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

doi:10.16085/j.issn.1000-6613.2017.06.019

化工进展 ›› 2017, Vol. 36 ›› Issue (06): 2101-2108.DOI: 10.16085/j.issn.1000-6613.2017.06.019

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

裴亮军, 李冬, 袁扬, 薛凤凤, 李稳宏

西北大学化工学院, 陕西西安 710069

收稿日期:2016-09-26 修回日期:2017-02-16 出版日期:2017-06-05 发布日期:2017-06-05
通讯作者: 李冬
作者简介:裴亮军(1990—),男,硕士研究生,从事煤焦油深加工研究。E-mail:2431454542@qq.com。
基金资助:
国家自然科学基金（21646009）、陕西省科技统筹创新工程计划项目（2014KTCL01-09）、陕西省教育厅产业化培育项目（14JF026，15JF031）及陕西省青年科技新星项目（2016KJXX-32）。

Composition and structural changes of low temperature coal tar asphaltenes precipitated in different n-alkane solvents

PEI Liangjun, LI Dong, YUAN Yang, XUE Fengfeng, LI Wenhong

School of Chemical Engineering, Northwest University, Xi'an 710069, Shaanxi, China

Received:2016-09-26 Revised:2017-02-16 Online:2017-06-05 Published:2017-06-05

摘要/Abstract

摘要： 利用X射线光电子能谱分析（XPS）、元素分析和FTIR对不同正构烷烃溶剂（正戊烷、正己烷、正庚烷）沉淀出的正戊烷沥青质（As-5）、正己烷沥青质（As-6）、正庚烷沥青质（As-7）、溶于正己烷不溶于正戊烷的沥青质[As-（5-6）]、溶于正庚烷不溶于正己烷的沥青质[As-（6-7）]、溶于正庚烷不溶于正戊烷的沥青质[As-（5-7）]共6种中低温煤焦油沥青质进行了表征，系统分析了元素的赋存形态、相对含量和官能团类型。结果表明，碳在沥青质表面主要以sp²碳和sp³碳的形式存在，二者相对含量之和均达85%以上，以C=O和COO—基团存在的C较少，且As-（5-7）的芳香度较小，As-7芳香度最大。6种沥青质表面的杂原子以O原子为主，主要以C—OH、C—O—C形式存在。N主要以吡啶、吡咯形态存在，两者含量之和均在70%以上，且含有少量的胺和质子化吡啶，As-（5-6）、As-（6-7）、As-（5-7）沥青质中胺类含量高于As-5、As-6、As-7，主要原因是前者芳香环侧链长度大于后者的。

关键词: 中低温煤焦油, 沥青质, 不同溶剂, X射线光电子能谱分析, 表面结构

Abstract: Asphaltenes were precipitated with different n- alkanes from medium/low temperature coal tar,including n-pentane asphaltene(As-5),n-hexane asphaltene(As-6),n-heptane asphaltene(As-7),soluble in n-hexane but insoluble in n-pentane[As-(5-6)],soluble in n-heptane but insoluble in n-hexane[As-(6-7)] and soluble in n-heptane but insoluble in n-pentane[As-(5-7)]. They were characterized by XPS,elemental analysis and FTIR. The occurrence state and content of element,functional groups of elements in asphaltenes were obtained and systematically discussed. The results showed that the sp²carbon and sp³carbon were the main forms of carbon and the total content reached 85%,while the C=O and COO— were fewer. The aromaticity(f_a) of As-(5-7) was obviously smaller than that of As-7. The heteroatoms on the surface of the six kinds of asphaltenes were mainly oxygen atoms existed in the form of C—OH and C—O—C mostly. The pyridine and pyrrolic were the main forms of nitrogen with the sum of relative content up to more than 70%. Nitrogen were detected as amine and the protonation pyridine with the smaller content in the total nitrogen functional groups. The amine content of As-(5-6),As-(6-7) and As-(5-7) asphaltenes were higher than As-5,As-6 and As-7 asphaltenes due to the aromatic ring side chain length of the former were larger than the latter.

Key words: medium/low temperature coal tar, asphaltene, different solvents, XPS, surface structure

中图分类号:

TE622.1

裴亮军, 李冬, 袁扬, 薛凤凤, 李稳宏. 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(06): 2101-2108.

PEI Liangjun, LI Dong, YUAN Yang, XUE Fengfeng, LI Wenhong. Composition and structural changes of low temperature coal tar asphaltenes precipitated in different n-alkane solvents[J]. Chemical Industry and Engineering Progress, 2017, 36(06): 2101-2108.

参考文献

[1] 雷雨辰,李冬,李稳宏,等. 煤焦油加氢精制催化剂的级配研究[J].石油学报(石油加工),2012,28(1):83-87. LEI Y C,LI D,LI W H,et al. Study on grading of coal tar hydrotreating catalysts[J]. Acta Petroleum Sinica(Petroleum Processing Section),2012,28(1):83-87.
[2] 李传,王继乾,隋李涛,等. 委内瑞拉稠油沥青质的XPS研究[J].石油学报(石油加工),2013,29(3):459-463. LI C,WANG J Q,SUI L T,et al. Study on XPS of Venezuela heavy oil asphaltene research[J]. Acta Petroleum Sinica (Petroleum Processing Section),2013,29(3):459-463.
[3] 裴贤丰. 低温煤焦油沥青质和胶质的分离与表征[J]. 洁净煤技术,2011,17(4):43-46. PEI X F. Separation and characterization of low temperature coal tar asphaltene and resin[J]. Clean Coal Technology,2011,17(4):43-45.
[4] KERSHAW J R,BLACK K J T. Structural characterization of coal-tar and petroleum pitches[J]. Energy & Fuels,1993,7(3):420-425.
[5] 黄澎. 高温煤焦油悬浮床加氢裂化研究[J]. 洁净煤技术,2011,17(3):61-63. HUANG P. Study on slurry-bed hydrocracking reactions of high temperature coal tar[J]. Clean Coal Technology,2011,17(3):61-63.
[6] 孙智慧,马海霞,李冬,等. 中低温煤焦油加氢前后沥青质组成和结构变化[J]. 煤炭学报,2014,39(7):1366-1371. SUN Z H,MA H X,LI D,et al. Composition and structure changes of asphaltenes from medium and low temperature coal tar before and after hydrotreating[J]. Journal of China Coal Society,2014,39(7):1366-1371.
[7] 杜庆阳,张晶晶,牛京超,等. 中低温煤焦油沥青烯的结构表征[J]. 化学工程,2014,42(7):57-59. DU Q Y,ZHANG J J,NIU J C,et al. Structure characterization of asphaltene from medium and low temperature coal tar[J]. Chemical Engineering,2014,42(7):57-59.
[8] 秦匡宗. 石油沥青质[M]. 北京:石油工业出版社,2002. QIN K Z. Petroleum asphaltene [M]. Beijing:Petroleum Industry Press,2002.
[9] 胡玉峰,杨兰英. 原油正构烷烃沥青质聚沉机理研究及沉淀量测定[J]. 石油勘探与开发,2000,27(5):109-111. HUN Y F,YANG L Y. Study on the mechanism of asphaltene coaglulation of crude oil and determination of the precipitation amount[J]. Petroleum Exploration and Development,2000,27(5):109-111.
[10] MEREL P,TABBAL M,CHAKER M,et al. Direct evaluation of the sp³,content in diamond-like-carbon films by XPS[J]. Applied Surface Science,1998,136(1/2):105-110.
[11] TURGEON S,PAYNTER R W. On the determination of carbon sp²/sp³ ratios in polystyrene polyethylene copolymers by photoelectron spectroscopy[J]. Thin Solid Films,2001,394(1/2):43-47.
[12] 许艳艳. 重油中氧含量分析方法及类型氧分布研究[D]. 中国石油大学,2011. Xu Y Y. Oxygen content analysis method and type oxygen distribution in heavy oil research [D]. China Petroleum University,2011.
[13] 范勐,孙学文,许志明,等. 渣油中溶于正庚烷但不溶于正戊烷沥青质性质分析[J].石油化工高等学校学报,2011,24(3):8-12. FAN M,SUN X W,XU Z M,et al. Characterization of residue (C₅—C₇)asphaltene(soluble in n-heptane but insoluble in n-pentane)[J]. Journal of Petrochemical Universities,2011,24(3):8-12.
[14] GARDNER S D,SINGAMSETTY C S K,BOOTH G L,et al. Surface characterization of carbon fibers using angle-resolved XPS and ISS[J]. Carbon,1995,33(5):587-595.
[15] 常海洲,王传格,曾凡桂,等. 不同还原程度煤显微组分组表面结构XPS对比分析[J]. 燃料化学学报,2006,34(4):389-394. CHANG H Z,WANG C G,ZEN F G,et al. XPS comparative analysis of coal macerals with different reducibility[J]. Journal of Fuel Chemistry and Technology,2006,34(4):389-394.
[16] SHINN J H. From coal to single stage and two-stage products:a reactive model of coal structure[J]. Fuel,1984,63(9):1187-1196.
[17] 吴乐乐,邓文安,李传,等.煤焦油重组分沥青质性质分析及对加氢裂化生焦影响的推测[J]. 燃料化学学报,2014,42(8): 938-944. WU L L,DENG W A,LI C,et al. Properties of coal tar heavy fraction and its relevance to coking inhydrocracking[J]. Journal of Fuel Chemistry and Technology,2014,42(8):938-944.
[18] 卢贵武,李英峰,宋辉,等.石油沥青质聚沉的微观机理[J]. 石油勘探与开发,2008,35(1):67-72. LU G W,LI Y F,SONG H,et al. Micromechanism of petroleum asphaltene aggregation[J]. Petroleum Exploration and Development,2008,35(1):67-72.
[19] 张桧然,沈本贤,孙辉,等. 南海原油胶质、沥青质结构表征及原油降黏研究[J]. 石油炼制与化工,2015,46(12):31-40. ZHANG K R,SHEN B X,SUN H,et al. The South China Sea resin and asphaltene structure characterization of crude oil and crude oil drop stick study[J]. Journal of Petroleum Refining and Chemical Industry,2015,46(12):31-40.
[20] HUS S,ALBOUDW A. Asphaltene depostion in flow systerm[D]. Calgary:The University of Calgary,2003.
[21] GAWEL I,BOCIARSKA D,BISKUPSKI P. Effect of asphaltenes on hydroprocessing of heavy oils and residua[J]. Applied Catalysis A General,2005,295(1):89-94.
[22] 刘艳华,车得福,李荫堂,等.X射线光电子能谱确定铜川煤及其焦中氮的形态[J].西安交通大学学报,2001,35(7):661-665. LIU Y H,CHE D F,LI Y T,et al. X-ray photoelectron spectroscopy determination of the forms of nitrogen in Tongchuan coal and its chars[J]. Journal of Xi'an Jiaotong University,2001,35(7):661-665.
[23] 姚明宇,刘艳华,车得福.宜宾煤中氮的形态及其变迁规律研究[J].西安交通大学学报,2003,37(7):759-763. YAO M Y,LIU Y H,CHE D F. Investigation of nitrogen functionality inYibin coal and its char[J]. Journal of Xi'an Jiaotong University,2003,37(7):759-763.
[24] GANZ H,KALKREUTH W. Application of infrared spectroscopy to the classification of kerogentypes and the evaluation of source rock and oil shale potentials[J]. Revista General De Legislación Y Jurisprudencia,2001,151(5): 325-360.
[25] 廖泽文,耿安松.沥青质傅里叶变换红外光谱(FT-IR)分析及其在有机地球化学研究中的应用[J]. 地球化学,2001,30(5):433-438. LIAO Z W,GENG A S. Characterization of FT-IR analysis of asphaltenes and its geochemical implications[J]. Geochimica,2001,30(5):433-438.

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

Composition and structural changes of low temperature coal tar asphaltenes precipitated in different n-alkane solvents

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