Research on coking performance of ethylene residue pitch components
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摘要: 乙烯渣油沥青作为乙烯渣油中的重质组分具有含碳量高、芳香度较高及杂原子（S、N）含量低的特点，被广泛用作制备石油基人造炭材料的优选原料。为充分研究乙烯渣油沥青的成焦性，本研究选取四种溶剂（甲醇、正丁醇、正庚烷、二甲基亚砜）对乙烯渣油沥青进行萃取分离，获得八种乙烯渣油沥青组分（四种可溶组分和四种不溶组分），并对获得的乙烯渣油沥青组分进行热转化和炭化处理（热转化温度和炭化温度分别为500和1400 ℃）获得系列乙烯渣油沥青焦。采用红外光谱、热重分析仪、1H-NMR对乙烯渣油沥青组分的基础物性进行研究；利用偏光显微镜、X射线单晶衍射仪、拉曼光谱仪、扫描电子显微镜等对系列石油系沥青焦结构进行研究。结果表明，乙烯渣油沥青不溶组分芳香性略高于可溶组分，且不溶组分支链略少于可溶组分；不溶组分热转化和炭化后得到的乙烯渣油沥青焦显微强度高于可溶组分获得的乙烯渣油沥青焦，且乙烯渣油沥青沥青焦HS-C的真密度高达2.0554 g/cm3。Abstract: Ethylene residue pitch (the heavy component in ethylene residue tar) was widely used as the preferred raw material for preparing petroleum based artificial carbon materials with the characteristics of high carbon content, high aromaticity, and low heteroatom (S, N) content. In order to a detailed study on the coking properties of ethylene residue pitch, 8 components of ethylene residue pitch (four soluble and four insoluble components) were obtained by extraction and separation method. Factually, methanol, n-butanol, n-hexane, and dimethyl sulfoxide were selected as the solvents to extract and separate the ethylene residue pitch. A series of petroleum based pitch coke were gained by the thermal conversion and carbonization treatment (thermal conversion temperature and carbonization temperature were 500 and 1400 ℃, respectively) of each pitch components. The basic physical properties of ethylene residue pitch components were studied using infrared spectroscopy, thermogravimetric analysis, and 1H-NMR. The micro-structure of a series of petroleum based pitch coke was studied by polarizing microscopy, X-ray single crystal diffraction, Raman spectroscopy, scanning electron microscopy. The results shown that: The aromaticity of insoluble components in ethylene residue pitch is slightly higher than that of soluble components, and the branching chains of insoluble components are slightly less than those of soluble components. The microstrength of ethylene residue pitch coke obtained by thermal conversion and carbonization of insoluble components is higher than that of ethylene residue pitch coke obtained by soluble components, and the true density of ethylene residue pitch coke HS-C is as high as 2.0554 g/cm3.
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Key words:
- ethylene residue pitch /
- components /
- coking performance /
- pitch coke
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图 2 乙烯渣油沥青组分的热转化及炭化流程示意图
Figure 2 Thermal conversion and calcination process of ethylene residue pitch components
图 4 DMOS在3100−2770 cm−1的分峰拟合谱（a），可溶组分（b）和不溶组分（c）的CH3/CH2、Iar指数
Figure 4 Curve-fitting spectrum in the zone of 3100−2770 cm−1 for soluble pitch (a), the distributions of Iar and CH3/CH2 of solubles(b) and insolubles (c)
图 5 ETP的1H-NMR谱图（a）和组分的芳香缩合度分布（b）
Figure 5 1H-NMR spectra of ETP (a) and aromatic condensation degree distribution of components (b)
图 8 沥青焦偏光图像
Figure 8 Polarizing image of pitch cokes
(a): ETP-C; (b): DMSOS-C; (c): HS-C; (d): BAS-C; (e): MTI-C; (f): BAI-C; (g): HI-C; (h): DMSOI-C.
图 9 焦炭的X射线衍射图 （a）可溶组分沥青焦，（b）不溶组分沥青焦，和ETP-C拟合谱（c）
Figure 9 X-ray diffraction pattern of cokes (a)Soluble component cokes, (b)Insoluble component cokes,and (c) curve-fitted graph of ETP-C
图 10 焦炭的拉曼光谱谱图
Figure 10 Raman spectrogram of cokes
(a): Soluble component cokes; (b): Insoluble component cokes; (c): curve-fitted graph of DMSOS-C.
图 11 焦炭拉曼拟合结果 （a）不溶组分沥青焦；（b）可溶组分沥青焦
Figure 11 Coke Raman fitting results (a)Insoluble component cokes; (b)Soluble component cokes
图 12 可溶组分沥青焦SEM图像
Figure 12 SEM of soluble component pitch cokes
(a): ETP-C; (b): DMSOS-C; (c): HS-C; (d): BAS-C; (e): MTI-C; (f): BAI-C; (g): HI-C; (h): DMSOI-C.
表 1 ETP的工业分析
Table 1 Proximate analysis of ETP
Sample Content w/% SP/℃ QI TI CV V ETP 0.41 0.59 32.64 76.93 126 
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表 2 沥青组分的工业分析
Table 2 Proximate analysis of pitch components
Sample Yield/% Content w/% SP/℃ QI TI CV V ETP 100 0.41 0.59 32.64 76.93 126 MTI 96.68 0.01 0.05 37.13 77.30 168 BAI 73.46 0.10 0.15 37.51 70.86 178 HI 68.31 1.03 9.93 43.76 66.59 178 DMSOI 34.57 0.37 0.60 37.41 75.13 124 MTS 3.32 − − 4.97 97.57 − BAS 26.54 − − 11.88 94.46 − HS 31.69 − − 12.93 93.20 − DMSOS 65.43 − − 28.46 83.24 51
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表 3 沥青组分的元素分析
Table 3 Ultimate analysis of pitch components
Sample Content w/% C/H C H N S O ETP 91.00 6.42 0.06 0.00 2.52 1.18 MTI 93.37 6.59 0.04 0.00 0.00 1.18 BAI 93.52 6.43 0.05 0.00 0.00 1.21 HI 89.21 6.07 0.06 0.00 4.66 1.22 DMSOI 90.30 6.28 0.06 1.33 2.03 1.20 DMSOS 91.19 6.35 0.08 0.16 2.23 1.20 HS 92.77 7.15 0.08 0.00 0.00 1.08 BAS 91.67 6.82 0.10 0.00 1.42 1.12 MTS 89.33 6.26 0.36 0.00 4.04 1.19
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表 4 偏光显微镜下各光学组织的测定标准
Table 4 Standard for the determination of various optical structures under polarizing microscope
Optical organization Size/μm Length Width Mf ≤1 <1 Mm 1−5 1−5 Mc 5−10 5−10 Ff >30 <10 Fc >30 >10 Le ≥10 ≥10
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表 5 组分的氢原子分布
Table 5 Distribution of hydrogen atoms in components
Sample hydrogen ratio Har HF Hα HN Hβ Hγ DMSOI 0.283 0.200 0.319 0.060 0.098 0.039 HI 0.257 0.296 0.248 0.055 0.087 0.057 BAI 0.392 0.158 0.317 0.064 0.045 0.023 MTI 0.274 0.231 0.284 0.061 0.091 0.059 ETP 0.158 0.263 0.481 0.043 0.029 0.026 DMSOS 0.237 0.286 0.272 0.064 0.076 0.064 HS 0.338 0.261 0.301 0.045 0.041 0.013 BAS 0.353 0.215 0.280 0.068 0.062 0.021 MTS 0.336 0.200 0.330 0.061 0.043 0.030
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表 6 系列生焦收率
Table 6 Yield of green cokes
Sample Yield/% ETP-G 52.75 DMSOS-G 43.66 BAS-G 33.45 HS-G 34.16 DMSOI-G 53.17 MTI-G 53.50 BAI-G 52.88 HI-G 54.18
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表 7 各组分沥青焦偏光
Table 7 Polarizing results of each pitch cokes
Sample Mf/% Mm/% Mc/% Ff/% Fc/% Le/% F+L/% ETP-C 2.00 7.86 5.34 7.81 13.39 63.60 84.80 MTI-C 0.45 11.86 7.21 7.56 13.96 58.95 80.47 BAI-C 0.96 9.52 5.96 0.98 1.46 81.12 83.56 HI-C 2.00 15.50 8.00 4.50 10.00 60.00 74.50 DMSOI-C 0.65 7.35 2.00 2.00 13.00 75.00 90.00 DMSOS-C 0.56 6.81 1.13 11.50 4.50 75.50 91.50 HS-C 1.62 4.86 2.83 10.93 13.36 66.40 90.69 BAS-C 1.50 7.49 4.56 6.25 10.70 69.50 86.45
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表 8 焦炭002峰拟合数据及计算
Table 8 Cokes 002 peak fitting data and calculation results
Sample 2θc/° βc d002/nm Lc/nm N n ETP-C 25.563 0.047 0.348 2.972 10 29 DMSOS-C 25.581 0.041 0.348 3.389 11 37 HS-C 25.662 0.041 0.348 3.199 10 33 BAS-C 25.630 0.044 0.347 3.411 11 37 MTI-C 25.609 0.044 0.348 3.167 10 33 BAI-C 25.607 0.044 0.347 3.218 10 34 HI-C 25.656 0.044 0.347 3.200 10 33 DMSOI-C 25.638 0.041 0.347 3.399 11 37
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表 9 系列沥青焦的拉曼特征参数
Table 9 Characteristic Raman index of series pitch coke
Sample Area/105 ID1 ID2 ID3 ID4 IG 1.937 0.583 0.533 0.770 0.407 MTI-C 1.017 0.275 0.248 0.226 0.308 BAI-C 2.011 0.411 0.445 0.456 0.782 HI-C 1.274 0.263 0.358 0.280 0.527 DMSOI-C 1.661 0.313 0.363 0.375 0.517 DMSOS-C 1.739 0.315 0.309 0.347 0.620 HS-C 2.101 0.282 0.359 0.488 0.918 BAS-C 1.201 0.166 0.256 0.306 0.578
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表 10 系列沥青焦炭宏观性能指标
Table 10 Index of macroscopic properties of series pitch coke
Sample TD/(g·cm−3) PR/(mΩ·mm) MS/% ETP-C 2.0145 484 66.0 DMSOS-C 1.8393 440 59.5 HS-C 2.0554 449 68.5 BAS-C 1.9744 467 71.5 MTI-C 2.0434 455 67.5 BAI-C 2.0100 475 75.0 HI-C 1.8402 450 70.5 DMSOI-C 2.0172 434 78.0
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