图 1
抚顺乙烯裂解工艺流程图
Figure 1.
Schematic for Fushun ethylene cracking process
引用本文:
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.
doi:
10.11944/j.issn.1000-0518.2018.06.170169
Citation: 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. doi: 10.11944/j.issn.1000-0518.2018.06.170169
Citation: 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. doi: 10.11944/j.issn.1000-0518.2018.06.170169
抚顺乙烯焦油的精馏分离与气相色谱-质谱联用分析
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。
English
Distillation Separation and Gas Chromatography/Mass Spectrometry Analysis of Fushun Ethylene Bottom Oil
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.
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乙烯是合成纤维、橡胶、塑料、乙醇等的基本化工原料，乙烯产量是衡量一个国家石油化工发展水平的重要标志之一。乙烯焦油是乙烯裂解原料在蒸汽裂解过程中原料及产品高温缩合的产物，裂解原料不同，乙烯焦油的产率也不同，一般产率为乙烯质量分数的10%~15%。随着石油储量减少，乙烯原料的重质化，其收率还会增加。我国人口众多，对资源的需求量大，因而乙烯产能巨大，乙烯主要通过煤制烯烃和油制烯烃两种途径获得。截至2016年底我国乙烯总产能达到2310.5万吨/年，其中油制乙烯产能占72.8%，其副产品乙烯焦油产量保守估计为230~350万吨/年，对于副产物如此大量乙烯焦油如何利用是石化行业面临的一个难题。在我国乙烯的裂解原料[2]主要为石脑油(初馏点~200 ℃的常压原油馏分)[1]。石脑油在高温下(600~800 ℃)发生C—H键与C—C键的断裂，生成乙烯和丙烯的同时烯烃之间也可发生聚合，环化生成芳香烃。因此，乙烯焦油主要成分是单环、多环芳烃、重芳烃馏分油，是富含芳烃的宝贵资源。芳烃是合成树脂、纤维、塑料、医药、染料、洗涤剂、炸药等的重要化工原料和中间体，2016年我国混合芳烃进口量约1099万吨，平均价格在500美元/吨以上。而当今在我国，大部分的乙烯焦油被当作燃料直接粗放燃烧掉，由于乙烯焦油反应活性大[2]，其含稠环芳烃在燃烧过程中易结焦生炭，使得乙烯焦油热稳定性差，同时乙烯焦油C/H比高，作为燃料利用既污染环境又造成芳烃资源浪费严重。
近年来，乙烯焦油的研究已有大量报道。如利用乙烯焦油合成石油树脂[3]，制取轻质液态燃料油燃料和芳烃溶剂油[4-6]，制备出中间相沥青与针状焦[7-11]。通过萃取，精馏以及加氢精制的方法从乙烯焦油中得到萘、α-甲基萘、β-甲基萘[12-15]。然而，目前没有从提取更多有价值的精细化学品的角度详细分析乙烯焦油组成的报道。气相色谱-质谱联用仪(GC-MS)可以得到相对分子质量小于600的化合物组成与结构信息[16-17]，为乙烯焦油组成分析提供有力科学依据。
当馏出温度＞280 ℃时，液相温度达350 ℃以上，乙烯焦油发生化学反应，结焦生炭倾向增大。因此，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，并结合优化程序升温条件对得到的12个馏分段中焦油组分进行GC-MS定性、定量分析。这为乙烯焦油全利用，尤其是其中高附加值芳环类精细化工产品的提取提供具有指导价值分析数据。
1. 实验部分
1.1 仪器和试剂
7890A-5975C型气相色谱-质谱联用仪(GC-MS，美国Agilent公司)：EI源，离子化电压70 eV，离子源温230 ℃, 扫描质量范围40~200 amu。进样量0.2 μL，分流比20:1，进样口温度280 ℃。以对芳烃有良好分离能力的HP-5MS色谱柱(30 m×0.25 mm×0.25 μm)为固定相。高纯He气为载气，载气流速1.0 mL/min。程序升温：初始温度65 ℃，保持3 min，以5 ℃/min的速率升温至100 ℃，以1 ℃/min的速率升温至105 ℃，保持2 min，2 ℃/min升温到130 ℃，保持2 min，10 ℃/min升温到250 ℃，以20 ℃/min升温到280 ℃，保持5 min。定性采用NIST2008标准谱库计算机检索，谱库难以确定的化合物则依据GC保留时间、主要离子峰、特征离子峰等与其他色谱和质谱资料对照解析，定量采用归一化面积校正法。
正己烷(分析纯，天津市大茂化学试剂厂)，茚、萘、α-甲基萘、β-甲基萘均购自Aladdin，分析纯。乙烯焦油由中国石油抚顺石化乙烯化工厂提供，乙烯裂解工艺如图 1所示。乙烯焦油的基本性质与组成分析见表 1。由表 1可见，乙烯焦油密度、粘度较大，冰点高，属重质馏分油。胶质和沥青质质量分数高，总计达31.50 %。相对于煤焦油，乙烯焦油是由轻质石脑油缩聚产生，含S、O、N化合物，金属离子，灰分质量分数少，故组成更干净，有望经分离与精制，提取精细化工产品。
图 1
表 1
表 1 抚顺乙烯焦油的基本性质与组成Table 1. Basic properties and compositions of Fushun ethylene bottom oil
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导出CSV
Routine analysis Measured value Elemental analysis Measured value Density(20 ℃)/(g·cm-3) 1.08 w(Nitrogen)/% 0.07 Viscosity(40 ℃)/(mm2·s-1) 48.26 w(Sulfur)/% 0.015 Freezing point/℃ 16.05 ρ(Fe)/(μg·g-1) 0.003 w(Carbon residue)/% 10.02 ρ(Ni)/(μg·g-1) 0.001 w(ash content)/% 0.0002 ρ(Ca)/(μg·g-1) 2.52 w(Colloid)/% 10.71 ρ(C) /(μg·g-1) 92.08 w(Asphaltene)/% 20.79 ρ(O) /(μg·g-1) 0.601 1.2 抚顺乙烯焦油的精馏分离
取抚顺乙烯焦油原料，常压蒸馏切割＜280 ℃馏分，抚顺乙烯焦油＜280 ℃馏分占焦油总量的52.2%。然后采用10 cm高瓷环填充柱进行常压精馏，将＜280 ℃馏分切割为12个馏分段，各馏分段的质量收率如表 2所示。由表 2可见，乙烯焦油收率较高为190~240 ℃馏分段，将这12个馏分段用正己烷溶剂1:1(体积比)稀释后，进行GC-MS分析。
表 2
表 2 抚顺乙烯焦油的精馏分离Table 2. Distillation separation of Fushun ethylene bottom oil下载:
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Fraction No. Boiling point range/℃ Yield/% 1 40~150 0.2490 2 150~170 0.2877 3 170~180 0.4079 4 180~190 0.9017 5 190~200 5.7535 6 200~210 13.3963 7 210~220 17.0030 8 220~230 14.5556 9 230~240 7.9863 10 240~250 3.9073 11 250~260 3.4350 12 260~280 10.3478 2. 结果与讨论
2.1 抚顺乙烯焦油＜280 ℃的馏分分析
图 2为抚顺乙烯焦油＜280 ℃的馏分的GC-MS总离子流色谱图，表 3为抚顺乙烯焦油＜280 ℃馏分组成的GC-MS分析结果。由图 2、表 3可见，＜280 ℃的馏分经GC-MS鉴定出化合物有90种，由烷烃和1~4环芳烃组成。其中烷烃为C13~C25各种烃，占10.792 %，可能是石脑油原料未充分裂解。芳香烃中单环25种苯类衍生物占11.154%；双环12种茚类衍物占11.869%，17种萘类衍生物占59.129%；3~4环苊、芴、蒽、菲、芘类衍生物占4.867%；其它占2.573%。乙烯焦油主要组成为双环芳烃，其中萘质量分数最高，占23.782%(保留时间RT=12.349 min)，其次为二氢萘占12.355%(RT=10.967 min，11.16 min)，β-甲基萘占9.473%(RT=17.012 min)，α-甲基萘占6.19%(RT=17.89 min)，茚占2.329%(RT=7.925 min)，联苯占1.452%(RT=21.628 min)。由GC-MS分析结果可也进一步看出，乙烯焦油中杂质较少，相比煤焦油，更适合作为提取芳烃类，尤其是作为双环芳烃的原料。此外芳烃质量分数高，质量热值大，也适于制造高级动力燃料，但另一方面，因芳烃质量分数高，反应活性较强[2]，乙烯焦油作为锅炉燃料使用时，结焦生炭倾向大。图 3为乙烯焦油中主要双环、三环芳烃的质谱图。
图 2
图 2 抚顺乙烯焦油＜280 ℃馏分的GC-MS总离子流图Figure 2. Total ion chromatogram of the fraction below 280 ℃ for Fushun ethylene bottom oil表 3
表 3 抚顺乙烯焦油＜280 ℃馏分组成的GC-MS分析结果Table 3. Detected GC-MS data for the < 280 ℃ fraction of Fushun ethylene bottom oil下载:
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Retention time/min Relative content/% Compound Retention time/min Relative content/% Compound 3.693 0.229 Ethylbenzene 22.415 1.544 Naphthalene, 1-ethyl- 4.218 0.244 Styrene 22.590 0.661 Naphthalene, 1-ethyl- 5.751 0.475 Benzene, 1-ethyl-2-methyl- 22.998 0.700 Naphthalene, 2, 6-dimethyl- 6.555 0.910 Benzene, 1-ethenyl-3-methyl- 23.860 1.308 Naphthalene, 2, 3-dimethyl- 7.400 0.417 Benzene, 2-propenyl- 24.006 0.557 Naphthalene, 2, 7-dimethyl- 7.662 0.496 Indane 24.892 0.475 Naphthalene, 2, 3-dimethyl- 7.925 2.329 Indene 25.737 0.312 Naphthalene, 2, 3-dimethyl- 8.041 0.369 Benzene, 1, 2-diethyl- 27.456 1.464 Acenaphthene 8.199 0.222 Benzene, 1, 2-diethyl- 27.748 0.510 1, 1′-Biphenyl, 4-methyl- 8.286 0.402 Benzene, 4-ethyl-1, 2-dimethyl- 28.203 0.226 1, 1′-Biphenyl, 4-methyl- 8.851 0.351 Benzene, 1-methyl-2-(1-methylethyl)- 28.721 0.248 Naphthalene, 1, 4, 6-trimethyl- 8.945 0.492 1H-Indene, 3-methyl- 29.053 0.438 1-Isopropenylnaphthalene 9.055 1.728 Benzene, 2-butenyl- 29.147 0.233 Pentadecane n-C15 9.324 0.422 Benzene, (2-methyl-1-propenyl)- 32.947 0.727 Fluorene 9.481 0.265 2, 4-Dimethylstyrene 33.518 0.226 Benzene, [1-(2, 4-cyclopentadien，(1-ylidene)ethyl- 9.895 0.295 Benzene, 1, 3-diethyl-5-methyl- 33.687 0.666 1, 1′-Biphenyl, 2-methyl- 10.075 0.274 2, 4-Dimethylstyrene 33.845 0.282 9H-Fluorene, 2-methyl- 10.157 0.360 2, 4-Dimethylstyrene 33.938 0.348 Naphthalene, 1-(2-propenyl)- 10.314 0.528 2, 4-Dimethylstyrene 34.206 0.525 Hexadecane n-C16 10.583 1.087 1H-Indene, 2, 3-dihydro-4-methyl- 36.298 0.250 9H-Fluorene, 1-methyl- 10.967 7.233 1, 4-Dihydronaphthalene 36.427 0.198 9H-Fluorene, 2-methyl- 11.160 5.113 1, 4-Dihydronaphthalene 36.602 1.254 Tetradecane n-C14 11.416 2.959 Cycloprop[a]indene, 1, 1a, 6, 6a-tetrahydro- 37.371 0.271 Dodecane, 2, 6, 11-trimethyl- 12.349 23.782 naphthalene 37.779 0.799 Phenanthrene 12.454 0.427 2-Ethyl-2, 3-dihydro-1H-indene 37.919 0.239 9H-Fluorene, 9-methylene- 12.611 0.686 Benzene, (3-methyl-2-butenyl)- 38.251 0.986 Hexadecane 13.223 0.199 1H-Indene, 1, 1-dimethyl- 38.822 0.249 Nonadecane, 9-methyl- 13.578 0.267 Benzene, cyclopentyl- 39.574 1.170 Heptadecane, 8-methyl- 13.951 0.448 Benzene, (1-ethyl-1-propenyl)- 39.790 0.304 Anthracene, 1-methyl- 14.412 0.351 1H-Indene, 1-ethenyl-2, 3-dihydro- 40.052 0.289 Hexadecane 14.738 0.755 2-Ethyl-1-H-indene 40.722 1.015 Tridecane, 7-hexyl- 14.855 0.531 1H-Indene, 1, 3-dimethyl- 41.125 0.430 Nonadecane, 9-methyl- 15.123 0.882 1H-Indene, 1, 3-dimethyl- 41.748 1.013 Eicosane 15.368 1.188 1H-Indene, 2, 3-dimethyl- 41.993 0.340 Pyrene 15.572 0.621 1H-Indene, 2, 3-dimethyl- 42.110 0.328 Eicosane, 10-methyl- 17.012 9.473 Naphthalene, 2-methyl- 42.687 0.768 Heneicosane 17.892 6.193 Naphthalene, 1-methyl- 43.019 0.203 Hexadecane 18.883 0.195 2-Methylbenzyl cyanide 43.573 0.481 Docosane 21.628 1.452 Biphenyl 44.336 0.226 Tetradecane 图 3
图 3 抚顺乙烯焦油＜280 ℃的馏分中主要芳烃的MS图Figure 3. Mass spectra for the main aromatic hydrocarbons in the < 280 ℃ fraction of Fushun ethylene bottom oil2.2 抚顺乙烯焦油不同馏分段组成分析
采用10 cm高瓷环填充柱对常压蒸馏得到抚顺乙烯焦油＜280 ℃馏分进行进一步切割，得12个馏分段，各馏分段的光学图片如图 4所示。由图 4可以清晰地看到切割温度不同，所得馏分呈现的颜色和状态不同，200 ℃以前馏分颜色与汽油(40~205 ℃)、轻柴油(180~370 ℃)接近。200~210 ℃和210~220 ℃两个馏分呈无色，且显示为固液两相。220~230 ℃馏分也呈固液两相，下层为白色固体，上层液体呈荧光蓝色。230~260 ℃馏分呈荧光蓝色，260~280 ℃馏分呈灰色。物理性质差别是化学组成不同的体现，不同颜色和状态也反映馏分组成上差别。
图 4
图 4 抚顺乙烯焦油12个馏分的光学图片Figure 4. Digital images of the 12 fractions for Fushun ethylene bottom oil对抚顺乙烯焦油＜280 ℃馏分所切割的12个馏分段进行了GC-MS分析。分析结果发现茚、茚满、2-丁烯基苯和1, 2-二甲基-4-乙基苯在190~200 ℃馏分内质量分数较高，分别为4.49%、4.6%、5.45%和2.66%。1, 4-二氢萘在200~210 ℃馏分中质量分数最高为9.046%。甲基茚与甲基氢茚集中分布在210~220 ℃馏分油中，质量分数量分别为4.24%和2.02%。在220~230 ℃馏分段内，萘的质量分数可达到41.15%；而β-甲基萘与α-甲基萘在250~260 ℃馏分内质量分数占16.73%与12.089%，在此馏分中联苯，1-乙基萘，二甲基萘质量分数分别为3.28 %、5.02 %和3.55 %；苊、芴、蒽、三甲基萘在260~280 ℃馏分中的质量分数分别占7.31%、2.08%、2.6%和3.44%。主要双环芳烃萘、β-甲基萘、α-甲基萘、1, 4-二氢萘在抚顺乙烯焦油各馏分段中的分布如图 5所示。由图 5可看出，随蒸馏温度的升高，萘、β-甲基萘、α-甲基萘、1, 4-二氢萘的质量分数分布趋势为先上升后下降。因焦油组成复杂，各组分在其中质量分数不是很高，精馏时平衡气化量小，导致4种主要双环芳烃在12个馏分中均有分布，但各组分在与其沸点接近的馏分中分布达到最大值。从抚顺乙烯焦油中提取萘需切割200~250 ℃馏分进行进一步的精制；提取β-甲基萘、α-甲基萘需切割230~260 ℃馏分段，提取1, 4-二氢萘需切割180~230 ℃馏分段。由此可见，抚顺乙烯焦油中几种主要芳烃类精细化工产品组分集中分布在200~250 ℃，对后续进一步的分离精制有重要指导意义。
图 5
图 5 主要芳烃在抚顺乙烯焦油各馏分段中的分布Figure 5. The distribution of main aromatic hydrocarbons in different fractions of Fushun ethylene bottom oil3. 结论
乙烯焦油是烃类裂解生产乙烯的副产物，产率为乙烯产量质量分数的10%~15%，随乙烯产能的增加，乙烯焦油量会持续增多，乙烯焦油传统的利用是被当作燃料直接粗放燃烧掉，由于乙烯焦油富含稠环芳烃在燃烧过程中易结焦生炭，使乙烯焦油热稳定性差，同时乙烯焦油C/H比高，作为燃料利用既污染环境又造成芳烃资源浪费严重。本文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，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，对所得12个馏分段进行GC-MS定性、定量分析。结果显示，抚顺乙烯焦油＜280 ℃馏分占焦油总量的52.2%，馏分中主要为芳香烃化合物，并且190~240 ℃的馏分的再利用价值较大，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。单环芳烃占5.800%，主要为1, 2-二乙基苯和2-丁烯基苯等；3~4环芳烃占2.532%，主要为苊、芴、蒽、菲、芘等。抚顺乙烯焦油中含量最多的双环芳烃为萘，其次为β-甲基萘、α-甲基萘、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%(质量分数)。由此可见，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。
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图 2 抚顺乙烯焦油＜280 ℃馏分的GC-MS总离子流图
Figure 2 Total ion chromatogram of the fraction below 280 ℃ for Fushun ethylene bottom oil
图 3 抚顺乙烯焦油＜280 ℃的馏分中主要芳烃的MS图
Figure 3 Mass spectra for the main aromatic hydrocarbons in the < 280 ℃ fraction of Fushun ethylene bottom oil
图 4 抚顺乙烯焦油12个馏分的光学图片
Figure 4 Digital images of the 12 fractions for Fushun ethylene bottom oil
图 5 主要芳烃在抚顺乙烯焦油各馏分段中的分布
Figure 5 The distribution of main aromatic hydrocarbons in different fractions of Fushun ethylene bottom oil
A.naphthalene; B.α-methylnaphthalene; C.β-methylnaphthalene; D.1, 4-dihydronaphthalene
表 1 抚顺乙烯焦油的基本性质与组成
Table 1. Basic properties and compositions of Fushun ethylene bottom oil
Routine analysis Measured value Elemental analysis Measured value Density(20 ℃)/(g·cm-3) 1.08 w(Nitrogen)/% 0.07 Viscosity(40 ℃)/(mm2·s-1) 48.26 w(Sulfur)/% 0.015 Freezing point/℃ 16.05 ρ(Fe)/(μg·g-1) 0.003 w(Carbon residue)/% 10.02 ρ(Ni)/(μg·g-1) 0.001 w(ash content)/% 0.0002 ρ(Ca)/(μg·g-1) 2.52 w(Colloid)/% 10.71 ρ(C) /(μg·g-1) 92.08 w(Asphaltene)/% 20.79 ρ(O) /(μg·g-1) 0.601 
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表 2 抚顺乙烯焦油的精馏分离
Table 2. Distillation separation of Fushun ethylene bottom oil
Fraction No. Boiling point range/℃ Yield/% 1 40~150 0.2490 2 150~170 0.2877 3 170~180 0.4079 4 180~190 0.9017 5 190~200 5.7535 6 200~210 13.3963 7 210~220 17.0030 8 220~230 14.5556 9 230~240 7.9863 10 240~250 3.9073 11 250~260 3.4350 12 260~280 10.3478
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表 3 抚顺乙烯焦油＜280 ℃馏分组成的GC-MS分析结果
Table 3. Detected GC-MS data for the < 280 ℃ fraction of Fushun ethylene bottom oil
Retention time/min Relative content/% Compound Retention time/min Relative content/% Compound 3.693 0.229 Ethylbenzene 22.415 1.544 Naphthalene, 1-ethyl- 4.218 0.244 Styrene 22.590 0.661 Naphthalene, 1-ethyl- 5.751 0.475 Benzene, 1-ethyl-2-methyl- 22.998 0.700 Naphthalene, 2, 6-dimethyl- 6.555 0.910 Benzene, 1-ethenyl-3-methyl- 23.860 1.308 Naphthalene, 2, 3-dimethyl- 7.400 0.417 Benzene, 2-propenyl- 24.006 0.557 Naphthalene, 2, 7-dimethyl- 7.662 0.496 Indane 24.892 0.475 Naphthalene, 2, 3-dimethyl- 7.925 2.329 Indene 25.737 0.312 Naphthalene, 2, 3-dimethyl- 8.041 0.369 Benzene, 1, 2-diethyl- 27.456 1.464 Acenaphthene 8.199 0.222 Benzene, 1, 2-diethyl- 27.748 0.510 1, 1′-Biphenyl, 4-methyl- 8.286 0.402 Benzene, 4-ethyl-1, 2-dimethyl- 28.203 0.226 1, 1′-Biphenyl, 4-methyl- 8.851 0.351 Benzene, 1-methyl-2-(1-methylethyl)- 28.721 0.248 Naphthalene, 1, 4, 6-trimethyl- 8.945 0.492 1H-Indene, 3-methyl- 29.053 0.438 1-Isopropenylnaphthalene 9.055 1.728 Benzene, 2-butenyl- 29.147 0.233 Pentadecane n-C15 9.324 0.422 Benzene, (2-methyl-1-propenyl)- 32.947 0.727 Fluorene 9.481 0.265 2, 4-Dimethylstyrene 33.518 0.226 Benzene, [1-(2, 4-cyclopentadien，(1-ylidene)ethyl- 9.895 0.295 Benzene, 1, 3-diethyl-5-methyl- 33.687 0.666 1, 1′-Biphenyl, 2-methyl- 10.075 0.274 2, 4-Dimethylstyrene 33.845 0.282 9H-Fluorene, 2-methyl- 10.157 0.360 2, 4-Dimethylstyrene 33.938 0.348 Naphthalene, 1-(2-propenyl)- 10.314 0.528 2, 4-Dimethylstyrene 34.206 0.525 Hexadecane n-C16 10.583 1.087 1H-Indene, 2, 3-dihydro-4-methyl- 36.298 0.250 9H-Fluorene, 1-methyl- 10.967 7.233 1, 4-Dihydronaphthalene 36.427 0.198 9H-Fluorene, 2-methyl- 11.160 5.113 1, 4-Dihydronaphthalene 36.602 1.254 Tetradecane n-C14 11.416 2.959 Cycloprop[a]indene, 1, 1a, 6, 6a-tetrahydro- 37.371 0.271 Dodecane, 2, 6, 11-trimethyl- 12.349 23.782 naphthalene 37.779 0.799 Phenanthrene 12.454 0.427 2-Ethyl-2, 3-dihydro-1H-indene 37.919 0.239 9H-Fluorene, 9-methylene- 12.611 0.686 Benzene, (3-methyl-2-butenyl)- 38.251 0.986 Hexadecane 13.223 0.199 1H-Indene, 1, 1-dimethyl- 38.822 0.249 Nonadecane, 9-methyl- 13.578 0.267 Benzene, cyclopentyl- 39.574 1.170 Heptadecane, 8-methyl- 13.951 0.448 Benzene, (1-ethyl-1-propenyl)- 39.790 0.304 Anthracene, 1-methyl- 14.412 0.351 1H-Indene, 1-ethenyl-2, 3-dihydro- 40.052 0.289 Hexadecane 14.738 0.755 2-Ethyl-1-H-indene 40.722 1.015 Tridecane, 7-hexyl- 14.855 0.531 1H-Indene, 1, 3-dimethyl- 41.125 0.430 Nonadecane, 9-methyl- 15.123 0.882 1H-Indene, 1, 3-dimethyl- 41.748 1.013 Eicosane 15.368 1.188 1H-Indene, 2, 3-dimethyl- 41.993 0.340 Pyrene 15.572 0.621 1H-Indene, 2, 3-dimethyl- 42.110 0.328 Eicosane, 10-methyl- 17.012 9.473 Naphthalene, 2-methyl- 42.687 0.768 Heneicosane 17.892 6.193 Naphthalene, 1-methyl- 43.019 0.203 Hexadecane 18.883 0.195 2-Methylbenzyl cyanide 43.573 0.481 Docosane 21.628 1.452 Biphenyl 44.336 0.226 Tetradecane
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