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摘要: 在合成气（CO+H2）与复合溶剂（水+有机溶剂）液化系统下研究了气氛、温度、催化剂类型对宝日希勒褐煤转化率、油气水产率和CO转化率等液化特征的影响，从而探讨其液化性能。结果表明，在高含水复合溶剂系统中，合成气气氛、反应温度430-450℃适宜宝日希勒褐煤液化转化，转化率可达到81.15%，油气水产率达到71.53%。该液化系统下，含铁、碱和硫复合型催化剂能有效地提高液化转化率和油气水产率，在430℃催化液化下褐煤转化率达92.27%，油气水产率达79.39%。该催化剂有效促进了煤中大分子的裂解和系统中水煤气变换反应进程，沥青质减少，油含量增多。液化油中多环芳烃衍生物在催化液化过程中向单环芳烃衍生物和烷烯烃转化，分子量降低，提高了油品质量。Abstract: The effects of atmosphere, temperature and catalysts on the BRXL lignite liquefaction conversion and the yield of oil, gas, and water were studied with syngas and complex solvents (water+organic solvent), and the characteristics of BRXL lignite liquefaction were also discussed. The results show that the atmosphere of syngas and the temperature of 430-450℃ are beneficial to coal liquefaction reaction under complex solvents system with catalyst. The coal conversion is 81.15%, and the yield of oil, gas, and water reaches to 71.53%. Besides, the composite catalyst (including iron, base, and sulfur) can effectively improve the coal conversion and the yield of oil, gas, and water. The coal conversion and the yield of oil, gas, and water at 430℃ reach to 92.27% and 79.39%, respectively. Also, the composite catalyst can effectively promote the cracking of macromolecules in coal and the enhancement of water-gas shift reaction, resulting in a decrease of asphaltene and an increase of oil yield. Moreover, the polycyclic aromatic hydrocarbons and derivatives in liquefaction oil can be converted to monocyclic aromatic hydrocarbons and derivatives and alkenes olefins during catalytic liquefaction, resulting in a decrease of compound molecular weight and an improvement of oil quality.
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Key words:
- lignite /
- syngas /
- complex solvent /
- direct coal liquefaction /
- catalyst
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图 6 正己烷可溶物的色谱图
Figure 6 Gas chromatogram of HEX soluble fraction
●: alkenes; ■: monocyclic aromatic hydrocarbons;
▲: ethers; ◆: polycyclic aromatic hydrocarbons and their derivatives表 1 煤样的工业分析、元素分析及岩相分析
Table 1 Proximate, ultimate and petrographic analysis of coal
Proximate analysis w/% Ultimate analysis w/% H/C
(atomic ratio)Mad Ad Vdaf FCdaf Cdaf Hdaf Ndaf St, d Odaf* 3.52 11.31 43.50 56.50 72.27 4.97 1.10 0.50 21.09 0.83 Petrographic analysis φ/% RMAXO vitrinite inertinite exinite maceral 88.44 8.03 1.57 1.96 0.34 St, d: total sulfur on dry basis; *: by difference; φ: percent of volume 
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表 2 不同气氛下褐煤液化转化率及产物产率
Table 2 Liquefaction conversion and product yields of lignite under different atmospheres
Atmosphere Conversion x/% Yield w/% YdPA YdAS YdOGM H2 79.46 9.00 7.05 63.41 N2 76.15 9.31 8.19 58.65 CO 83.44 9.52 7.51 66.41 Syngas 81.15 4.83 4.79 71.53
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表 3 不同温度下褐煤液化转化率及产物产率
Table 3 Liquefaction conversion and product yields of lignite under different temperatures
Temperature t/℃ Conversion x/% Yield w/% YdPA YdAS YdOGM 400 73.73 24.12 13.1 36.51 430 78.55 12.8 9.68 56.07 450 81.15 4.83 4.79 71.53
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表 4 不同催化剂下褐煤液化转化率及产物产率
Table 4 Liquefaction conversion and product yields of lignite under different catalysts
Catalyst Conversion x/% Yield w/% YdPA YdAS YdOGM no catalyst 64.67 13.15 13.76 37.76 A 67.66 11.17 9.19 47.3 B 69.11 11.02 10.36 47.73 C 78.55 12.8 9.68 56.07 D 74.57 8.31 6.79 59.47 E 92.27 7.29 5.59 79.39
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表 5 液化油的液相组成分及分类
Table 5 Compound distribution and classification of oil
Catalyst Relative content w/% alkanes olefins heterocycles phenols MAHD PAHD no catalyst 6.38 6.79 10.83 30.66 45.35 C 23.33 1.98 9.80 30.51 34.48 E 28.58 0.81 7.75 36.09 26.77 MAHD: monocyclic aromatic hydrocarbons and derivatives; PAHD: polycyclic aromatic hydrocarbons and derivatives
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