煤焦油重组分甲苯不溶物结构组成及对悬浮床加氢裂化生焦的影响

吴乐乐; 李金璐; 邓文安; 张英红; 李传

煤焦油重组分甲苯不溶物结构组成及对悬浮床加氢裂化生焦的影响

1.
中国石油大学(华东)重质油国家重点实验室, 山东青岛 266580;
2.
中海油能源发展股份有限公司安全环保分公司, 天津 300456

基金项目: 国家重点基础研究发展规划(973计划,2012CB214901,2014CB238905);国家自然科学基金(41172146/D0208);中央高校基本科研业务费专项资金(14CX05032A)。

详细信息

通讯作者:
邓文安,博士,教授,E-mail:dengwenan@upc.edu.cn。

中图分类号: TQ524;TE662
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出版历程
- 收稿日期: 2015-01-15
- 修回日期: 2015-03-05
- 刊出日期: 2015-08-30

Structure of toluene insoluble coal tar heavy fraction and its relevance to the coking behavior in slurry-bed hydrocracking

1.
State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Huadong), Qingdao 266580, China;
2.
CNOOC Ener Tech-Safety & Environmental Protection Co., Tianjin 300456, China

摘要

摘要: 以煤焦油常压渣油(CTAR)为原料在3000mL环流反应器悬浮床加氢装置上进行了中试实验,并分别从CTAR和加氢产物中提取了甲苯不溶物(TI)及焦炭,通过元素分析、SEM、XRD、FT-IR、XPS等手段对TI及焦炭进行对比分析,明确了TI的结构组成并将其与加氢裂化生焦情况进行了关联。结果表明,CTAR悬浮床加氢工艺具有轻油收率高、生焦总量小、没有壁相焦的特点。TI由煤焦油生产过程中带入的碳质、矿物质颗粒及稠环芳烃有机物构成,O是其中含量最高的杂原子,Ca、Si、Al、Na来源于煤焦油中矿物质,C和O主要存在于C-C、C-H、C-O-C、C-OH结构中,N主要以吡咯和胺的形式存在,S主要以脂肪类S存在。TI具有明显的片层堆积结构,在作用力下容易破碎为具有较大比表面积及吸附能力的微米级微晶及碳质颗粒,和硫化后的催化剂颗粒一起为加氢反应提供载焦中心,优先吸附大分子自由基从而明显减少壁相焦的生成。
- 煤焦油重组分 /
- 悬浮床加氢 /
- 甲苯不溶物 /
- 生焦
Abstract: The hydrogenation of coal tar atmospheric residue (CTAR) was conducted in a slurry-bed hydrocracking pilot plant with a 3000mL loop reactor; the toluene insoluble (TI) fraction and coke were separated from CTAR and hydrogenation product, respectively. The properties of TI and coke were analyzed by means of element analysis, SEM, XRD, FT-IR and XPS; the relevance of TI structure to the coking behavior in the hydrogenation process was then investigated. The results show that the slurry-bed hydrocracking of CTAR has the features of high light oil yield, little coke, and almost no coke on the reactor surface. TI consists of carbonaceous, mineral particles and polycyclic aromatic hydrocarbons originated from the coal tar production process. O is the dominant heteroatom, whereas Ca, Si, Al, and Na are derived from minerals in CTAR. Furthermore, C and O are mainly present as C-C, C-H, C-O-C and C-OH, whereas N-containing groups appear as pyrrole and amine and S is mainly in the form of aliphatic sulfur. Obviously, TI has a layered stack structure, which can be easily broken to smaller carbonaceous and mineral particles (several microns) with larger specific surface area and adsorption capacity. These particles, together with the sulfurized catalyst, act as the coke centers, which are effective to adsorb macromolecular radicals and then reduce the opportunity of coking on the reactor surface.
- coal tar heavy fraction /
- slurry-bed hydrocracking /
- toluene insoluble /
- coking

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参考文献(29)

李彻, 张传名, 周月桂. 220t/h燃油锅炉改烧煤焦油的试验研究[J]. 发电设备, 2007, 21(3): 177-180. (LI Che, ZHANG Chuan-ming, ZHOU Yue-gui. Trial-changing a 220 t/h oil fired boiler to firing coal tar[J]. Power Gener Assem, 2007, 21(3): 177-180.)

GU Z L, CHANG N, HOU X P, WANG J P, LIU Z K. Experimental study on the coal tar hydrocracking process in supercritical solvents[J]. Fuel, 2012, 91(1): 33-39.

KAN T, WANG H Y, HE H X, LI C S, ZHANG S J. Experimental study on two-stage catalytic hydroprocessingof middle-temperature coal tar to clean liquid fuels[J]. Fuel, 2011, 90(11): 3404-3409.

LI D, LI Z, LI H W, LIU Q C, FENG Z L, FAN Z. Hydrotreating of low temperature coal tar to produce clean liquid fuels[J]. J Anal Appl Pyrolysis, 2013, 100: 245-252.

李冬, 李稳宏, 高新, 杨小彦, 滕家辉, 崔楼伟, 赵鹏. 中低温煤焦油加氢改质工艺研究[J]. 煤炭转化. 2009, 32(4): 81-83. (LI Dong, LI Wen-hong, GAO Xin, YANG Xiao-yan, TENG Jia-hui, CUI Lou-wei, ZHAO Peng. Hydro-upgrading process of medium/low temperature coal tar[J]. Coal Convers, 2009, 32(4): 81-83.)

YEN T F, WU W H, CHILINGAR G V. A study of the structure of petroleum asphaltenes and related substances by proton nuclear magnetic resonance[J]. Energy Sources, 1984, 7(3): 275-304.

李传, 邓文安, 李向伟, 沐宝泉, 李庶峰, 文萍, 付明朗. 重油加氢催化剂用于中低温煤焦油加氢改质的中试研究[J]. 炼油技术与工程, 2011, 41(9): 32-35. (LI Chuan, DENG Wen-an, LI Xiang-wei, MU Bao-quan, LI Shu-feng, WEN Ping, FU Ming-lang. Pilot test of middle/low temperature coal tar oil hydrogenation upgrading using heavy oil fixed-bed hydrotreatingcatalysts[J]. Pet Refin Eng, 2011, 41(9): 32-35.)

尚猛, 李传, 邓文安, 田广华, 阙国和. 渣油悬浮床加氢裂化油溶性催化剂的性能[J]. 石油学报 (石油加工), 2011, 27(3): 362-365. (SHANG Meng, LI Chuan, DENG Wen-an, TIAN Guang-hua, QUE Guo-he. Behaviour of oil soluble catalyst for the residue slurry-bed hydrocracking[J]. Acta Petrol Sin, 2011, 27(3): 362-365.)

尚猛. 油溶性催化剂和助剂在渣油悬浮床加氢裂化中的研究. 青岛: 中国石油大学(华东), 2010. (SHANG Meng. Study on oil-soluble catalysts and accessory ingredients in the residue slurry-bed hydrocracking. Qingdao: China University of Petroleum, 2010.)

邓文安, 田广华, 张数义, 罗辉, 阙国和. 复配助剂对渣油悬浮床加氢裂化反应的抑焦作用[J]. 石油学报 (石油加工), 2009, 25(6): 831-835. (DENG Wen-an, TIAN Guang-hua, ZHANG Shu-yi, LUO Hui, QUE Guo-he. The effect of compound adjuvant on coke formation in residue slurry-bed hydrocracking[J]. Acta Petrol Sin, 2009, 25(6): 831-835.)

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 Peng. Study on slurry-bed hydrocracking reactions of high temperature coal tar[J]. Clean Coal Technol, 2011, 17(3): 61-63.)

吴乐乐, 邓文安, 李传, 张英红, 王晓杰. 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): 938-942. (WU Le-le, DENG Wen-an, LI Chuan, ZHANG Ying-hong, WANG Xiao-jie. Properties analysis of coal tar heavy fraction asphaltene and relevance evaluation with coking in hydrocracking[J]. J Fuel Chem Technol, 2014, 42(8): 938-942.)

李冬, 刘鑫, 孙智慧, 李稳宏, 马伟. 煤焦油中甲苯不溶物的性质和组成分析[J]. 石油学报 (石油加工), 2014, 30(1): 76-79. (LI Dong, LIU Xin, SUN Zhi-hui, LI Wen-hong, MA Wei. Property and composition analysis of toluene insoluble materials in coal tar[J]. Acta Petrol Sin, 2014, 30(1): 76-79.)

许志明, 王宗贤, KOTL YAR L S, CHUNG K H. 油砂沥青改质产品中甲苯不溶物的表征[J]. 石油学报 (石油加工), 2004, 11(1): 69-73. (XU Zhi-ming, WANG Zong-xian, KOTL YAR L S, CHUNG K H. Characterization of toluene insoluble materials in various oil sand bitumen derived streams[J]. Acta Petrol Sin, 2004, 11(1): 67-73.)

舒歌平. 煤炭液化技术[M]. 北京: 煤炭工业出版社, 2003. (SHU Ge-ping. The coal liquefaction technology[M]. Beijing: Coal Industry Press, 2003.)

DERBYSHIRE F. Catalysis in coal liquefaction: Status and directions for research[J]. Prep Div Fuel Chem ACS, 1988, 33(1): 188-197.

王刚, 高金森, 徐春明, 冯钰. 催化裂化过程中热裂化反应与二次反应的研究[J]. 燃料化学学报, 2005, 33(4): 440-443. (WANG Gang, GAO Jin-sen, XU Chun-ming, FENG Yu. Studies on the thermal cracking and secondary reactions in FCC process[J]. J Fuel Chem Technol, 2005, 33(4): 440-443.)

王继乾. 添加物对渣油热反应生焦的影响及作用机理研究. 青岛: 中国石油大学(华东), 2006. (WANG Ji-qian. Effect of additives on coke formation and its mechanism during residue thermal reaction. Qingdao: China University of Petroleum, 2006.)

李庶峰, 王继乾, 沐宝泉, 阙国和. 渣油加氢裂化反应中碳黑作载焦剂的研究[J]. 石油炼制与化工, 2005, 36(5): 4-7. (LI Shu-feng, WANG Ji-qian, MU Bao-quan, QUE Guo-he. Effect of carbon black a coke trap in residue hydrocracking reaction[J]. Petrol Process Petrochem, 2005, 36(5): 4-7.)

丰芸, 李寒旭, 丁立明. 利用XRD分析高温下淮南煤灰矿物质变化[J]. 安徽建筑工业大学学报, 2008, 16(5): 53-57. (FENG Yun, LI Han-xu, DING Li-ming. Study of Huainan coal ash mineral variation under high temperature with XRD[J]. J Anhui Univ Archit Ind, 2008, 16(5): 53-57.)

胡定强, 王兆辉, 田永胜. 大型焦炉煤油QI含量偏的原因分析[J]. 煤炭转化, 2011, 34(3): 57-60. (HU Ding-qiang, WANG Zhao-hui, TIAN Yong-sheng. Analytical study on over-high QI in coal tar from a large coke oven[J]. Coal Convers, 2011, 34(3): 57-60.)

刘瑞国, 徐斌, 薛改凤. 原生QI结构和性质的研究[J]. 炭素技术, 1997, 16(5): 22-25. (LIU Rui-guo, XU Bin, XUE Cai-feng. Study on the structure and the property of primary QI[J]. Carbon Technol, 1997, 16(5): 22-25.)

任绍梅, 熊杰明. 煤沥青中原生QI性质分析[J]. 炭索技术, 2008, 27(1): 13-15. (REN Shao-mei, XIONG Jie-ming. The analysis of primary QI in coal tar[J]. Carbon Technol, 2008, 27(1): 13-15.)

WANG S Q, TANG Y G, SCHOBERT H H, GUO YN, SU Y F. FT-IR and ¹³C-NMR Investigation of coal component of late Permian coals from china[J]. Energy Sources, 2011, 25(12): 5672-5677.

梁虎珍, 王传格, 曾凡桂, 李美芬, 相建华. 应用红外光谱研究脱灰对伊敏褐煤结构的影响[J]. 燃料化学学报, 2014, 42(2): 129-132. (LIANG Hu-zhen, WANG Chuan-ge, ZENG Fan-gui, LI Mei-fen, XIANG Jian-hua. Effect of demineralization on lignite structure from Yinmin coalfield by FT-IR investigation[J]. J Fuel Chem Technol, 2014, 42(2): 129-132.)

徐晓, 吴奇虎. 煤利用化学[M]. 北京: 化学工业出版社, 1991: 203-209. (XU Xiao, WU Qi-hu. Chemistry of coal utilization[M]. Beijing: Chemical Industry Press, 1991: 203-209.)

徐秀峰, 张蓬洲. 用 XPS表征氧、氮、硫元素的存在形态[J]. 煤炭转化, 1996, 19(1): 72-77. (XU Xiu-feng, ZHANG Peng-zhou. The XPS study of forms of oxygen, nitrogen and sulphur elements in gas coal[J]. Coal Convers, 1996, 19(1): 72-77.)

朱宏斌, 倪燕慧, 唐黎华, 郑志胜, 朱子彬. 烟煤快速加氢热解的研究Ⅵ煤和半焦中氮化学形态剖析[J]. 燃料化学学报, 2001, 29(2): 124-128. (ZHU Hong-bin, NI Yan-hui, TANG Li-hua, ZHENG Zhi-sheng, ZHU Zi-bin. Research of coal flash hydropyrolysis Ⅵ Chemical type analysis of nitrogen in coal and semi-coke[J]. J Fuel Chem Technol, 2001, 29(2): 124-128.)

SISKIN M, KELEMEN S R, EPPIG C P. Asphaltene molecular structure and chemical influences on the morphology of coke produced in delayed coking[J]. Energy Fuels, 2006, 20(3): 1227-1234.

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