Analysis of medium temperature coal tar pitch group composition and its effect on the structure of mesophase pitch
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摘要: 以甲苯-吡啶、正庚烷-四氢呋喃为溶剂,采用索氏抽提分离中温沥青(ZCTP)的族组分并解析其组成与结构。结果表明,与ZCTP相比,甲苯不溶-吡啶可溶物(TI-PS)和正庚烷不溶-四氢呋喃可溶物(HI-THFS)的热稳定性更高,残炭率增至56.95%和47.63%,失重量分别减小41.51%和28.85%;此外,TI-PS和HI-THFS的C=C含量分别比ZCTP高6.69%和3.26%,为75.57%和73.14%,吡啶氮含量分别提升约16和8个百分点。以TI-PS和HI-THFS为原料分别制得中间相沥青M-TI-PS和M-HI-THFS。其中,M-HI-THFS以中小区域型为主,并伴有部分细镶嵌结构,光学各向异性含量较低;M-TI-PS光学各向异性含量约为80%,且形成了广域型光学织构;然而ZCTP难以形成稳定的区域型光学织构,只能形成马赛克型光学织构。Abstract: Medium temperature coal tar pitch (ZCTP) was separated by Soxhlet extraction using toluene-pyridine and n-heptane-tetrahydrofuran as solvents to obtain the group components. Then, their composition and structure were analyzed. The results show that, in comparison with ZCTP, toluene-insoluble pyridine soluble (TI-PS) and n-heptane-insoluble tetrahydrofuran soluble (HI-THFS) are more thermally stable, exhibiting a decrease weight loss of 41.51% and 28.85% and an increase residual carbon rate of 56.95% and 47.63%, respectively. In addition, the C=C contents of TI-PS and HI-THFS are 6.69% and 3.26% higher than that of ZTCP, reaching 75.57% and 73.14%, and the pyridine nitrogen contents of TI-PS and HI-THFS increase about 16 and 8 percentage points. Both TI-PS and HI-THFS were used to prepare mesophase pitch. It is found that M-HI-THFS is mainly consisted of small and medium area type with some fine mosaic structure and low optical anisotropy content. While M-TI-PS has about 80% optical anisotropy content and displays a wide range of optical weave. However, it is difficult for ZCTP to form a stable regional optical fabric structure, just exhibiting a mosaic optical fabric.
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表 1 沥青的工业分析与元素分析
Table 1 Element and proximate analyses of three kinds of pitches
Sample proximate analysis ${w_{ {\rm{ad} } }/{\% } }$ ultimate analysis $ w/{\% }$ H/C O/C M V FC* A C H O* N S ZCTP 1.00 74.75 23.42 0.83 83.58 9.18 5.56 1.56 0.12 1.32 0.059 TI-PS 0.95 48.69 49.87 0.49 85.61 6.92 4.35 3.07 0.15 0.97 0.038 HI-THFS 0.93 54.72 43.73 0.62 84.24 8.36 4.95 2.32 0.13 1.19 0.044 *: by difference, ad: air-dried basis M: moisture, V: volatile, FC: fixed carbon, A: ash 表 2 沥青组分中C、O和N的赋存形式及相对含量
Table 2 Forms and relative contents of C, O and N in pitch
Type Assignment Binding energy /eV Relative content/ % ZCTP TI-PS HI-THFS C 1s C = C 284.3 70.83 75.57 73.14 C−C 285.2 22.93 18.48 20.85 C−O 286.2 6.24 5.95 6.01 O 1s C = O 531.2 13.90 11.35 12.16 C−O 532.3 64.84 60.32 62.68 COO− 533.4 21.26 28.83 22.16 N 1s N-6 398.9 47.55 63.61 55.16 N-5 400.0 52.45 36.39 44.84 -
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