effects of different heating times on the specific surface area (a) and pore volume (b) of activated carbon from bamboo shoot shell

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图 5 不同加热时间竹箨活性炭的N₂吸附–脱附等温线（a）和孔径分布（b）图

Figure 5. N₂ adsorption-desorption isotherms (a) and pore size distribution (b) of activated carbon from bamboo shoot shell at different heating times

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图 6 不同加热温度（a）和加热时间（b）的竹箨活性炭的拉曼光谱图

Figure 6. Raman spectra of activated carbon from bamboo shoot shell at different heating temperatures (a) and heating times (b)

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图 7 竹箨活性炭的XPS谱图

Figure 7. XPS spectra of activated carbon from bamboo shoot shell

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图 8 不同活化条件下竹箨活性炭对As（Ⅲ）（a）和As（Ⅴ）（b）的吸附量

Figure 8. Adsorption capacity of activated carbon from bamboo shoot shell on As (Ⅲ) (a) and As (V) (b) under different activation conditions

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表 1 不同加热温度下竹箨活性炭的比表面积和孔隙结构参数

Table 1 Specific surface area and pore structure of activated carbon from bamboo shoot shell at different heating temperatures

加热条件 Heating condition	比表面积 Specific surface area/（m²·g⁻¹）			微孔比表面积比率 Ratio of micropore specific surface area/%	孔容 Pore volume/（cm³·g⁻¹）			微孔孔容比率 Ratio of micropore volume/%	平均孔径 Average pore size/nm
加热条件 Heating condition	微孔 Micropore	介孔 Mesoporous	总和 Total	微孔比表面积比率 Ratio of micropore specific surface area/%	微孔 Micropore	介孔 Mesoporous	总和 Total	微孔孔容比率 Ratio of micropore volume/%	平均孔径 Average pore size/nm
950 ℃，30 min	772.2	177.6	949.8	81.3	0.379	0.144	0.523	72.5	0.427
1 000 ℃，30 min	843.8	135.1	978.9	86.2	0.416	0.143	0.559	83.2	0.413
1 050 ℃，30 min	762.6	489.1	1 251.7	60.9	0.446	0.251	0.697	64.0	0.448
1 100 ℃，30 min	605.7	656.1	1 261.8	48.0	0.449	0.268	0.717	62.6	0.457

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表 2 不同加热时间竹箨活性炭的比表面积和孔隙结构参数

Table 2 Specific surface area and pore structure of activated carbon from bamboo shoot shell at different heating times

样品 Sample	比表面积 Specific surface area/（m²·g⁻¹）			微孔比表面积比率 Ratio of micropore specific surface are/%	孔容 Pore volume/（cm³·g⁻¹）			微孔孔容比率 Ratio of micropore volume/%	平均孔径 Average pore size/nm
样品 Sample	合计 Total	微孔 Micropore	介孔 Mesoporous	微孔比表面积比率 Ratio of micropore specific surface are/%	合计 Total	微孔 Micropore	介孔 Mesoporous	微孔孔容比率 Ratio of micropore volume/%	平均孔径 Average pore size/nm
1 050 ℃，15 min	1 136.3	711.3	245.0	62.6	0.638	0.415	0.223	65.0	0.438
1 050 ℃，30 min	1 251.7	762.6	489.1	60.9	0.697	0.446	0.251	64.0	0.448
1 050 ℃，45 min	1 517.8	572.9	944.9	37.7	0.859	0.486	0.373	56.6	0.463
1 050 ℃，60 min	1 571.4	375.5	1 195.9	23.9	0.947	0.488	0.461	51.5	0.471

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表 3 活性炭砷吸附量对比研究

Table 3 Comparative study on arsenic adsorption capacity of activated carbon

样品 Sample	比表面积 Specific surface area/（m²·g⁻¹）	砷吸附量 Arsenic adsorption capacity/（mg·g⁻¹）		制备方法 Preparation method	数据来源 Data source
样品 Sample	比表面积 Specific surface area/（m²·g⁻¹）	As（Ⅲ）	As（Ⅴ）	制备方法 Preparation method	数据来源 Data source
黄麻活性炭 Jute stick activated carbon	1 624	4.50	—	H₂O	Asadullah等，2014^[21] Asadullah et al, 2014
黄麻活性炭 Jute stick activated carbon	750	5.50	—	H₃PO₄
载铁黄麻活性炭 Iron-loaded activated carbon	1 266	9.70	—	FeSO₄ + H₃PO₄
颗粒活性炭 Granular activated carbon		2.87	2.30	Fe + Mn	Nikic等，2019^[22] Nikic et al, 2019
竹箨活性炭 Activated carbon from bamboo shoot shell	1 251.7	3.87	3.17	热解自活化 Pyrolysis self-activation	本研究 Our research

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