Preparation of medium and low temperature coal tar-based mesocarbon microbeads

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

Abstract

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

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

CLC Number:

TQ316

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.

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.

Figures/Tables 16

References 29

1	SUN Shuai, WANG Chengyang, CHEN Mingming, et al. A method to observe the structure of the interface between mesocarbon microbeads and pitch[J]. Journal of Colloid and Interface Science, 2014, 426: 206-208.
2	MORIYAMA R, HAYASHI J I, CHIBA T. Effects of quinoline-insoluble particles on the elemental processes of mesophase sphere formation[J]. Carbon, 2004, 42: 2443-2449.
3	LI Tongqi. Structural characteristics of mesophase spheres prepared from coal tar pitch modified by phenolic resin[J]. Chinese J. Chem. Eng., 2006, 14(5): 660-664.
4	MA Zhichao, LIN Qilang, CAI Qiuhong, et al. Effect of rosin addition on preparation of mesocarbon microbeads[J]. Journal of Functional Materials, 2012, 43(8): 1052-1055.
5	XIA Wenli, CHEN Jianming, SHU Xin, et al. The technological conditions of preparation of mesophase pitch by simultaneous hydrogenation-thermal condensation[J]. Journal of Functional Materials, 2012, 43(3): 367-371.
6	王红玉. 中间相炭微球制备与形成机理的研究[D]. 太原: 太原理工大学, 2008.
	WANG Hongyu. Study on the preparation and formation mechanism of mesophase carbon microspheres[D]. Taiyuan: Taiyuan University of Technology, 2008.
7	李春艳. 中间相碳微球的制备与研究[D]. 长沙: 长沙理工大学, 2013.
	LI Chunyan. Preparation and study of mesophase carbon microspheres[D]. Changsha: Changsha University of Science and Technology, 2013.
8	陈雷. 沥青中间相炭材料的形成及其微结构与缺陷的研究[D]. 长沙: 湖南大学, 2018.
	CHEN Lei. Formation of asphalt mesophase carbon materials and their microstructure and defects[D]. Changsha: Hunan University, 2018.
9	颜丙峰, 毛学锋, 王光耀, 等. 两种原料共炭化制取中间相炭微球[J]. 煤炭转化, 2018, 41(1): 40-48.
	YAN Bingfeng, MAO Xuefeng, WANG Guangyao, et al. Preparation of mesophase carbon microspheres by co-carbonization of two raw materials[J]. Coal Conversion, 2018, 41(1): 40-48.
10	GREINKE R A, LEWIS I C. Carbonization of naphthalene and dimethylnaphthalene[J]. Carbon, 1984, 22: 305-314.
11	裴亮军, 李冬, 袁扬, 等. 不同正构烷烃溶剂沉淀中低温煤焦油沥青质的结构组成变化规律[J]. 化工进展, 2017, 36(6): 2101-2108.
	PEI Liangjun, LI Dong, YUAN Yang, et al. The change of structural composition of low temperature coal tar asphaltenes in solvent precipitation of different normal paraffins[J]. Chemical Industry and Engineering Progress, 2017, 36(6): 2101-2108.
12	姚春雷, 全辉, 张忠清. 中、低温煤焦油加氢生产清洁燃料油技术[J]. 化工进展, 2013, 32(3): 501-507.
	YAO Chunlei, QUAN Hui, ZHANG Zhongqing. Hydrogenation of medium and low temperature coal tars for production of clean fuel oil[J]. Chemical Industry and Engineering Progress, 2013, 32(3): 501-507.
13	张晓静. 中低温煤焦油加氢技术[J]. 煤炭学报, 2011, 36(5): 840-844.
	ZHANG Xiaojing. Hydrogenating process for coal tar from mid-low-temperature coal carbonization[J]. Journal of China Coal Society, 2011, 36(5): 840-844.
14	赵璞, 裴贤丰, 王之正. 中低温煤焦油加工利用现状研究[J]. 煤质技术, 2016, 6: 11-16.
	ZHAO Pu, PEI Xianfeng, WANG Zhizheng. Study on the present situation of medium/low temperature coal tar processing and utilization[J]. Coal Quality Technology, 2016，6: 11-16.
15	宋剑. 中、低温煤焦油加氢生产清洁燃料油技术研究[J]. 化工管理, 2015, 20: 160.
	SONG Jian. Study on the technology of hydrogenation of medium and low temperature coal tar to produce clean fuel oil[J]. Chemical Management, 2015, 20: 160.
16	闫厚春, 范雯阳, 廖朝辉, 等. 中低温煤焦油的加工利用现状[J]. 应用化工, 2019, 48(8): 1904-1907.
	YAN Houchun, FAN Wenyang, LIAO Zhaohui, et al. Current status of processing and utilization of medium and low temperature coal tar[J]. Applied Chemical Industry，2019，48（8）:1904-1907.
17	陈泊韬, 张典典, 卢剑娴. 粉葛深加工技术研究及开发[J]. 农产品加工学刊, 2013, 10: 57-59．
	CHEN Botao, ZHANG Diandian, LU Jianxian. Research and development of powder deep processing technology[J]. Agricultural Products Processing Journal, 2013, 10: 57-59.
18	张伟, 崔保银, 王磊, 等. 精制煤焦油软沥青的组成、结构及其热反应性能[J]. 煤化工, 2016, 44(5): 47-50.
	ZHANG Wei, CUI Baoyin, WANG Lei, et al. Composition, structure and thermal reaction performance of refined coal tar soft bitumen[J]. Coal Chemical Industry, 2016, 44(5): 47-50.
19	吕君, 高丽娟, 朱亚明, 等. 中低温煤焦油沥青组成及结构的表征[J]. 材料导报, 2016, 30(8): 127-131.
	Jun LÜ, GAO Lijuan, ZHU Yaming, et al. Characterization of composition and structure of medium and low temperature coal tar pitch[J]. Materials Review, 2016, 30(8): 127-131.
20	解小玲. 对煤基沥青中间相形成因素及针状焦结构影响的研究[D]. 太原: 太原理工大学, 2014.
	XIE Xiaoling. Study on the formation factors of coal-based asphalt mesophase and needle coke structure[D]. Taiyuan: Taiyuan University of Technology, 2014.
21	王亮. 原料组成对针状焦形成的影响[D]. 北京: 中国石油大学, 2009.
	WANG Liang. Effect of raw material composition on the formation of needle coke[D]. Beijing: China University of Petroleum, 2009.
22	孙鸣, 陈静, 代晓敏, 等. 陕北中低温煤焦油重油减压馏分的GC-MS分析[J]. 化学工程, 2015, 43(9): 52-57.
	SUN Ming, CHEN Jing, DAI Xiaomin, et al. GC-MS analysis of vacuum oil fractions of medium and low temperature coal tar in northern Shaanxi[J]. Chemical Engineering, 2015, 43(9): 52-57.
23	单长春, 刘春法, 张秀云, 等. 针状焦光学显微结构分析研究[J]. 燃料与化工, 2008, 1: 35-38.
	SHAN Changchun, LIU Chunfa, ZHANG Xiuyun, et al. Analysis of optical microstructure of needle coke[J]. Fuel&Chemical Industry, 2008, 1: 35-38.
24	秦匡宗, 郭绍辉. 石油沥青质[M]. 北京: 石油工业出版社, 2002: 6-62.
	QIN Kuangzong, GUO Shaohui. Petroleum asphaltenes[M]. Beijing: Petroleum Industry Press, 2002: 6-62.
25	王子军. 石油沥青质的化学和物理-I石油沥青质的定义和分离[J]. 石油沥青, 1995, 4(2): 35-37.
	WANG Zijun. Petroleum asphaltenes chemistry and physics-I petroleum asphaltenes definition and separation [J]. Petroleum Asphalt, 1995, 4(2): 35-37.
26	冯新娟, 闵小建, 郑化安, 等. 中低温煤焦油重油正庚烷萃余物的反应(甲醛)分离与分析[J]. 燃料化学学报, 2018, 46(1): 15-26.
	FENG Xinjuan, MIN Xiaojian, ZHENG Huaan, et al. Separation and analysis of the reaction of formaldehyde (meth) in heavy oil coal tar heavy oil n-heptane[J]. Journal of Fuel Chemistry, 2018, 46(1): 15-26.
27	高丽娟, 赵雪飞, 赖仕全, 等. 煤精制软沥青庚烷可溶组的结构表征[J]. 云南化工, 2018, 4: 1-5.
	GAO Lijuan, ZHAO Xuefei, LAI Shiquan, et al. Structural characterization of coal-refined soft asphalt heptane soluble group[J]. Yunnan Chemical Industry, 2018, 4: 1-5.
28	李娟, 王灿, 詹亮, 等. 预氧化对中间相沥青泡沫炭结构和性能的影响机制研究[J]. 无机材料学报, 2009, 2: 315-319.
	LI Juan, WANG Can, ZHAN Liang, et al. Study on the influence mechanism of preoxidation on the structure and properties of mesophase asphalt foamed carbon[J]. Journal of Inorganic Materials, 2009, 2: 315-319.
29	凌立成, 陈玉琴, 吴东, 等. 中间相沥青纤维的氧化稳定化及炭化[J]. 炭素技术, 1995, 6: 14-20.
	LING Licheng, CHEN Yuqin, WU Dong, et al. Oxidation stabilization and carbonization of mesophase pitch fibers[J]. Carbon Technology, 1995, 6: 14-20.

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