萘沥青及热转化产物的性质和结构表征

doi:10.16085/j.issn.1000-6613.2019-1556

摘要/Abstract

摘要：

以萘为原料，5%、10%、20%质量分数AlCl₃为催化剂，采用自升压法制备了3种萘沥青（NP-5%、NP-10%、NP-20%），对其进行了工业分析、FTIR、GPC以及TG/DTG表征，并且利用PLM、SEM、Raman和XRD等手段对其中间相热转化产物（MNP-4h、MNP-4.5h、MNP-6h）和炭化产物（CNP-5%、CNP-10%、CNP-20%）的微观结构进行了研究。结果表明，3种萘沥青的收率都在80%以上，其分子量分布在147～3940范围内，质均分子量都为255左右；3种萘沥青的芳香性指数（I_ar）分别为0.05、0.27、0.36，支链化指数（CH₃/CH₂）分别为0.65、0.06、0.02，在750℃的残炭率分别为27%、31%、30%。PLM观察发现，3种中间相热转化产物的显微结构分别为中间相小球体、中间相纺锤状以及纤维状结构。从MNP-4h中可萃取得到产率为8%的中间相小球，其表面光滑、粒径均匀，直径在5～7μm。Raman分析表明，3种中间相热转化产物的I_G/I_all分别为15%、17%、30%，说明延长热转化时间，可增加产物碳微晶的规整性。3种炭化产物的显微结构都以镶嵌结构为主，其碳微晶层间距都为0.35nm，而CNP-5%具有最大的微晶尺寸。

关键词: 萘沥青, 热转化, 催化, 聚合, 显微结构

Abstract:

Three naphthalene pitches (NP-5%, NP-10% and NP-20%) were prepared by self-rising pressure method of naphthalene as raw material with 5%, 10% and 20% AlCl₃ as catalyst. The naphthalene pitches were studied by proximate analysis, FTIR, GPC and TG/DTG characterization. The microstructures of its corresponding mesophase thermal conversion products (MNP-4h、MNP-4.5h、MNP-6h) and carbonization products (CNP-5%, CNP-10% and CNP-20%) were studied by polarizing microscope, SEM, Raman spectrum and XRD. The results showed that the yield of the three naphthalene pitches was all more than 80%, and the molecular weight distribution of naphthalene pitch was mainly in the range of 147—3940. The mass average molecular weights of the three naphthalene pitches were about 255. The corresponding aromaticity index (I_ar) of three naphthalene pitches was 0.05, 0.27 and 0.36. The branched index (CH₃/CH₂) was 0.65, 0.06 and 0.02. The residual carbon yields at 750℃ were 27%, 31% and 30%, respectively. The polarized light microscope observation found that the optical microstructure of three naphthalene pitches was homogeneously distributed mesophase spheres, mesophase spindle-shaped and fibrous structures, respectively. The yield of mesophase spheres after extraction and drying of MNP-4h was 8%. The spheres had a smooth surface and a uniform particle size, ranging from 5μm to 7μm in diameter. The results of Raman spectrum indicated that the content of I_G/I_all of three mesophase thermal conversion products were 15%, 17% and 30%, respectively. The above results proved that the regularity of carbon crystallites can be increased by prolonging thermal conversion time. The optical microstructures of three carbonization products were mainly mosaic structures, and the layer spacing of the three carbonized products carbon crystallites was 0.35nm. Among them, CNP-5% had the largest carbon crystallite size.

Key words: naphthalene pitch, thermal conversion, catalysis, polymerization, microstructure

中图分类号:

TQ522.65

洪海球, 邓宋, 赖仕全, 岳莉, 赵雪飞. 萘沥青及热转化产物的性质和结构表征[J]. 化工进展, 2020, 39(7): 2724-2733.

Haiqiu HONG, Song DENG, Shiquan LAI, Li YUE, Xuefei ZHAO. Properties and structural characterization of naphthalene pitch and its thermal conversion products[J]. Chemical Industry and Engineering Progress, 2020, 39(7): 2724-2733.

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