煤-油临氢缓和液化半焦晶相结构分析

炼油技术与工程 ›› 2022, Vol. 52 ›› Issue (3): 6-9.

煤-油临氢缓和液化半焦晶相结构分析

孙昱东,顾强,王昱心,刘琦

中国石油大学(华东)化学工程学院，山东省青岛市 266580

收稿日期:2022-01-05 出版日期:2022-03-15 发布日期:2022-03-16
作者简介:孙昱东，教授，博士，2011年毕业于华东理工大学化学工艺专业，主要从事石油加工和重质油化学方面的教学与科研工作。联系电话：0532-86980605，E-mail：ydsun@upc.com。

Crystal structure analysis of semicoke in coal-oil co-processing under mild condition in hydrogen

Sun Yudong, Gu Qiang, Wang Yuxin, Liu Qi

College of Chemical Engineering, China University of Petroleum, Qingdao,Shandong 266580

Received:2022-01-05 Online:2022-03-15 Published:2022-03-16

摘要/Abstract

摘要： 以鄂尔多斯煤为原料，加氢后的煤焦油为溶剂油，在高压釜内进行煤-油共炼反应，采用元素分析、工业分析、X射线衍射(XRD)、扫描电子显微镜等对原料煤和半焦微晶结构进行分析。结果表明：煤与半焦主要由C和O元素组成，此外还含有少量的H，S，N等元素；与原料煤相比，半焦的H/C摩尔比减少0.23，挥发分和固定碳质量分数分别降低15.77，1.64百分点，灰分升高17.87百分点；煤和半焦的XRD谱图中出现大量无机矿物质特征衍射峰，主要来源于煤和半焦中的灰分；高温、高氢压环境下，煤发生裂解与聚合反应，煤中芳香结构缩聚明显，有机质碳原子排列趋于定向且规则，石墨化程度增加；原料煤表面光滑，排列有序，粒径较大，而半焦表面粗糙，排列无序，粒径较小，表面有大量孔隙。

关键词: 煤-油共炼, 半焦, 晶相结构, 微观参数, 外观形貌

Abstract: Taking Ordos coal as raw material and coal tar after hydrogenation as solvent oil, the coal-oil co-processing was carried out in an autoclave. The microcrystalline structure of raw coal and semicoke was analyzed by ultimate analysis, industrial four component analysis, X-ray diffraction and scanning electron microscope. The results showed that coal and semicoke are mainly composed of carbon and oxygen, and a small amount of H, S, N and other elements. The H/C ratio of semicoke is less than that of coal by 0.23. The content of volatile and fixed carbon in semicoke decreased by 15.77 and 1.64 percentage points, but the content of ash increased by 17.87 percentage points. A large number of characteristic diffraction peaks of inorganic minerals appear in XRD spectra, mainly from the ash of coal and semicoke. Under the conditions of high temperature and high pressure hydrogen, the pyrolysis and polymerization led to the increasing of aromaticity, regularity of carbon arrangement and increasing of graphitization in semicoke. The surface of coal is smooth and regular which with large particle size. The surface of semicoke is rough and irregular which with small particle size and a large number of pores on the surface.

Key words: Coal-oil co-processing, semicoke, crystal structure, microcrystalline parameters, surface morphology

孙昱东, 顾强, 王昱心, 刘琦. 煤-油临氢缓和液化半焦晶相结构分析[J]. 炼油技术与工程, 2022, 52(3): 6-9.

Sun Yudong, Gu Qiang, Wang Yuxin, Liu Qi. Crystal structure analysis of semicoke in coal-oil co-processing under mild condition in hydrogen[J]. Petroleum Refinery Engineering, 2022, 52(3): 6-9.

参考文献

[1]赵杰,曾明明,陈晓菲,等.半焦生产低水分熄焦工艺技术展望[J].煤炭加工与综合利用,2021(3):78-80.

[2] 张亚婷,李萌,李可可,等.半焦基多孔石墨化炭可控制备及其吸附性能研究[J].炭素技术,2020,39(4):36-40.

[3] 王丽,张蓬洲.煤的XRD的结构分析[J].煤炭转化,1997,20(1):50-53.

[4] ALHUMAIDAN F S,HAUSER A,RANA M S,et al.Changes in asphaltene structure during thermal cracking of residual oils:XRD study [J].Fuel,2015,150:558-564.

[5] 戴鑫,杨涛,杨天华,等.煤-油共炼残渣性质分析[J].石油炼制与化工,2019,50(1):89-95.

[6] ZHOU Y,ALBIJANIC B,TADESSE B,et al.Surface properties of aged coal and their effects on bubble-particle attachment during flotation[J].Advanced powder technology,2020,31(4):1490-1499.

[7] 杨康,李辉,嵇鹰,等.燃烧过程中煤氮热迁移特性研究进展[J].环境工程,2015,33(5):81-84.

[8] 陈皓侃,李保庆,张碧江.反应条件对煤加氢热解产物分布的影响[J].燃料化学学报,1997(1):50-55.

[9] 赵凌云.临氢缓和条件下的煤-油共炼技术研究及初步工艺设计[D].青岛:中国石油大学(华东),2016.

[10]张锐,夏阳超,谭金龙,等.低阶煤分子碳结构的分析与研究[J].中国煤炭,2018,44(12):88-94.

[11] QI X J,GUO X,XUE L C,et al.Effect of iron on Shenfu coal char structure and its influence on gasification reactivity[J].Journal of analytical and applied pyrolysis,2014,110:401-407.

[12] LI C,MENG H,YANG T ,et al.Study on catalytic performance of oil-soluble iron-nickel bimetallic catalyst in coal/oil co-processing[J].Fuel,2018,219:30-36.

[13] 王庆晖,王爱宽,邵培.山西沁水盆地寺河煤矿煤微晶结构及化学组成特征分析[J].煤质技术,2021,36(1):36-42.