抚顺乙烯焦油的精馏分离与气相色谱-质谱联用分析

doi:10.11944/j.issn.1000-0518.2018.06.170169

摘要/Abstract

摘要：

为避免乙烯焦油作为燃料粗放燃烧造成的芳烃资源浪费与环境污染,我们以抚顺乙烯焦油为原料,常压蒸馏切割<280 ℃馏分,然后采用填充柱进行常压精馏,将<280 ℃馏分切割为12个馏分段(40~150 ℃、150~170 ℃、170~180 ℃、180~190 ℃、190~200 ℃、200~210 ℃、210~220 ℃、220~230 ℃、230~240 ℃、240~250 ℃、250~260 ℃和260~280 ℃),以达到对抚顺乙烯焦油的精馏分离。以HP-5MS毛细管填充柱为色谱柱,对得到的12个馏分段进行气相色谱-质谱联用定性、定量分析,为乙烯焦油中芳烃的提取和乙烯焦油深加工利用提供具有指导价值的分析数据。结果显示,抚顺乙烯焦油<280 ℃馏分占焦油总量的52.2%,主要由1~4芳香烃组成。单环、三环和四环芳烃质量分数较少,单环芳烃主要为苯的衍生物,质量分数为5.8%,3环和4环芳烃占2.998%,主要为苊、芴、蒽、菲、芘等。抚顺乙烯焦油中质量分数最多的双环芳烃为萘,其次为β-甲基萘、α-甲基萘和1,4-二氢萘,它们在各馏分段的最高分布分别为41.152%、16.729%、12.089%和9.046%。由此乙烯焦油可作为提取高附加值芳环类精细化工产品的良好原料。

关键词: 乙烯焦油, 常压精馏, 气相色谱-质谱联用, 芳烃

Abstract:

In order to avoid the aromatics waste and environmental pollution caused by ethylene bottom oil as a crude fuel for combustion, Fushun ethylene bottom oil was subjected to atmospheric distillation to obtain a fraction below 280 ℃. To achieve separation of ethylene bottom oil, the fraction below 280 ℃ was cut into 12 fractions(40~150 ℃, 150~170 ℃, 170~180 ℃, 180~190 ℃. 190~200 ℃, 200~210 ℃. 210~220 ℃, 220~230 ℃, 230~240 ℃, 240~250 ℃, 250~260 ℃. 260~280 ℃) by atmospheric distillation unit equipped with packed columns. The obtained 12 fractions were analyzed qualitatively and quantitatively by gas chromatography/mass spectrometry with an HP-5MS capillary column as the stationary phase. We hope it could provide valuable analytical data for the extraction of aromatic hydrocarbons, and the deep processing and utilization of ethylene bottom oil. The results indicate that the distillate below 280 ℃account for 52.2% of the total amount of ethylene bottom oil in Fushun, and mainly contained aromatic hydrocarbons with 1 to 4 rings. The mass fraction of monocyclic, tricyclic and tetracyclic aromatic hydrocarbons is small. The monocyclic aromatic hydrocarbons are mainly derivatives of benzene and indene that account for 5.8% and 6.172% of ethylene bottom oil in Fushun, respectively. The tricyclic and tetracyclic aromatic hydrocarbons account for 2.998% and mainly are acenaphthene, fluorene, anthracene, phenanthrene, pyrene and so on. The most abundant bicyclic aromatic hydrocarbons in Fushun ethylene bottom oil are naphthalene, followed by β-methylnaphthalene, α-methylnaphthalene and 1,4-dihydronaphthalene with mass fraction of 41.152%, 16.729%, 12.089% and 9.046%, respectively. This research shows that ethylene bottom oil in Fushun can be used as good feedstock for extracting high value-added aromatic fine chemicals.

Key words: ethylene bottom oil, atmospheric distillation, gas chromatography/mass spectrometry, aromatic hydrocarbons

代晓玉,乔海燕,韩冬云,曹祖宾,张幸珂. 抚顺乙烯焦油的精馏分离与气相色谱-质谱联用分析[J]. 应用化学, 2018, 35(6): 714-721.

DAI Xiaoyu,QIAO Haiyan,HAN Dongyun,CAO Zubin,ZHANG Xingke. Distillation Separation and Gas Chromatography/Mass Spectrometry Analysis of Fushun Ethylene Bottom Oil[J]. Chinese Journal of Applied Chemistry, 2018, 35(6): 714-721.

参考文献

[1]	WANG Songhan.Ethylene Process and Technology(the Best)[M]. Beijing:China Petrochemical Press,2012:15-25(in Chinese). 王松汉. 乙烯工艺与技术(精华本)[M]. 北京:中国石化出版社, 2012: 15-25.
[2]	GE Chuanzhang,LONG Donghui,QIAO Wenming,et al. Structure Analysis and Pyrolysis Behavior of Ethylene Residue[J]. J Pet Sci(Pet Process),2014,30(6):1052-1058(in Chinese). 葛传长,龙东辉,乔文明,等. 乙烯渣油结构解析及其热解行为[J]. 石油学报(石油加工),2014,30(6):1052-1058.
[3]	Wu M B,Shi Y Y,Li S B,et al. Synthesis and Characterization of Condensed Poly-Nuclear Aromatic Resin Using Heavy Distillate from Ethylene Tar[J]. New Carbon Mater,2013,55(6):377-377.
[4]	Kan T,Wang H,Li C,et al. Liquid Fuels From Ethylene Tar by Two-stage Catalytic Hydroprocessing[J]. Energy Sources(Part A Recovery Util Environ Eff),2015,37(21):2317-2322.
[5]	YANG Jinghua,CAO Zubin,ZHUANG Dan.Aromatic Solvent Naphtha Produced By-Product C9 Factions[J]. Chem Ind Eng Prog,2007,26(9):1323-1327(in Chinese). 杨靖华,曹祖宾,庄丹. C9馏分制备芳烃溶剂油[J]. 化工进展,2007,26(9):1323-1327.
[6]	Wu M,Shi Y,Li S,et al. Synthesis and Characterization of Condensed Polynuclear Aromatic Resin Derived from Ethylene Tar[J]. China Pet Process Petrochem Technol,2012,14(4):42-47.
[7]	YANG Zhiwu.Preparation and Study of Pitch-Based General Purpose Carbon Fibers from Ethylene Tar[D]. Tianjin:Tianjin University,2012(in Chinese). 杨志武. 乙烯焦油沥青基通用级炭纤维的制备及研究[D]. 天津:天津大学,2012.
[8]	Andreikov E I,Amosova I S,Dikovinkina Y A,et al. Pyrolysis of Polystyrene in Coal Tar and Ethylene Tar Pitches[J]. Russ J Appl Chem,2012,85(1):89-97.
[9]	Cheng X,Zha Q,Zhong J,et al. Needle Coke Formation Derived from Co-Carbonization of Ethylene Tar Pitch and Polystyrene[J]. Fuel,2009,88(11):2188-2192.
[10]	Yang J,Nakabayashi K,Jin M,et al. Preparation of Isotropic Pitch-based Carbon Fiber Using Hyper Coal Through Co-carbonation with Ethylene Bottom Oil[J]. J Ind Eng Chem,2016,34:34397-34404.
[11]	Yang J,Nakabayashi K,Jin M,et al. Preparation of Isotropic Spinnable Pitch and Carbon Fiber by the Bromination-Dehydrobromination of Biotar and Ethylene Bottom Oil Mixture[J]. J Mater Sci,2017,52(2):1165-1171.
[12]	Han D Y,Cao Z B,Li Y F.Investigation of Naphthalene Extraction from Ethylene Tar[J]. Energy Sources(Part A Recovery Util Environ Eff),2014,36(9):993-998.
[13]	LI Yanfang,CAO Zubin,LI Dandong,et al. Isolation of β-Methylnaphthalene from Ethylene Tar Through Extraction-Rectification[J]. Chem Ind Eng Prog,2010,29(11),2049-2052(in Chinese). 李艳芳,曹祖宾,李丹东,等. 萃取-精馏法从乙烯焦油中提取β-甲基萘[J]. 化工进展,2010,29(11):2049-2052.
[14]	ZHANG Zeng,KAN Yiqun,LIU Feng,et al. Extraction of Naphthalene. Extraction of Naphthalene, 1-Methylnaphthalene and 2-Methylnaphyhalene from Ethylene Tar:CN,102134500.B[P],2013-05-15(in Chinese). 张曾,阚一群,刘峰,等. 从乙烯焦油中提取萘,1-甲基萘和2-甲基萘的方法:中国,102134500 B[P].2013-05-15.
[15]	YANG Dongping. Ethylene Tar Integrated Processing Technology: CN,1970688.B[P],2010-05-12(in Chinese). 杨东平. 乙烯焦油综合加工工艺:中国,1970688B[P],2010-05-12
[16]	Islas C A,Suelves I,Carter J F,et al. Pyrolysis-Gas Chromatography/Mass Spectrometry of Fractions Separated from a Low-Temperature Coal Tar:An Attempt to Develop a General Method for Characterising Structures and Compositions of Heavy Hydrocarbon Liquids[J]. Rapid Commun Mass Spectrom,2002,16(8):774-784.
[17]	Morgan T J,George A,Áliarez P,et al. Characterization of Molecular Mass Ranges of Two Coal Tar Distillate Fractions(Creosote and Anthracene Oils) and Aromatic Standards by LD-MS, GC-MS, Probe-MS and Size-Exclusion Chromatography[J]. Energy Fuels,2008,22(5):3275-3292.