• 论文
主办单位:煤炭科学研究总院有限公司、中国煤炭学会学术期刊工作委员会
神华煤直接液化工艺中溶剂分子结构解析
  • Title

    Solvents’ molecular structure analysis in direct liquefaction of Shenhua coal

  • 作者

    范欢欢白佳凯李旺王兴宝冯杰李文英

  • Author

    FAN Huanhuan,BAI Jiakai,LI Wang,WANG Xingbao,FENG Jie,LI Wenying

  • 单位

    太原理工大学省部共建煤基能源清洁高效利用国家重点实验室

  • Organization
    State Key Laboratory of Clean and Efficient Coal Utilization,Taiyuan University of Technology
  • 摘要

    煤直接液化工艺中除催化剂外溶剂的组成和结构也是直接影响煤的转化率和液体产物 油收率关键因素。 近 10 a 稳定运行在催化剂操作条件无变化情况下发现位于鄂尔多斯市伊金 霍洛旗神华煤直接液化工厂的油收率与神华上海研究院中试装置的油收率结果有些许差距。 为 此对分别来自神华上海研究院中试供氢溶剂(RS-S)和鄂尔多斯煤直接液化工厂供氢溶剂(RSE的物理化学结构如官能团和芳香结构等采用红外光谱同步荧光光谱全二维气相色谱质谱 联用仪进行了定性定量分析。 在此基础上采用密度泛函理论计算了溶剂分子中氢化芳烃的 C键键能及化学环境对其影响的因素。 结果表明种溶剂主要以带取代基的不饱和芳烃为 主芳环数集中在 2~4 ;RS-中氢化芳烃含量要比 RS-高 15.79%环烷烃含量要比 RS-的 低17.11%说明 RS-被过度加氢RS-的供氢能力要高于 RS-E;在一定程度上芳环上不同取 代基可以促进 C键的断裂当取代基取代四氢萘 位时对 C1键键能的影响最大吸电子 取代基比给电子取代基对四氢萘 C1键解离能的影响更明显。 C键键能与解离 原子后 原子上的自旋密度值呈现正相关性原子解离后 C1 的自旋密度越小C1键键能越低C1越容易断裂;随着芳环数的增加C键键解离能降低更容易断裂导致稠环芳香族化合物更容 易被加氢饱和。 良好的供氢溶剂应该是由带取代基的2~4环不饱和芳香烃组成的混合物


  • Abstract

    In direct coal liquefaction,in addition to catalyst,the composition and structure of solvent are key factors that directly affect the rate of coal conversion and the oil yield in liquid product. After nearly ten years of stable operation,with no change in the catalyst and operating conditions,a slight difference was found between the oil yield of Shenhua coal direct liquefaction plant located in Ejin Horo Banner,Ordos and the oil yield results of the Shenhua Shanghai Research Institute pilot plant. Thus,the physicochemical structures of hydrogendonor solvents from the Shenhua Shanghai Research Institute(RS-S)and the Ordos Coal Direct Liquefaction Plant(RS-E),respectively,were investigated,such as functional groups and aromatic structures,etc. Qualitative and quantitative analyses have been performed using the infrared spectroscopy and simultaneous fluorescence spectroscopy,and the group selective twodimensional gas chromatographymass spectrometry/hydrogen flameionization detector method. Based on the above analysis,the C—H bond dissociation energy

    (BDE) of hydrogenated aromatics in solvent molecules and the factors influenced by the chemical environment were calculated using the density functional theory calculations. Results show that both the hydrogendonor solvents are dominated by unsaturated aromatics with substituents,and have the condensed aromatic rings,mainly the bicyclic,tricyclic,and tetracyclic aromatic systems. The content of partially hydrogenated aromatics is the highest in the analyzed two hydrogendonor solvents. The content of partially hydrogenated aromatics in RSS is 15.79% higher than that in RS-E,and the content of cycloalkanes is 17.11% lower than that in RS-E,indicating that the liquefied solvent of RS-E is overhydrogenated,and the hydrogen supplying capacity of RS-S is higher than that of RS-E. Different substituents can promote the dissociation of C—H bonds to some extent. When a substituent is located in the tetralin 1 position,the effect BDE,BDEC1—H value is strong,and the electronwithdrawing substituent has a more pronounced effect on BDEC—H of tetralin than electrondonating substituent. The BDE is linearly correlated with the spin density value of the C atom after the dissociation of the H atom. As the number of aromatic rings increases,the BDEC—H decreases,making it easier to break,resulting in polycyclic aromatic hydrocarbons that are more likely to be saturated by hydrogenation. In short,a good hydrogen donor solvent should be a mixture of methyl substituted,2-4 rings unsaturated aromatic hydrocarbons.


  • 关键词

    煤直接液化工艺供氢溶剂分子结构C—H 键解离能

  • KeyWords

    direct coal liquefaction;H donor solvents;molecular structure;C—H bond;dissociation energy

  • 引用格式
    范欢欢,白佳凯,李旺,等.神华煤直接液化工艺中溶剂分子结构解析[J].煤炭学报,2022,47(10):3189 -3211.
    FAN Huanhuan,BAI Jiakai,LI Wang,et al.Solvents’molecular structure analysis in direct liquefaction of Shenhua coal
    [J].Journal of China Coal Society,2022,47(10):3805-3811.
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