纺织学报 ›› 2024, Vol. 45 ›› Issue (08): 107-115.doi: 10.13475/j.fzxb.20230501501

• 纤维材料 • 上一篇    下一篇

石油沥青/聚丙烯腈静电纺碳纳米纤维的制备工艺优化及其性能

王永政1, 黄林涛1,2, 宋付权1,3()   

  1. 1.浙江海洋大学 石油化工与环境学院, 浙江 舟山 316022
    2.宁波杉杉硅基材料有限公司, 浙江 宁波 315100
    3.常州大学 石油与天然气工程学院, 江苏 常州 213000
  • 收稿日期:2023-05-05 修回日期:2023-11-03 出版日期:2024-08-15 发布日期:2024-08-21
  • 通讯作者: 宋付权(1970—),男,教授,博士。主要研究方向为非常规油气藏渗流机制和采收率提高技术。E-mail:songfuquan@cczu.edu.cn。
  • 作者简介:王永政(1990—),男,实验师,硕士。主要研究方向为油气采收率提高机制及应用研究。
  • 基金资助:
    国家自然科学基金面上项目(12272350);国家重大专项(2017ZX05072005)

Process optimization and properties of petroleum pitch/polyacrylonitrile electrospun carbon nanofibers

WANG Yongzheng1, HUANG Lintao1,2, SONG Fuquan1,3()   

  1. 1. School of Petrochemical Engineering and Environment, Zhejiang Ocean University, Zhoushan, Zhejiang 316022, China
    2. Ningbo Shanshan Silicon Base Material Co., Ltd., Ningbo, Zhejiang 315100, China
    3. School of Oil and Gas Engineering, Changzhou University, Changzhou, Jiangsu 213000, China
  • Received:2023-05-05 Revised:2023-11-03 Published:2024-08-15 Online:2024-08-21

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摘要：

为实现石油沥青的高值化利用,通过静电纺丝技术制备了沥青/聚丙烯腈复合纳米纤维,并经过预氧化和炭化处理制备了复合碳纳米纤维。采用Box-Behnken响应面法研究了纺丝参数对纤维直径的影响,通过调整石油沥青比例和热处理温度研究了预氧化和炭化过程中纤维的结构转变。结果表明:影响纤维直径的静电纺丝参数主次顺序依次为推流速度、纺丝电压和接收距离;响应面法模型预测值与最佳工艺条件下纤维直径实测值的相对误差为9.13%;当预氧化温度为250 ℃时,预氧化丝具有最大芳构化指数,其相应预氧化度最高;炭化温度与复合碳纳米纤维的石墨化程度呈正相关,随着炭化温度的升高,纤维直径大幅减小,复合碳纳米纤维石墨结构有序性逐渐增加。

关键词: 石油沥青, 聚丙烯腈, 静电纺丝, 碳纳米纤维, Box-Behnken响应面法

Abstract:

Objective Due to the complexity of its own components and structure, long-term low-value utilization of petroleum pitch often causes it to become an environmental pollutant. The research aims to achieve the high-value utilization of petroleum pitch by preparing pitch based composite carbon nanofibers, reducing the production cost and environmental pollution, and providing a reliable preparation method and process support for the application of carbon nanofibers in adsorption, energy storage and other fields.

Method Petroleum pitch and polyacrylonitrile were dissolved in various solvents and mixed at different ratios to prepare the spinning solution for composite nanofiber production. Electrospinning technology was utilized to create the nanofibers from the solutions, and the spinning parameters including flow rate, voltage, and tip-to-collector distance were optimized using Box-Behnken response surface methodology. The composite nanofibers then underwent pre-oxidation and carbonization treatments at varying temperatures. The structural transformation of the fibers was analyzed by X-ray diffraction, fourier transform infrared spectroscopy, scanning electron microscope, and Raman spectroscopy. The effect of petroleum pitch ratio and carbonization temperature on the graphitization degree of the carbon nanofibers was investigated.

Results The main factors affecting the fiber diameter were found to be the flow rate, spinning voltage and tip-to-collector distance, in descending order of significance. The optimal electrospinning conditions were obtained to be 0.64 mL/h flow rate, 15.28 kV voltage, and 13.08 cm distance, resulting in an average fiber diameter of 342.43 nm with a relative error of 9.13% compared to the predicted value. The regression model was found to have high reliability and accuracy, as demonstrated by the response surface analysis and verification experiments. The structural transformation of the composite fibers during pre-oxidation and carbonization was analyzed systematically. The aromaticity index of the pre-oxidized fibers was found to be significantly affected by the pre-oxidation temperature, reaching the maximum value of 77.56% at 250 ℃. The linear structure of polyacrylonitrile was verified to convert into a ladder-shaped structure during pre-oxidation, and dehydrogenation reaction occurred in the molecular chain of the pre-oxidized fibers. The effect of petroleum pitch ratio and carbonization temperature on the graphitization degree of the carbon nanofibers was investigated. It was found that increasing the petroleum pitch ratio could improve the graphitization degree to some extent, and that the minimum value of R (the intensity ratio of D peak to G peak in Raman spectra) was obtained when the pitch ratio was 20%-30%. Increasing the carbonization temperature was found to reduce the fiber diameter and increase the crystallite size and interlayer spacing of the carbon nanofibers, indicating a gradual increase in the ordered structure of graphite with the increase in heat treatment temperature.

Conclusion Petroleum pitch/polyacrylonitrile composite carbon nanofibers were successfully prepared using the electrospinning technology, and the spinning parameters were optimized using response surface methodology. The structural transformation and graphitization degree of the composite fibers during pre-oxidation and carbonization processes were investigated. It was found that the optimal pre-oxidation temperature was 250 ℃, and increasing the petroleum pitch ratio and carbonization temperature could improve the graphitization degree of the carbon nanofibers to some extent. Potential applications of the composite carbon nanofibers were identified in adsorption, energy storage, and catalyst support fields. Further research is needed to explore their performance and mechanism in these fields. Some challenges and limitations of the research method were also pointed out, including the difficulty of controlling the uniformity and orientation of the fibers, and the influence of solvent selection and environmental factors on the fiber morphology.

Key words: petroleum pitch, polyacrylonitrile, electrospinning, carbon nanofiber, Box-Behnken response surface method

中图分类号: 

  • TQ127.1

表1

静电纺丝工艺参数因素编码水平"

因素
水平		 推流速度/(mL·h-1) 纺丝电压/kV 接收距离/cm
-1 0.6 13 11
0 0.9 15 13
1 1.2 17 15

表2

响应面法实验设计方案及结果"

实验
序号		 推流速度/
(mL·h-1)		 纺丝电
压/kV		 接收距
离/cm		 纤维直
径/nm
1 1.2 15 15 615.04
2 0.9 17 11 982.83
3 1.2 17 13 405.58
4 0.6 13 13 261.84
5 0.9 13 15 851.93
6 0.9 13 11 1 002.82
7 0.9 15 13 571.90
8 0.9 15 13 613.21
9 1.2 15 11 425.12
10 0.9 17 15 1 234.09
11 0.6 17 13 250.75
12 0.6 15 15 207.33
13 0.9 15 13 563.07
14 0.6 15 11 296.04
15 1.2 13 13 385.82

表3

纤维直径的回归模型方差分析"

方差来源 平方和 自由度 均方 F值 P值
模型 1.34×106 9 1.49×105 29.37 0.000 8
A 8.32×104 1 8.32×104 16.39 0.009 8
B 1.72×104 1 1.72×104 3.39 0.125 1
C 5.08×103 1 5.08×103 1.00 0.363 0
AB 237.93 1 237.93 0.046 9 0.837 1
AC 1.94×104 1 1.94×104 12.82 0.147 9
BC 4.04×104 1 4.04×104 7.97 0.037 0
A2 7.29×105 1 7.29×105 143.69 <0.000 1
B2 1.30×105 1 1.30×105 25.62 0.003 9
C2 2.26×105 1 2.26×105 44.59 0.001 1
残差 2.54×104 5 5.07×103 — —
失拟项 2.39×104 3 7.98×103 11.14 0.083 5
误差 1.43×103 2 716.42 — —
总和 1.37×106 14 — — —
R2=0.981 4 信噪比=17.272 1

图1

因素交互对纤维直径影响的响应曲面图"

图2

石油沥青/PAN复合纳米纤维及其在不同温度下预氧化丝的XRD图谱"

表4

不同温度下预氧化丝的芳构化指数"

预氧化温度/℃ 芳构化指数/% 晶粒尺寸/nm
220 73.22 0.92
250 77.56 1.01
280 76.40 1.07
310 75.04 1.15

图3

不同预氧化温度下预氧化丝的红外光谱图"

图4

不同炭化温度下石油沥青/PAN碳纳米纤维SEM照片及其直径分布图"

图5

不同碳化温度下复合碳纳米纤维XRD谱图"

表5

石油沥青/PAN碳纳米纤维的XRD分析数据"

炭化温度/℃ d002/nm Lc/nm La/nm
700 0.367 1.24 1.34
900 0.360 1.28 1.68
1 100 0.351 1.31 2.17
1 300 0.349 1.39 2.89

图6

不同石油沥青比例对应碳纳米纤维的Raman谱图"

图7

不同炭化温度下碳纳米纤维的Raman光谱及其Gaussian分峰拟合图"

表6

不同炭化温度下碳纳米纤维Raman参数"

炭化温
度/℃		 R WD/
cm-1		 WG/
cm-1		 FWHM(D)/
cm-1		 FWHM(G)/
cm-1
700 1.349 1 357.82 1 580.86 351.35 261.64
900 1.100 1 348.19 1 585.43 308.20 117.09
1 100 1.046 1 342.68 1 578.55 286.35 108.24
1 300 1.006 1 337.43 1 579.07 264.56 105.97
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