熔纺Kraft硬木木质素基活性炭纤维的活化工艺及性能研究

doi:10.3969/j.issn.1673-5854.2019.02.005

生物质化学工程 ›› 2019, Vol. 53 ›› Issue (2): 26-34.doi: 10.3969/j.issn.1673-5854.2019.02.005

熔纺Kraft硬木木质素基活性炭纤维的活化工艺及性能研究

殷二强,王世超,相恒学,周哲*(),朱美芳

东华大学材料科学与工程学院, 纤维材料改性国家重点实验室，上海 201620

收稿日期:2018-02-07 出版日期:2019-03-30 发布日期:2019-04-09
通讯作者: 周哲 E-mail:zzhe@dhu.edu.cn
作者简介:殷二强(1992—),男,山西吕梁人，硕士生，主要从事木质素的开发利用研究
基金资助:
教育部创新团队项目(IRT_16R13)

Preparation and Properties of Melt-spun Kraft Hardwood Lignin-based Activated Carbon Fibers

Erqiang YIN,Shichao WANG,Hengxue XIANG,Zhe ZHOU*(),Meifang ZHU

State Key Laboratory for Modification of Chemical Fibers and Ploymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China

Received:2018-02-07 Online:2019-03-30 Published:2019-04-09
Contact: Zhe ZHOU E-mail:zzhe@dhu.edu.cn
Supported by:
教育部创新团队项目(IRT_16R13)

摘要/Abstract

摘要：

以熔融纺丝制备的Kraft硬木木质素纤维(HKL)为原料，经炭化得到木质素基炭纤维(HKL-CF)，再采用水蒸气活化法制备了活性炭纤维(HKL-ACF)，通过红外光谱仪和扫描电镜研究了水蒸气活化对活性炭纤维化学结构和表面形貌的影响，采用全自动物理吸附仪、X射线衍射仪和拉曼光谱仪等研究了活化时间、活化温度和活化水蒸气流量对所制备活性炭纤维的比表面积、孔结构和微晶结构的影响规律。研究表明，水蒸气活化处理提高了活性炭纤维中的C—O和C＝C结构含量；随着活化时间的延长，活性炭纤维的比表面积增大，且随活化温度和水蒸气流量的提高呈现出先增大后减小的趋势；晶粒尺寸随着活化时间和温度的提高，逐渐变小，纤维表面的石墨化程度随活化时间的增加，逐渐变大；活化温度800 ℃，活化时间4 h，水蒸气流量1 mL/min下制备的活性炭纤维的BET比表面积最高可达2 081.34 m²/g，总孔容最大为1.60 cm³/g。

关键词: Kraft硬木木质素, 熔融纺丝, 水蒸气活化, 活性炭纤维

Abstract:

Kraft hardwood lignin activated carbon fiber(HKL-ACF) was prepared from carbon fiber(HKL-CF) by water vapor activation using melt-spun kraft hardwood lignin(HKL) fiber as raw material. On this basis, the effects of water vapor activation on the chemical structure and morphology of activated carbon fibers were investigated by infrared spectrometer and scanning electron microscopy. And the effects of different activation time, activation temperature and water vapor flow rate on specific surface area, pore structure and microcrystalline structure of the carbon fiber were studied by automatic physical adsorption instrument, X-ray diffractometer and Raman spectrometer. The results showed that the chemical structure of carbon fiber was changed greatly after water vapor activation, and the contents of C—O and C＝C were increased. At the same time, the specific surface area increased with the increase of activation time, and increased firstly and then decreased with the increase of activation temperature and water vapor flow rate. With the increase of activation time and temperature, the grain size became smaller. The degree of graphitization of the fiber surface became larger with the increase of activation time. The maximum BET specific surface area of activated carbon fiber was 2 081.34 m²/g and the maximum pore volume was 1.60 cm³/g under the activation temperature of 800 ℃, activation time of 4 h, and water vapor flow rate of 1 mL/min.

Key words: Kraft hardwood lignin, melt spinning, water vapor activation, activated carbon fiber

中图分类号:

TQ35
TQ341+9

殷二强,王世超,相恒学,周哲,朱美芳. 熔纺Kraft硬木木质素基活性炭纤维的活化工艺及性能研究[J]. 生物质化学工程, 2019, 53(2): 26-34.

Erqiang YIN,Shichao WANG,Hengxue XIANG,Zhe ZHOU,Meifang ZHU. Preparation and Properties of Melt-spun Kraft Hardwood Lignin-based Activated Carbon Fibers[J]. Biomass Chemical Engineering, 2019, 53(2): 26-34.

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参考文献 13

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样品 sample	活化时间/h activation time	BET比表面积 (S_BET)/(m²·g^-1) BET specific surface area	微孔比表面积 (S_micro)/(m²·g^-1) surface area of microporous	介孔比表面积 (S_meso)/(m²·g^-1) surface area of mesoporous	总孔容(V_tot)/ (cm³·g^-1) total pore volume	介孔孔容(V_meso)/ (cm³·g^-1)pore volume of mesoporous	平均孔径 (D)/nm average pore diameter
HKL-ACF-0.5h	0.5	700.65	679.55	28.11	0.30	0.03	1.71
HKL-ACF-1h	1	1440.62	1357.73	111.50	0.63	0.10	1.74
HKL-ACF-2h	2	1765.22	1572.95	271.43	0.86	0.25	1.96
HKL-ACF-3h	3	1890.32	1496.67	471.84	1.05	0.40	2.28
HKL-ACF-4h	4	2081.34	1435.02	859.93	1.60	0.88	3.07

样品 sample	活化温度/℃ activation temperature	BET比表面积 (S_BET)/(m²·g^-1) BET specific surface area	微孔比表面积 (S_micro)/(m²·g^-1) surface area of microporous	介孔比表面积 (S_meso)/(m²·g^-1) surface area of mesoporous	总孔容(V_tot)/ (cm³·g^-1)total pore volume	介孔孔容 (V_meso)/(cm³·g^-1) pore volume of mesoporous	平均孔径 (D)/nm average pore diameter
HKL-ACF-T650	650	659.24	638.36	26.34	0.28	0.03	1.73
HKL-ACF-T700	700	1773.77	1517.20	330.18	0.90	0.29	2.03
HKL-ACF-T750	750	1958.31	1400.39	557.93	1.05	0.45	2.15
HKL-ACF-T800	800	1765.22	1572.95	271.43	0.86	0.25	1.96
HKL-ACF-T850	850	1751.19	1344.79	730.77	1.14	0.59	2.60

样品 sample	水蒸气流量/ (mL·min^-1) steam flow rate	BET比表面积 (S_BET)/(m²·g^-1) BET specific surface area	微孔比表面积 (S_micro)/(m²·g^-1) surface area of microporous	介孔比表面积 (S_meso)/(m²·g^-1) surface area of mesoporous	总孔容(V_tot)/ (cm³·g^-1) total pore volume	介孔孔容 (V_meso)/(cm³·g^-1) pore volumeof mesoporous	平均孔径 (D)/nm average pore diameter
HKL-ACF-W0.5	0.5	1079.30	999.57	93.06	0.48	0.09	1.79
HKL-ACF-W1	1	1765.22	1572.95	271.43	0.86	0.25	1.96
HKL-ACF-W2	2	2067.67	1405.87	945.92	1.53	0.97	2.95
HKL-ACF-W3	3	1919.69	1382.71	653.05	1.55	0.91	3.24

样品 sample	晶面间距 (d₀₀₂)/nm interplanar distance	微晶尺寸 (L_c002)/nm crystallite size	微晶宽度 (L_a002)/nm crystallite width	轴向石墨层数 L_c002/d₀₀₂ axial graphite sheet number	石墨化程度 I_D/I_G graphitization degree
HKL-CF	0.374	0.788	1.629	2.11	1.609
HKL-ACF-0.5h	0.371	0.829	1.715	2.237	1.807
HKL-ACF-1h	0.373	0.784	1.621	2.104	1.569
HKL-ACF-2h	0.390	0.749	1.548	1.919	1.527
HKL-ACF-3h	0.389	0.733	1.516	1.886	1.521
HKL-ACF-4h	—	—	—	—	—
HKL-ACF-T650	0.366	0.836	1.728	2.282	1.471
HKL-ACF-T700	0.373	0.793	1.639	2.128	1.590
HKL-ACF-T750	0.370	0.785	1.623	2.122	1.563
HKL-ACF-T800	0.390	0.749	1.548	1.919	1.527
HKL-ACF-T850	—	—	—	—	—
HKL-ACF-W0.5	0.360	0.787	1.627	2.184	1.453
HKL-ACF-W1	0.390	0.749	1.548	1.919	1.527
HKL-ACF-W2	0.374	0.754	1.560	2.017	1.503
HKL-ACF-W3	0.379	0.780	1.613	2.058	1.542

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熔纺Kraft硬木木质素基活性炭纤维的活化工艺及性能研究

Preparation and Properties of Melt-spun Kraft Hardwood Lignin-based Activated Carbon Fibers

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