原料组成对针状焦结构的影响

刘杰; 史雪梅; 崔楼伟; 范晓勇; 施俊合; 徐贤; 田佳勇; 田育成; 郑金欣; 李冬

doi:10.1016/S1872-5813(21)60026-9

原料组成对针状焦结构的影响

doi: 10.1016/S1872-5813(21)60026-9

刘杰^{1, 2,},
史雪梅³,
崔楼伟⁴,
范晓勇^{1, 2, 5},
施俊合^{1, 2},
徐贤^{1, 2},
田佳勇^{1, 2},
田育成^{1, 2},
郑金欣^{1, 2},
李冬^{1, 2, ,}

1.
西北大学化工学院，陕西西安 710069
2.
陕西省资源化工应用技术工程研究中心，陕西西安 710069
3.
西安航天动力试验技术研究所，陕西西安 710100
4.
西北化工研究院有限公司，陕西西安 710061
5.
榆林学院化学与化工学院，陕西榆林 719000

详细信息

作者简介:
刘杰：1506559628@qq.com

通讯作者:
E-mail: lidong@nwu.edu.cn

中图分类号: TQ523.4
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- 被引次数: 0
出版历程
- 收稿日期: 2020-11-19
- 修回日期: 2020-12-30
- 网络出版日期: 2021-03-08
- 刊出日期: 2021-04-10

Study on the influence of raw material composition on the structure of needle coke

LIU Jie^{1, 2
,},
SHI Xue-mei³,
CUI Lou-wei⁴,
FAN Xiao-yong^{1, 2, 5},
SHI Jun-he^{1, 2},
XU Xian^{1, 2},
TIAN Jia-yong^{1, 2},
TIAN Yu-cheng^{1, 2},
ZHENG Jin-xin^{1, 2},
LI Dong^{1, 2
, ,}

1.
School of Chemical Engineering, Northwest University, Xi′an 710069, China
2.
Shaanxi Provincial Resource Chemical Application Technology Engineering Research Center, Xi′an 710069, China
3.
Xi′an Aerospace Propulsion Institute, Xi′an 710100, China
4.
Northwest Research Institute of Chemical Industry Co., Ltd., Xi′an 710061, China
5.
School of Chemistry and Chemical Engineering, Yulin University, Yulin 719000, China

摘要

摘要: 在330–390 °C、8 MPa、加氢时间为1.5 h和剂油比为1∶40的条件下对中低温煤焦油原料进行加氢处理，得到精制原料后再通过热聚合煅烧等过程制得针状焦。通过元素分析、红外光谱（FT-IR）、气相色谱-质谱联用仪（GC-MS）等检测方法分析了精制原料组成，并采用扫描电子显微镜（SEM）、X射线衍射仪（XRD）和偏光显微镜等方法测试了不同原料所制备出的针状焦结构，研究了加氢温度和精制原料组成对针状焦结构的影响。结果表明，提高缓和加氢精制温度有利于脱除杂原子（尤其是S），但当加氢温度为390 °C时，原料中的芳烃会因为裂解和缩聚而发生两极分化。此外，精制原料中3环和4环芳烃的含量越高，所制备出针状焦石墨化程度越高。
- 煤焦油加氢 /
- 精制原料 /
- 针状焦 /
- 光学结构
Abstract: The refined raw material was first prepared from the low-medium temperature coal tar through hydrogenation for 1.5 h under 330–390 °C and 8 MPa, with a catalyst/oil mass ratio of 1∶40, which was then used to produce needle coke through thermal polymerization and calcination. The composition of refined raw materials was analyzed by elemental analysis, Fourier-transform IR spectroscopy (FT-IR) and gas chromatography-mass spectrometry (GC-MS) and the structure of needle coke was characterized by scanning electron microscope (SEM), X-ray diffractometer (XRD) and polarizing microscope; the effect of raw material composition (related to the hydrogenation temperature) on the structure of needle coke was then investigated. The results indicate that a proper increase in the hydrofining temperature is beneficial to the removal of heteroatoms (especially sulfur). By hydrogenation at 390 °C, the aromatics in the feedstock are polarized due to the cracking and polycondensation. In addition, a higher content of tricyclic and tetracyclic aromatics in the refined raw materials may also lead to a higher graphitization degree for the needle coke product.
- coal tar hydrogenation /
- refined raw materials /
- needle coke /
- optical structure

HTML全文

FIG. 619. FIG. 619.

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图 1 不同加氢温度下精制原料的红外光谱谱图

Figure 1 FT-IR spectra of the refined raw materials obtained by hydrogenation at different temperatures

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图 2 不同精制原料所制备的针状焦SEM照片

Figure 2 SEM images of the needle coke samples prepared from the different refined raw materials

note: NC-HRP-330, NC-HRP-350, NC-HRP-370 and NC-HRP-390 refer to needle coke prepared from refined raw materials obtained at 330, 350, 370 and 390 °C, respectively

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图 3 不同精制原料所制备的针状焦XRD谱图

Figure 3 XRD patterns of the needle coke samples prepared from the different refined raw materials

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图 4 不同精制原料制备的偏光显微照片

Figure 4 Polarized light micrographs of the needle coke products prepared from different refined raw materials

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表 1 原料的元素分析

Table 1 Elemental composition of the raw low-medium temperature coal tar (LTCT)

Material	Mass composition/%					H/C atomic ratio	Quinoline insoluble/%
Material	C	H	O	N	S	H/C atomic ratio	Quinoline insoluble/%
LTCT	82.48	8.53	7.57	1.08	0.34	1.241	1.04
note: low-medium temperature coal tar is referred to as LTCT

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表 2 不同加氢温度下所得到的精制原料的元素分析

Table 2 Elemental analysis results of refined raw materials at different hydrogenation temperatures

Sample	Mass composition/%					H/C atomic ratio	QI/%
Sample	C	H	O	N	S	H/C atomic ratio	QI/%
LTCTP	84.50	7.89	6.40	0.98	0.23	1.120	0.66
HRP-330	84.68	7.97	6.25	0.91	0.19	1.129	0.51
HRP-350	84.94	8.12	5.97	0.83	0.14	1.147	0.46
HRP-370	84.95	8.33	5.85	0.76	0.11	1.177	0.40
HRP-390	85.10	8.37	5.74	0.72	0.07	1.180	0.31
note: HRP-330, HRP-350, HRP-370 and HRP-390 refer to the refined raw asphalt samples obtained by hydrogenation at 330, 350, 370 and 390 °C, respectively

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表 3 不同精制原料的分子类型

Table 3 Molecular types and their contents in the refined raw materials obtained by hydrogenation at different temperatures

Sample	Content w/%
Sample	alkanes	alkene	aromatic hydrocarbon	oxygenated compounds	nitrogenous compounds	sulfur compounds
LTCTP	39.92	1.09	42.37	13.83	2.17	0.62
HRP-330	41.02	0.54	44.73	11.27	1.93	0.51
HRP-350	42.97	0.41	45.49	9.33	1.38	0.42
HRP-370	44.16	0.17	45.78	8.26	1.32	0.31
HRP-390	43.45	0	47.42	7.83	1.04	0.26

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表 4 不同精制原料的芳烃类型

Table 4 Types of aromatics and their contents in the refined raw materials obtained by hydrogenation at different temperatures

Sample	Content w/%
Sample	1-ring	2-ring	3-ring	4-ring	5-ring	1+1S	2+1S	3+1S	4+1S
LTCTP	0.14	8.45	22.47	5.38	0.68	0.03	2.05	3.17	0
HRP-330	0.07	9.12	23.71	6.26	0.49	0.09	1.65	3.34	0
HRP-350	0.34	7.57	24.79	7.36	0.93	0.27	1.68	2.36	0.19
HRP-370	0.67	8.39	23.84	7.42	0.87	0.43	1.72	2.21	0.23
HRP-390	0.61	10.81	22.67	7.53	1.06	0.83	1.67	2.13	0.11
note: “ n-ring” refers to the molecules containing n aromatic rings; “ n + 1S” refers to the molecule containing n aromatic rings combined with one saturated ring

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表 5 不同精制原料所制备的针状焦微晶结构参数

Table 5 Crystal structure parameters of the needle coke products prepared from different refined raw materials

Sample	2θ₀₀₂/(°)	d₀₀₂/nm	B₀₀₂/(°)	2θ₁₀₀/(°)	B₁₀₀/(°)	L_a/nm	L_c/nm	G/%
NC-LTCTP	25.82	0.3449	0.953	43.010	0.900	19.402	8.459	−10.47
NC-HRP-330	25.90	0.3438	0.977	43.320	0.919	19.021	8.253	2.33
NC-HRP-350	25.96	0.3430	0.907	42.861	0.860	20.294	8.891	11.63
NC-HRP-370	25.94	0.3433	0.918	42.291	0.935	18.670	8.784	8.14
NC-HRP-390	25.84	0.3446	0.961	43.122	0.895	19.518	8.389	−6.98

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