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摘要: 采用13C-NMR技术表征出汪清三个矿区油页岩的碳原子化学结构, 并获得碳骨架结构的12个重要参数。利用热重和傅里叶红外联用技术 (TG-FTIR) 得出了在50℃/min升温速率和热解终温600℃下油页岩热解时轻质气体的生成规律。采用基于燃料化学结构的FLASHCHAIN模型对热解产物的析出进行了模拟, 并与实验结果相比较。结果表明, FLASHCHAIN模型用来模拟汪清油页岩热解时, 在520℃之前有较好的效果, 当温度高于520℃时, 由于二次热解反应及页岩中矿物质分解对热解过程的影响, 导致模型的预测值与实验值存在一定的误差, 且随着温度的升高两者之间的误差也随之加大。
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关键词:
- 油页岩 /
- 13C-NMR /
- 热重红外 /
- FLASHCHAIN
Abstract: The carbon atom chemical structure of three Wangqing oil shales was characterized by 13C-NMR techniques, and twelve important parameters of the carbon skeleton structure were obtained.Thermogravimetric-Fourier transform infrared spectroscopy (TG-FTIR) tests were used to obtain the formation of light gases during pyrolysis at 50℃/min and the final temperature of 600℃.The FLASHCHAIN model, which was established based on the structure of fuel, was employed to simulate the evolution of pyrolysis products and compared with the experimental tests.The results show that the model has a good simulation below 520℃, some errors occur above 520℃ due to the influence of secondary pyrolysis reactions and decomposition of minerals in the shale.The errors increase gradually with the increasing pyrolysis temperature.-
Key words:
- oil shale /
- 13C-NMR /
- TG-FTIR /
- FLASHCHAIN
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图 2 FLASHCHAIN模型机理示意图
Figure 2. Schematic illustration of the machanisms in Flashchain
①: bridge scission; ②: gas from spontaneous condensation of bridges into char links; ③: phase equilibrium
图 3 50℃/min升温速率下热解产物产量的预测曲线与实验曲线
Figure 3. Prediction curve and the experimental curves of the yield of the product at 50℃/min heating rate
图 4 50℃/min升温速率下热解产物产量的预测曲线与实验曲线
Figure 4. Prediction and experimental curves of the product yield at 50℃/min
表 1 油页岩样品的工业分析、元素分析和原子比
Table 1. Proximate analysis, ultimate analysis and atomic ratio of oil shale samples
Sample Proximate analysis wad/% Ultimate analysis wad/% Atomic ratio M V A FC C H O N S H/C O/C WQ1 2.22 17.60 78.18 2.00 14.30 1.07 5.76 0.69 0.26 0.90 0.30 WQ3 1.78 15.02 81.17 2.03 11.23 1.41 5.44 0.55 0.20 1.51 0.36 WQ5 1.86 16.11 80.28 1.75 12.03 1.50 5.56 0.63 0.21 1.50 0.35 
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表 2 碳化学位移归属
Table 2. Assignments for peaks in 13C-NMR spectra
Chemical shift δ Carbon functionality WQ1 WQ3 WQ5 14-16 aliphatic methyl 2.48 2.22 3.02 16-22 aromatic methyl 7.75 6.06 9.94 22-36 methylene and aliphatic C (2) carbon 47.43 34.05 58.36 36-50 methine and quaternary carbon 18.91 12.97 21.49 50-55 oxy-methylene 2.79 2.32 1.57 55-75 oxy-methine 3.10 0.72 0.69 75-90 oxy-quaternary 0.31 0.75 0.00 100-129 ortho-oxyaromatic protonated 20.46 11.89 21.70 129-137 bridgehead aromatic carbon 8.06 6.84 10.59 137-148 aromatic branched 6.20 4.56 6.38 148-164 oxy-aromatic carbon 2.79 2.69 2.09 164-188 carboxyl 0.31 0.31 0.00 188-220 carbonyl 0.62 0.00 0.00
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表 3 油页岩样品碳骨架结构参数
Table 3. Carbon structural parameters of oil shale sample
Sample fa f′a fac faH faN faP faS faB fal falH fal* falO WQ1 35.18 35.18 0 15.90 19.28 2.17 4.82 6.27 64.82 56.14 8.68 4.82 WQ3 36.07 36.07 0 13.39 22.68 3.03 5.13 7.70 63.93 56.36 7.57 4.27 WQ5 35.64 35.64 0 15.25 20.39 1.47 4.48 7.44 64.36 57.72 6.64 1.59 note：fa: total aromatic carbon；f′a: aromatic carbons；fac: carbonyl carbon；faH: protonated aromatic carbon；faN: non-protonated aromatic carbon；faP: phenolic hydroxyl carbon；faS: alkyl substituted aromatic carbon；faB: bridgehead aromatic carbon；fal: totalaliphatic carbon；falH: methylene or methane carbon；fal* : methyl and quaternary carbon；falO: oxygen-kinked aliphatic carbon
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表 4 结构参数的命名及计算公式
Table 4. Nomenclature and equations of structural parameters
No. Symbol Structural parameter Equation 1 xb ratio of aromatic bridging carbons and
aromatic ring carbons${x_{\rm{b}}}=\frac{{f_{\rm{a}}^{\rm{B}}}}{{{{f'}_{\rm{a}}}}}$ 2 Ca carbons of aromatic cluster ${x_{\rm{b}}}=\frac{{1 -tan{\rm{h}}\frac{{\left ({{C_{\rm{a}}} -{C_0}} \right)}}{m}}}{2}{{x'}_{\rm{b}}} + \frac{{1 + tan{\rm{h}}\left ({\frac{{{C_{\rm{a}}} -{C_0}}}{m}} \right)}}{2}{{x''}_{\rm{b}}}$ 3 Ccl cluster carbons ${C_{{\rm{cl}}}}={C_{\rm{a}}} + {C_{{\rm{al}}}}$ 4 Cal aliphatic carbons ${C_{{\rm{al}}}}={C_{\rm{a}}}\frac{{{f_{{\rm{al}}}}}}{{{f_{\rm{a}}}}}$ 5 Cp circumferential carbons ${C_{\rm{p}}}={C_{{\rm{cl}}}}\left ({f_{\rm{a}}^{\rm{H}} + f_{\rm{a}}^{\rm{S}} + f_{\rm{a}}^{\rm{B}}} \right)$ 6 Ra aromatic rings ${R_{\rm{a}}}=\frac{1}{2}\left ({{C_{\rm{a}}} -{C_{\rm{p}}}} \right) + 1$
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表 5 油页岩样品的团簇结构参数
Table 5. Structural parameters of oil shale aromatic cluster
Sample xb Ca Ccl Cal Cp Ra WQ1 0.1714 8.53 24.37 15.84 6.15 2.19 WQ3 0.2134 10.64 29.50 18.86 7.73 2.46 WQ5 0.2087 10.40 29.18 18.78 7.93 2.24
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