中低温煤焦油基炭微球的制备

doi:10.16085/j.issn.1000-6613.2019-0829

摘要/Abstract

摘要：

通过馏分切割、温和加氢相结合对中低温煤焦油进行精制处理，精制后的原料采用分级热聚制备中间相炭微球。考察了精制处理条件对原料性质、中间相炭微球宏观外貌及微晶结构的影响。采用FTIR、GC-MS、族组成、元素分析对原料进行表征，采用SEM、XRD对中间相炭微球进行表征。结果表明：中低温煤焦油中300～430℃馏分油是制备中间相炭微球的较佳馏分。300～430℃馏分油中正庚烷可溶物（HS）质量分数高达84.76%，吡啶不溶物（PI）质量分数低至0.23%，杂原子含量低，芳烃化合物的环数为2～4环。300～430℃馏分油在T_H=350℃、p=8MPa、t=1.5h、剂油比1∶40（质量比）的条件下温和加氢得到的精制原料，经420℃热聚6h得制备的中间相炭微球宏观外貌、微晶结构较好。中低温煤焦油基炭微球的粒径范围为5～15μm，小球表面光滑，微观结构为地球仪型，经1450℃高温煅烧后，石墨化度达到12.33%。

关键词: 中低温煤焦油, 中间相炭微球, 精制处理, 温和加氢, 馏分切割

Abstract:

The refining treatment of medium and low temperature coal tar was carried out by fraction cutting and mild hydrogenation. Mesocarbon microbeads were prepared from refined raw materials by staged thermal polymerization. The effects of refining treatment conditions on the properties of raw materials, macroscopic appearance and microcrystalline structure of mesocarbon microbeads were investigated. The raw materials were characterized by FTIR, GC-MS, group composition and elemental analysis, and the mesocarbon microbeads were characterized by SEM and XRD. The results showed that the distillate oil at 300—430℃ in medium and low temperature coal tar was better fraction for preparing mesocarbon microbeads. The content of n-heptane soluble (HS) and pyridine insoluble (PI) was 84.76% and 0.23%, respectively, while heteroatom was low and the ring number of aromatic compounds was 2—4. The refined raw materials were obtained by mild hydrogenation of 300—430℃ distillate oil under the conditions of T_H=350℃, p=8MPa, t=1.5h, the mass ratio of catalyst to distillate oil is 1∶40, and mesocarbon microbeads which were prepared from refined raw materials by thermal polymerization at 420℃ for 6h had better macroscopic appearance and microcrystalline structure. The particle size of mesocarbon microbeads ranges from 5μm to 15μm. The surface of the mesocarbon microbeads was smooth and the microstructure was globe-shaped. After calcination at 1450℃, the degree of graphitization reached 12.33%.

Key words: medium and low temperature coal tar, mesophase carbon microspheres, refining treatment, mild hydrogenation, fraction cutting

中图分类号:

TQ316

郑金欣,田育成,郝博天,淡勇,李稳宏,黄晔,高峰,李冬. 中低温煤焦油基炭微球的制备[J]. 化工进展, 2020, 39(2): 649-657.

Jinxin ZHENG,Yucheng TIAN,Botian HAO,Yong DAN,Wenhong LI,Ye HUANG,Feng GAO,Dong LI. Preparation of medium and low temperature coal tar-based mesocarbon microbeads[J]. Chemical Industry and Engineering Progress, 2020, 39(2): 649-657.

图/表 16

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密度（20℃）/g·cm^-3	黏度（50℃）/mm²·s^-1	H/C原子比	元素分析/%					族组成/%
密度（20℃）/g·cm^-3	黏度（50℃）/mm²·s^-1	H/C原子比	C	H	O	S	N	HS	HI-TS	TI-PS	PI	收率
1.037	15.26	1.241	82.48	8.53	7.57	0.34	1.08	70.89	18.26	4.52	1.02	94.69

密度（20℃）/g·cm^-3	黏度（50℃）/mm²·s^-1	H/C原子比	元素分析/%					族组成/%
密度（20℃）/g·cm^-3	黏度（50℃）/mm²·s^-1	H/C原子比	C	H	O	S	N	HS	HI-TS	TI-PS	PI	收率
1.037	15.26	1.241	82.48	8.53	7.57	0.34	1.08	70.89	18.26	4.52	1.02	94.69

样品名称	烷烃/%	烯烃/%	芳烃/%	氧化物/%	氮化物/%	硫化物/%
中低温煤焦油	38.99	2.45	39.59	16.35	2.08	0.54
200～400℃馏分油	42.14	1.93	33.47	20.39	1.67	0.40
300～430℃馏分油	43.77	1.64	44.66	7.53	1.98	0.42
＞300℃软沥青	43.90	1.30	43.89	8.11	2.21	0.59

样品名称	烷烃/%	烯烃/%	芳烃/%	氧化物/%	氮化物/%	硫化物/%
中低温煤焦油	38.99	2.45	39.59	16.35	2.08	0.54
200～400℃馏分油	42.14	1.93	33.47	20.39	1.67	0.40
300～430℃馏分油	43.77	1.64	44.66	7.53	1.98	0.42
＞300℃软沥青	43.90	1.30	43.89	8.11	2.21	0.59

样品名称	1环/%	2环/%	3环/%	4环/%	1+1/%	2+1/%	3+1/%
中低温煤焦油	0.87	12.93	12.62	3.59	7.56	1.51	0.51
200～400℃馏分油	0.61	10.24	13.04	5.29	0	2.28	2.01
300～430℃馏分油	0	5.31	29.34	7.08	0.78	1.31	0.84
＞300℃软沥青	0	4.39	28.17	7.29	0.50	1.76	1.78