煤系针状焦煅烧过程中焦炭微晶结构的演变规律

程俊霞; 朱亚明; 高丽娟; 赵雪飞

煤系针状焦煅烧过程中焦炭微晶结构的演变规律

辽宁科技大学化工学院, 辽宁鞍山 114051

基金项目:

国家自然科学基金 U1361126

辽宁省自然科学基金 20180551218

辽宁省教育厅项目 2017LNQN04

辽宁科技大学优秀人才培养项目 2018RC07

辽宁科技大学青年基金 2016QN25

辽宁科技大学青年基金 2017QN06

辽宁科技大学开放基金资助 USTLKFSY201701

详细信息

通讯作者:
赵雪飞, E-mail:zhao_xuefei@sohu.com

中图分类号: TQ52
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- 被引次数: 0
出版历程
- 收稿日期: 2020-07-21
- 修回日期: 2020-08-25
- 网络出版日期: 2021-01-23
- 刊出日期: 2020-09-10

Evolution of coke microcrystalline structure during calcination process of coal-based needle coke

College of Chemical Engineering, University of Science and Technology Liaoning, Anshan 114051, China

Funds:

The project was supported by the National Natural Science Foundation of China U1361126

Natural Science Foundation of Liaoning Province 20180551218

Liaoning Provincial Department of Education Project 2017LNQN04

Excellent Talent Training Project of University of Science and Technology Liaoning 2018RC07

Youth Fund of University of Science and Technology Liaoning 2016QN25

Youth Fund of University of Science and Technology Liaoning 2017QN06

Open Fund of University of Science and Technology Liaoning USTLKFSY201701

More Information

Corresponding author: ZHAO Xue-fei, E-mail:zhao_xuefei@sohu.com

摘要

摘要: 以煤系针状焦的生焦为原料，在2和5℃/min的升温速率下进行煅烧，采用FT-IR、XRD、Raman光谱等分析手段研究煅烧过程中针状焦微晶结构的演变规律。结果表明，随着煅烧温度的升高，针状焦中碳微晶的直径L_a、炭微晶的高度L_c、晶体中的片层含量N以及每层中平均碳原子数n、趋于规整的石墨微晶含量I_g逐渐升高。但是受挥发分逸出和生焦收缩的影响，L_c出现了明显的"拐点"。新增片层与原有片层间存在的随机"层错"，导致层间距d₀₀₂的波动。相同温度下升温速率越快，晶格尺寸越小，片层含量N及每层平均碳原子数n越少，L_c出现"拐点"的温度越靠后。理想石墨微晶含量（I_G/I_all）随温度的升高逐渐增加；而具有缺陷的石墨微晶间在煅烧过程中不断相互转化，最终发育为理想石墨微晶。碳网平面上C-C键平均键长α则随着煅烧温度的升高明显增加。
- 煤系针状焦 /
- XRD /
- Raman /
- 微晶结构 /
- C-C键平均键长
Abstract: The evolution of the microstructure of needle coke during calcination process has been determined by FT-IR, XRD, and Raman spectroscopy, in which the needle cokes were obtained by calcination at heating rates of 2 and 5 ℃/ min with the coal-based green needle coke as the raw materials, respectively. The results show that the diameter of carbon microcrystal L_a, the height of carbon microcrystal L_c, the lamella content in the crystal (N), the average carbon number in each layer (n), and the content of tending regular graphite micro crystals (I_g) in the needle coke increase gradually with the rising of the calcination temperature. However, the value of L_c appears an "inflection point" due to the escape of volatiles and shrinkage of green needle coke. The layer spacing d₀₀₂ fluctuates due to the random "layer fault" between the new layer and the original layer. The higher the heating rate, the smaller the characteristic carbon microcrystal parameters (L_a, L_c, N, and n) of needle coke, and the latter the temperature of "inflection point" for L_c appears. Also, the content of perfect graphite microcrystallite (I_G/I_all) increases gradually with the increasing of temperature, and the defective graphite microcrystallites transforms to each other continuously during calcination process, finally being developed into the graphite microcrystals. The average bond length α of C-C bond in the carbon planes would become larger with the increase of calcination temperature.
- coal-based needle coke /
- XRD /
- Raman /
- microcrystalline structure /
- average bond length of C-C bond

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图 1 针状焦在不同温度下的煅烧收率

Figure 1 Yield of needle cokes after calcination at different temperatures

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图 2 针状焦的红外光谱谱图

Figure 2 FT-IR spectra of needle cokes (a): 2 ℃/min; (b): 5 ℃/min

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图 3 (a) 原料生焦2800-3000 cm^-1分子结构分析(b)针状焦的红外结构参数

Figure 3 (a) Structure analysis of a green needle coke in 2800-3000 cm^-1 interval, (b) FT-IR structural parameters of needle cokes

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图 4 针状焦的XRD谱图

Figure 4 XRD spectra of needle coke

(a): 2 ℃/min; (b): 5 ℃/min; (c): NC-2-700 002 peak-fitting spectra; (d): NC-5-700 002 peak-fitting spectra

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图 5 针状焦的Raman谱图

Figure 5 Raman spectra of needle coke

(a): 2 ℃/min; (b): 5 ℃/min; (c): curve-fitted Raman spectra of NC-2-700; (d): curve-fitted Raman spectra of NC-5-700

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表 1 针状焦的基本性质

Table 1 Basic properties analysis of green needle coke

Sample	Ash/%	Volatile /%	True density /(g·cm^-3)	Ultimate analysis /% (mass composition)
Sample	Ash/%	Volatile /%	True density /(g·cm^-3)	C	H	O	N	S
Green needle coke	0.02	5.7	1.41	93.63	2.98	2.29	0.91	0.18

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表 2 针状焦XRD参数计算

Table 2 Calculation of XRD parameters of needle cokes

Sample	d₀₀₂ /nm	L_c/nm	L_a/nm	I_g/ %	N	n
NC-2-700	0.351	1.86	4.09	66.64	6	12
NC-2-800	0.351	2.22	4.27	70.26	7	17
NC-2-900	0.347	2.03	4.65	75.48	7	15
NC-2-1000	0.348	2.45	4.65	81.61	8	21
NC-2-1100	0.342	2.58	4.87	84.12	9	23
NC-2-1200	0.340	2.74	4.88	86.66	9	26
NC-5-700	0.353	1.75	3.80	62.85	6	11
NC-5-800	0.355	2.05	4.04	66.56	7	15
NC-5-900	0.349	2.20	4.29	71.60	7	17
NC-5-1000	0.351	2.15	4.41	75.83	7	17
NC-5-1100	0.342	2.48	4.45	81.09	8	22
NC-5-1200	0.342	2.70	4.81	83.28	9	25

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表 3 Raman各参数计算

Table 3 Calculation results of Raman parameters

Sample	I_D1/I_all/ %	I_D2/I_all/ %	I_D3/I_all/ %	I_D4/I_all/ %	I_G/I_all/ %	α/pm
NC-2-700	53.90	6.02	8.69	7.47	23.92	141.27
NC-2-800	45.45	6.36	10.15	13.41	24.63	141.29
NC-2-900	49.34	6.54	8.44	10.65	25.03	141.38
NC-2-1000	45.74	6.58	11.63	10.96	25.09	141.39
NC-2-1100	41.69	5.66	10.10	16.58	25.97	141.40
NC-2-1200	50.07	6.21	8.62	8.87	26.23	141.72
NC-5-700	50.93	7.09	8.33	10.52	23.13	141.22
NC-5-800	45.44	5.85	14.51	10.52	23.67	141.25
NC-5-900	43.36	7.65	10.77	13.95	24.27	141.37
NC-5-1000	40.05	7.04	14.96	13.91	24.04	141.37
NC-5-1100	41.86	6.05	11.67	15.07	25.34	141.41
NC-5-1200	44.64	6.98	11.83	10.63	25.91	141.48

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