乙烯焦油窄馏分炭化性能研究

于洋洋; 位强; 王峰; 焦守辉; 邱志鹏; 王丽丽; 刘贺; 陈坤; 郭爱军

doi:10.1016/S1872-5813(21)60151-2

乙烯焦油窄馏分炭化性能研究

doi: 10.1016/S1872-5813(21)60151-2

中国石油大学(华东)化学工程学院重质油国家重点实验室，山东青岛 266580

基金项目: 国家自然科学基金(21776313, 21908248)，山东省重点研发计划(2017GGX70108)，中央高校专项研究基金(20CX02206A)，重质油国家重点实验室项目(25F21040114)和研究生创新工程(YCX2021056)资助

详细信息

作者简介:
于洋洋：s19030077@s.upc.edu.cn

通讯作者:
Tel: 0532-86980607，Fax: 0532-86981787，E-mail: ajguo@upc.edu.cn

中图分类号: TE626.8+7
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出版历程
- 收稿日期: 2021-06-24
- 修回日期: 2021-08-02
- 网络出版日期: 2021-09-06
- 刊出日期: 2022-03-28

Carbonization characteristics of ethylene tar narrow fractions

State Key Laboratory of Heavy Oil, College of Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, China

Funds: The project was supported by the National Natural Science Foundation of China (21776313, 21908248), the Key Technology Research and Development Program of Shandong (2017GGX70108), the Fundamental Research Funds for the Central Universities (20CX02206A), and the Development Fund of State Key Laboratory of Heavy Oil Processing (25F21040114), and Graduate Innovation Project (YCX2021056)

摘要

摘要: 为研究乙烯焦油作为生产针状焦原料的可行性，以某炼厂乙烯焦油及对其蒸馏切割所得窄馏分油为研究对象，通过元素分析、红外光谱（FT-IR）、核磁共振氢谱（¹H NMR）、生焦诱导期测定及焦化进料热稳定性模拟等方法，对油样的基本性质、结构组成和热稳定性进行研究，并通过偏光显微镜、X射线衍射仪（XRD）、扫描电子显微镜（SEM）等方法对各油样在不同炭化条件下的产物性能进行分析。结果表明，乙烯焦油全馏分沥青质含量高达22.04%，且烯烃等热反应活性组分含量较高，热稳定性较差，生焦诱导期仅为34 min。蒸馏处理所得馏分油不含沥青质，热反应活性组分含量较低，热稳定性变好，生焦诱导期均大于55 min。窄馏分油由于分子分布范围较窄、热反应活性组分含量低，相较于全馏分形成的半焦具有更好的各向异性结构和微晶结构。两段炭化相较于一段炭化更有利于中间相的融并发育及有序排列，形成纤维状的广域流线型结构。两段炭化制得焦炭热膨胀系数（CTE）的值均优于一段炭化，馏分油（ET-C）在两段炭化条件下制得针状焦的CTE值为2.49×10⁻⁶ ℃⁻¹，符合针状焦CTE值不大于2.60×10⁻⁶ ℃⁻¹的标准。
- 乙烯焦油 /
- 热稳定性 /
- 两段炭化 /
- 针状焦
Abstract: In this study, the feasibility of using ethylene tar (ET) as raw material for needle coke production was investigated. The basic properties, structural compositions, and thermal stability of ethylene tar and its narrow fractions were studied by elemental analysis, Fourier transform-infrared spectroscopy (FT-IR), ¹H nuclear magnetic resonance (¹H NMR), the coke induction period, and simulation of thermal stability of coking feed. The properties of the products were analyzed by a polarized light microscope, X-ray diffraction (XRD), and scanning electron microscopy (SEM). The results showed that the content of asphaltenes was up to 22.04% in ET, and the thermal stability was poor due to the high content of olefin and other thermally sensitive components. Thus, the coke induction period of ET was only 34 min. After distillation, narrow fractions had no asphaltenes and a low quantity of heat-sensitive components, resulting in improved fraction thermal stability with coke induction period of more than 55 min. Due to its narrow molecular distribution and low content of heat-sensitive components of narrow fractions, the semi-cokes formed from narrow fractions possessed better anisotropic and microcrystalline structures than those formed from the ET. Compared with one-stage carbonization, the two-stage carbonization was more conducive to the coalescence, development, and orientation of mesophase, leading to the formation of a fibrous wide-area streamline structure. The needle coke prepared from the fraction of ET-C had a lower thermal expansion coefficient (CTE), as low as 2.49 ×10⁻⁶ ℃⁻¹, meeting the CTE requirement of needle coke.
- ethylene tar /
- thermal stability /
- two-stage carbonization /
- needle coke

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FIG. 1392. FIG. 1392.

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图 1 炭化反应釜简图

Figure 1 Carbonization reactor diagram

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图 2 ET及窄馏分生焦趋势

Figure 2 Coke formation trend of ET and its narrow fractions

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图 3 五种油样焦化进料热稳定性模拟

Figure 3 Thermal stability simulation of five oil samples

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图 4 ET及窄馏分红外光谱谱图

Figure 4 FT-IR spectra of ET and its narrow fractions

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图 5 ET及其窄馏分 ¹H NMR谱图

Figure 5 ¹H NMR spectra of ET and its narrow fractions

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图 6 ET及其窄馏分不同炭化条件所得半焦偏光显微照片

Figure 6 Polarized light microscopic images of green cokes derived from carbonization of ET and its narrow fractions under different carbonization conditions

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图 7 两种炭化条件下各油样半焦的XRD谱图

Figure 7 XRD spectra of green cokes derived from ET and its narrow fractions under two carbonization conditions

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图 8 ET与ET-C在两种炭化条件下制备焦炭的SEM照片

Figure 8 SEM images of calcined cokes prepared from ET and ET-C obtained at two carbonization conditions

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表 1 ET及窄馏分基本性质

Table 1 Selected properties of ET and its narrow fractions

Item	ET	ET-A	ET-B	ET-C
H w /%	7.46	7.47	7.37	7.32
C w /%	92.08	92.01	92.29	92.30
S w /%	0.16	0.03	0.04	0.09
N w /%	0.08	0	0	0
C/H (atomic ratio)	1.036	1.034	1.051	1.058
Ash /(μg·g⁻¹)	26	0	0	0
QI w /%	0.06	0	0	0
Carbon residue w /%	15.21	0.82	1.28	1.44
Saturates w /%	9.06	13.9	8.72	4.37
Aromatics w /%	58.67	85.34	88.75	90.87
Resins w /%	10.23	0.76	2.53	6.76
Asphaltenes w /%	22.04	0	0	0

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表 2 斑点等级评价标准

Table 2 Evaluation standards of spot number

Spot number	Characterizing features
1	the spot is uniform and there is no inner spot
2	there is subtle and indistinct inner spot
3	there is distinct thin inner spot, and is slightly darker than background color
4	there is distinct inner spot, and is darker than background color
5	the inner spot is almost solid state, and is much darker than background color

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表 3 ET及窄馏分中类型氢含量及分布

Table 3 Hydrogen distribution of ET and its narrow fractions

Hydrogen type	Chemical shift δ^[20]	Hydrogen content /%
Hydrogen type	Chemical shift δ^[20]	ET	ET-A	ET-B	ET-C
H_ar	9.0–6.0	47.72	56.73	52.53	47.06
H_o	6.0–4.5	1.65	1.33	1.31	1.37
H_α	4.0–2.0	36.13	31.13	29.67	33.45
H_n	2.0–1.6	6.22	2.46	4.88	5.55
H_β	1.6–1.0	7.17	6.72	9.55	10.54
H_γ	1.0–0.5	1.13	1.62	1.96	2.03
H_β/ H_γ	–	6.37	4.14	4.87	5.20
^* H_ar: aromatic hydrogens; H_o: hydrogens in olefin; H_n: naphthenic hydrogen; H_α: aliphatic hydrogens in α-position to the aromatic carbon; H_β: aliphatic hydrogens in β-position to the aromatic carbon; H_γ_: aliphatic hydrogens in γ-position to the aromatic carbon

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表 4 各油样在两种炭化条件下产物的微晶结构参数

Table 4 XRD crystal parameters of the green cokes derived from ET and its narrow fractions under two carbonization conditions

Sample	2θ（002）/(°)	β₀₀₂	d₀₀₂/Å	L_c/nm
ET-O	25.432	0.0942	3.502	1.4928
ET-A-O	25.457	0.0938	3.499	1.4998
ET-B-O	25.479	0.0931	3.496	1.5109
ET-C-O	25.525	0.0929	3.490	1.5138
ET-T	25.463	0.0937	3.498	1.5007
ET-A-T	25.568	0.0922	3.484	1.5261
ET-B-T	25.635	0.0903	3.475	1.5584
ET-C-T	25.743	0.0885	3.461	1.5903

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表 5 各油样在两种炭化条件下所得针状焦的热膨胀系数

Table 5 CTE of the needle cokes derived from ET and its narrow fractions under two carbonization conditions

Sample	CTE*/ (1×10⁻⁶·℃⁻¹)
Sample	one-stage carbonization	two-stage carbonization
ET	3.35	3.08
ET-A	3.17	2.83
ET-B	3.09	2.72
ET-C	2.84	2.49
Commercial needle coke-1	2.47
Commercial needle coke-2	2.39
*Requirement: 2.6×10⁻⁶℃⁻¹，according to RIPP method^[25]

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