A study on upgrading light coal tar to aerospace fuel
-
摘要: 本研究以煤炭科学技术研究院有限公司提供的轻质煤焦油为原料,开展了提质改性制备航空航天燃料的工艺研究。针对煤焦油原料的特点,设计了一次脱硫-馏分切割-二次脱硫-加氢饱和的工艺路线。使用实验室自制的NiMoW/Al2O3加氢脱硫催化剂和Pd/Al2O3加氢饱和催化剂,通过系统实验获得了最佳工艺操作条件,其中,加氢脱硫的最佳工艺条件为 300 ℃、5 MPa;加氢饱和的最佳工艺条件为 240 ℃、5 MPa。经处理,油品的硫含量由323 mg/kg下降至8.5 mg/kg。原料中的苯、萘等芳烃化合物经处理转化为环烷烃。最终产物油中主要组成为环烷烃与链烷烃,含量分别为58.38%与29.65%。所制备的产品油具有高热值、低硫含量和低不饱和烃的特点,具有作为航空航天燃料应用的潜力。Abstract: In this paper, light coal tar derived from China Coal Research Institute was used as raw material to conduct a research on developing a chemical process to produce aerospace fuel. In view of the characteristics of the coal tar, a route comprising of primary desulfurization- fraction cutting- secondary desulfurization- hydrogenation saturation was designed. The optimal pressure and temperature were determined to be 5 MPa and 300 °C for hydrodesulfurization on NiMoW/Al2O3, and 5 MPa and 240 °C for hydrogenation saturation on Pd/Al2O3. After treatment, the sulfur content decreased from 323 to 8.5 mg/kg. The benzenes, naphthalenes and other aromatic compounds in the raw oil were converted into cycloalkanes. The main components of the final product were cycloalkanes and chain alkanes, and the contents were 58.38% and 29.65% respectively. The final product exhibited high heating value, low sulfur content and low unsaturated aromatic hydrocarbons, which possessed great potential to be used in aerospace fuels.
-
Key words:
- coal tar /
- hydrodesulfurization /
- hydrogenation saturation /
- aerospace fuel
-
表 1 原料油的性质
Table 1 Properties of the raw oil
Density
(15 ℃)/
(g·cm−3)Density
(20 ℃)/
(g·cm−3)Viscosity
(25 ℃)/
(m2·s−1)Heat of
combustion
/(MJ·kg−1)0.8857 0.8820 4.35 42.68 表 2 原料油的馏分沸程分析
Table 2 Distillation analysis of the raw oil
IBP Temperature/℃ FBP 10% 20% 30% 40% 50% 60% 70% 80% 90% 70 96 137 180 215 245 273 291 307 315 327 表 3 原料油的元素分析
Table 3 Elements of the raw oil
w/% C H O N S 85.72 12.30 1.77 0.13 0.0323 表 4 原料油的成分组成
Table 4 Composition of raw oil
Items Content w/% Chain alkanes 24.47 Chain olefins 5.44 Cycloalkanes (total: 12.44) monocyclic alkanes 8.15 bicyclic alkanes 3.82 polycyclic alkanes 0.47 Aromatic hydrocarbons (total: 52.12) benzenes 6.72 indenes 2.23 naphthalenes 14.19 biphenyls 5.35 polycyclic aromatic hydrocarbons 23.62 Oxygen-containing compounds 4.69 Nitrogen-containing compounds 0.84 Total 100.00 表 5 馏分切割后油品成分组成
Table 5 Composition of product oil after fraction cutting
Items Content w/% Chain alkanes 17.85 Chain olefin 6.58 Cycloalkanes (total: 16.78) monocyclic alkanes 6.31 bicyclic alkanes 9.68 polycyclic alkanes 0.79 Aromatic hydrocarbons (total: 45.22) benzenes 10.93 indenes 5.41 naphthalenes 22.93 biphenyls 1.48 polycyclic aromatic hydrocarbons 4.47 Oxygen-containing compounds 10.18 Nitrogen-containing compounds 3.39 Total 100.00 表 6 二次脱硫后油品成分组成
Table 6 Composition of product oil after secondary HDS
Items Content w/% Chain alkanes 17.94 Chain olefin 7.52 Cycloalkanes (total: 26.06) monocyclic alkanes 10.03 bicyclic alkanes 14.55 polycyclic alkanes 1.48 Aromatic hydrocarbons (total: 41.42) benzenes 9.62 indenes 5.10 naphthalenes 20.19 biphenyls 1.75 polycyclic aromatic hydrocarbons 4.76 Oxygen-containing compounds 5.72 Nitrogen-containing compounds 1.34 Total 100.00 表 7 加氢饱和后油品成分组成
Table 7 Composition of product oil after hydrogenation saturation
Items Content w/% Chain alkanes 29.65 Cycloalkanes (total: 58.38) monocyclic alkanes 22.22 bicyclic alkanes 28.76 polycyclic alkanes 7.40 Aromatic hydrocarbons (total: 9.35) benzenes 2.23 indenes 1.13 naphthalenes 3.73 biphenyls 0.25 polycyclic aromatic hydrocarbons 2.02 Oxygen-containing compounds 2.17 Nitrogen-containing compounds 0.45 Total 100.00 表 8 加氢饱和产品油馏分烃类组成
Table 8 The composition of product oil after hydrogenation saturation
Fraction hydrocarbon composition Content w/% Chain alkanes 28.7 Monocyclic alkanes 31.2 Bicyclic alkanes 30.4 Tricyclic alkanes 5.9 Total cycloalkanes 67.5 Total saturated hydrocarbons 96.2 Alkylbenzene 3.8 Indan or tetrahydroindene 0 Indenes 0 Total monocyclic aromatics 3.8 Naphthalene 0 Naphthalenes 0 Acenaphthene 0 Acenaphthylenes 0 Total bicyclic aromatic hydrocarbons 0 Tricyclic aromatic hydrocarbons 0 Total aromatics 3.8 Colloid 0 Total 100.0 表 9 产品油性质测试
Table 9 Properties of product oil
Items Product JP-900 Density/(g·cm−3) 0.8187 0.87 Heat of combustion/(MJ·kg−1) 46.397 42.8 Aromatic content 3.8 w% 1.9 v% Sulfur content/% 0.00085 0 Flash point/℃ 41 61 -
[1] 蒋丽华. 航煤加氢精制技术研究进展[J]. 广东化工,2020,47(8):94−95. doi: 10.3969/j.issn.1007-1865.2020.08.042JIANG Li-hua. The research process in the hydrofining technology of jet fuel[J]. Guangdong Chem Ind,2020,47(8):94−95. doi: 10.3969/j.issn.1007-1865.2020.08.042 [2] 任帅, 杨军, 郭生飞, 康强强, 王树宽. 煤焦油加氢制轻质油品技术进展[J]. 广州化工,2020,48(14):22−24. doi: 10.3969/j.issn.1001-9677.2020.14.009REN Shuai, YANG Jun, GUO Sheng-fei, KANG Qiang-qiang, WANG Shu-kuan. Technical progress of coal tar hydrogenation to light oil products[J]. Guangzhou Chem Ind,2020,48(14):22−24. doi: 10.3969/j.issn.1001-9677.2020.14.009 [3] 沈东, 姚峻峰, 鲁晓峰, 康红艳, 穆秋艳, 候戌琪. 中低温煤焦油加氢技术进展及应用分析[J]. 煤化工,2020,48(2):48−52. doi: 10.3969/j.issn.1005-9598.2020.02.014SHEN Dong, YAO Jun-feng, LU Xiao-feng, KANG Hong-yan, MU Qiu-yan, HOU Xu-qi. Progress and application analysis for hydrogenation technology of low and medium-temperature coal tar[J]. Coal Chem Ind,2020,48(2):48−52. doi: 10.3969/j.issn.1005-9598.2020.02.014 [4] 永成. 煤焦油加氢制燃料油品[J]. 化工管理,2019,(29):194−195. doi: 10.3969/j.issn.1008-4800.2019.29.132YONG Cheng. Hydrogenation of coal tar to produce fuel[J]. Chem Ent Manage,2019,(29):194−195. doi: 10.3969/j.issn.1008-4800.2019.29.132 [5] 周秋成, 席引尚, 马宝岐. 我国煤焦油加氢产业发展现状与展望[J]. 煤化工,2020,48(3):3−8+49. doi: 10.3969/j.issn.1005-9598.2020.03.002ZHOU Qiu-cheng, XI Yin-shang, MA Bao-qi. Development situation and trend of coal tar hydrogenation industry in China[J]. Coal Chem Ind,2020,48(3):3−8+49. doi: 10.3969/j.issn.1005-9598.2020.03.002 [6] 张金峰, 沈寒晰, 吴素芳, 刘彦婷, 郑阿龙. 煤焦油深加工现状和发展方向[J]. 煤化工,2020,48(4):76−81. doi: 10.3969/j.issn.1005-9598.2020.04.019ZHANG Jin-feng, SHEN Han-xi, WU Su-fang, LIU Yan-ting, ZHENG A-long. Present situation and development direction of coal tar deep processing[J]. Coal Chem Ind,2020,48(4):76−81. doi: 10.3969/j.issn.1005-9598.2020.04.019 [7] 杨敬伟. 煤焦油加氢工艺反应性的研究[J]. 化工管理,2020,(23):122−123. doi: 10.3969/j.issn.1008-4800.2020.23.059YANG Jing-wei. Study on the reactivity of coal tar hydrogenation process[J]. Chem Ent Manage,2020,(23):122−123. doi: 10.3969/j.issn.1008-4800.2020.23.059 [8] 冯雷庆. 延迟焦化工艺在煤焦油加工中的应用[J]. 化工设计通讯,2018,44(8):6. doi: 10.3969/j.issn.1003-6490.2018.08.006FENG Lei-qing. Application of delayed coking process in coal tar processing[J]. Chem Eng Des Commun,2018,44(8):6. doi: 10.3969/j.issn.1003-6490.2018.08.006 [9] 孟宇, 朱仕元, 高平强. 低温煤焦油的综合利用[J]. 价值工程,2019,38(32):265−266.MENG Yu, ZHU Shi-yuan, GAO Ping-qiang. Comprehensive utilization of low temperature coal tar[J]. Value Eng,2019,38(32):265−266. [10] 王凤武. 煤焦油洗油组分提取及其在精细化工中的应用[J]. 煤化工,2004,(2):26−28. doi: 10.3969/j.issn.1005-9598.2004.02.007WANG Feng-wu. Extraction of washing oil distillate from tar and its application in fine chemical industry[J]. Coal Chem Ind,2004,(2):26−28. doi: 10.3969/j.issn.1005-9598.2004.02.007 [11] 闫厚春, 范雯阳, 崔鹏, 廖朝辉, 王理想, 李青松. 中低温煤焦油的加工利用现状[J]. 应用化工,2019,48(8):1904−1907. doi: 10.3969/j.issn.1671-3206.2019.08.032YAN Hou-chun, FAN Wen-yang, CUI Peng, LIAO Zhao-hui, WANG Li-xiang, LI Qing-song. Current status of processing and utilization of medium and low temperature coal tar[J]. Appl Chem Ind,2019,48(8):1904−1907. doi: 10.3969/j.issn.1671-3206.2019.08.032 [12] 张汉东. 煤焦油产品在精细化工中的应用[J]. 精细化工,1987,(1):55−58.ZHANG Han-dong. Application of coal tar products in fine chemical industry[J]. Fine Chem,1987,(1):55−58. [13] 屠约峰. 煤焦油加氢利用工艺和催化剂研究进展[J]. 石油化工应用,2018,37(3):6−10. doi: 10.3969/j.issn.1673-5285.2018.03.002TU Yue-feng. Research progress of technology and catalyst for hydrogenation of coal tar[J]. Petrochem Ind Appl,2018,37(3):6−10. doi: 10.3969/j.issn.1673-5285.2018.03.002 [14] 崔文岗, 李冬, 樊安, 潘柳依, 牛梦龙, 李稳宏. 低温煤焦油加氢制备清洁燃料油品中试试验研究[J]. 化工进展,2018,37(6):2192−2202.CUI Wen-gang, LI Dong, FAN An, PAN Liu-yi, NIU Meng-long, LI Wen-hong. Pilot-scale study of upgrading a low temperature coal tar distillate for the production of clean fuels[J]. Chem Ind Eng Prog,2018,37(6):2192−2202. [15] 何剑洪, 张毅. 煤焦油加氢工艺技术[J]. 辽宁化工,2019,48(4):377−379. doi: 10.3969/j.issn.1004-0935.2019.04.028HE Jian-hong, ZHANG Yi. Discussion on the hydrogenation technology of coal tar[J]. Liaoning Chem Ind,2019,48(4):377−379. doi: 10.3969/j.issn.1004-0935.2019.04.028 [16] 何彦兵, 甘伊楠. 中低温煤焦油加氢技术研究[J]. 化工管理,2017,(16):87. doi: 10.3969/j.issn.1008-4800.2017.16.059HE Yan-bing, GAN Yi-nan. Research on hydrogenation technology of medium and low temperature coal tar[J]. Chem Ent Manage.,2017,(16):87. doi: 10.3969/j.issn.1008-4800.2017.16.059 [17] 韩伟, 杜宗罡, 杨军, 冯弦, 吴华, 范晓勇, 李冬. 中低温煤焦油制备火箭煤油研究[J]. 工业催化,2019,27(6):67−71. doi: 10.3969/j.issn.1008-1143.2019.06.011HAN Wei, DU Zong-gang, YANG Jun, FENG Xian, WU Hua, FAN Xiao-yong, LI Dong. Study on preparation of rocket kerosene from mid-low-temperature coal tar[J]. Ind Catal,2019,27(6):67−71. doi: 10.3969/j.issn.1008-1143.2019.06.011 [18] ROAN M A, BOEHMAN A L. The effect of fuel composition and dissolved oxygen on deposit formation from potential JP-900 basestocks[J]. Energ Fuel,2004,18(3):835−843. doi: 10.1021/ef034050b [19] BALSTER L M, CORPORAN E, DEWITT M J, EDWARDS J T, ERVIN J S, GRAHAM J L, LEE S Y, PAL S, PHELPS D K, RUDNICK L R, SANTORO R J, SCHOBERT, H H, SHAFER L M, STRIEBICH R C, WEST Z J, WILSON G R, WOODWARD R, ZABARNICK S. Development of an advanced, thermally stable, coal-based jet fuel[J]. Fuel Process Technol,2008,89(4):364−378. doi: 10.1016/j.fuproc.2007.11.018 [20] GANG Y, ZHANG X, LEI X, GUO H Y, LI W H, LI D. Hydroprocessing of low-temperature coal tar to produce jet fuel[J]. RSC Adv,2018,8(42):23663−23670. doi: 10.1039/C8RA04531C