陕北中低温煤焦油中含氧有机化合物的质谱分析
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摘要
中低温煤焦油中含氧有机化合物的含量较高,其中诸多含氧有机化合物是高附加值的有机化学品。本研究采用气相色谱/质谱联用仪(GC-MS)和负离子模式电喷雾傅里叶变换离子回旋共振质谱仪(NIESIFTICRMS)分析了陕北中低温煤焦油中的含氧有机化合物(OCOCs),旨在了解OCOCs的组成结构,为有效分离OCOCs提供科学依据。结果表明,用GC-MS检测到的OCOCs中,含1个氧原子(O_1,主要为芳酚)和2个氧原子(O_2)的化合物的相对含量分别为99.4%和0.6%;用NIESIFTICRMS检测到的OCOCs中碳原子数、氧原子数和芳环数范围分别为8～35、1～5和1～4,其中O_1和O_2占绝大多数;检测到的主要酸性OCOCs是苯酚、苯二酚和苯甲酸及其烷基取代物以及环烷和链烷酸,其中O_1的主要成分是1～4环的一元芳酚。GCMS与NIESIFTICRMS优势互补,是从分子水平上了解中低温煤焦油中OCOCs组成结构的有效工具。
The total content of oxygen-containing organic compounds( OCOCs) in middle/low temperature coal tar( M/LTCT) are relatively high. Many OCOCs in M/LTCT are value-added organic compounds. In this investigation,a gas chromatograph-mass spectrometer( GC-MS) and negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometer( NIESIFTICRMS) were used to analyze OCOCs in a M/LTCT from Northern Shaanxi,aiming at understanding the composition and structures of the OCOCs to provide scientific basis for efficiently separating the OCOCs. The results showed that one oxygen-containing species( O_1,most of which are arenols) and two oxygen-containing species( O_2) in the GC-MS-detectable OCOCs accounted for 99.4% and 0.6%,respectively; numbers of carbon,oxygen and aromatic rings in the OCOCs detected with the NIESIFTICRMS were 8-35,1-5 and 1-4,respectively,and O_1 and O_2 were predominantly abundant among the OCOCs; the main acidic OCOCs were phenol,benzenediols,benzoic acid and their alkyl-substitutes along with cyclanoic and chain alkanoic acids,and the main species were arenols with 1-4 aromatic rings among O_1. GC-MS and NIESIFTICRMS have complementary advantages,and are proved to be effective tools for understanding the composition and structures of OCOCs in M/LTCT at molecular level.
The total content of oxygen-containing organic compounds( OCOCs) in middle/low temperature coal tar( M/LTCT) are relatively high. Many OCOCs in M/LTCT are value-added organic compounds. In this investigation,a gas chromatograph-mass spectrometer( GC-MS) and negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometer( NIESIFTICRMS) were used to analyze OCOCs in a M/LTCT from Northern Shaanxi,aiming at understanding the composition and structures of the OCOCs to provide scientific basis for efficiently separating the OCOCs. The results showed that one oxygen-containing species( O_1,most of which are arenols) and two oxygen-containing species( O_2) in the GC-MS-detectable OCOCs accounted for 99.4% and 0.6%,respectively; numbers of carbon,oxygen and aromatic rings in the OCOCs detected with the NIESIFTICRMS were 8-35,1-5 and 1-4,respectively,and O_1 and O_2 were predominantly abundant among the OCOCs; the main acidic OCOCs were phenol,benzenediols,benzoic acid and their alkyl-substitutes along with cyclanoic and chain alkanoic acids,and the main species were arenols with 1-4 aromatic rings among O_1. GC-MS and NIESIFTICRMS have complementary advantages,and are proved to be effective tools for understanding the composition and structures of OCOCs in M/LTCT at molecular level.
引文
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26 Pan N,Cui D C,Li R L,Shi Q,Chung K H,Long H Y,Li Y Y,Zhang Y H,Zhao S Q,Xu C M.Energy Fuels,2012,26(9):5719-5728
27 Robb D B,Smith D R,Blades M W.J.Am.Soc.Mass Spectrom.,2008,19(7):955-963
28 Bae E,Na J G,Chung S H,Kim H S,Kim S.Energy Fuels,2010,24(4):2563-2569
29 Schaub T M,Rodgers R P,Marshal A G.Energy Fuels,2005,19(4):1566-1573
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2 SHUI Heng-Fu,ZHANG De-Xiang,ZHANG Chao-Qun.Separation and Refining of Coal Tar.Beijing:Chemical Industry Press,2007:440-443水恒福,张德祥,张超群.煤焦油分离与精制.北京:化学工业出版社,2007:440-443
3 ZHANG Yang,SUN Hui-Qing,BAI Xiao-Yan,WANG Li-Bin.Clean Coal Technology,2009,15(6):57-60张飏,孙会青,白效言,王利斌.洁净煤技术,2009,15(6):57-60
4 CHEN Fan-Rong,MA Xiao-Xun,CAO Wei.Coal Conversion,2013,36(4):52-56陈繁荣,马晓迅,曹魏.煤炭转化,2013,36(4):52-56
5 HAO Hua-Rui,GAO Ping-Qiang,YAN Qin-Sheng,LI Mei.Applied Chemical Industry,2016,45(10):1866-1868郝华睿,高平强,闫秦生,李梅.应用化工,2016,45(10):1866-1868
6 ZHANG Xiao-Jing.Journal of China Coal Society,2011,36(10):840-844张晓静.煤炭学报,2011,36(10):840-844
7 SUN Ming,FENG Guang,WANG Ru-Cheng,XU Long,MA Xiao-Xun,Petrochemical Technology,2011,40(6):667-672孙鸣,冯光,王汝成,徐龙,马晓迅.石油化工,2011,40(6):667-672
8 ZHANG Jun-Min,LIU Gong.Coal Conversion,2010,33(3):92-96张军民,刘弓.煤炭转化,2010,33(3):92-96
9 WANG Xi-Kui,JIN Zu-Liang,XU Xiao-Bai.Environmental Chemistry,1989,8(4):16-22王西奎,金祖亮,徐晓白.环境化学,1989,8(4):16-22
10 Sun M,Ma X X,Yao Q X,Wang R C,Ma Y X,Feng G,Shang J X,Xu L,Yang Y H.Energy Fuels,2011,25(3):1140-1145
11 Burgess W A,Pittman J J,Marcus R K,Thies M C.Energy Fuels,2010,24(8):4301-4311
12 George A,Morgan T J,Alvarez P,Millana M,Heroda A A,Kandiyotia R.Fuel,2010,89(10):2953-2970
13 Shi Q,Pan N,Long H Y,Cui D C,Guo X F,Long Y H,Chung H K,Zhao S Q,Xu C M.Energy Fuels,2013,27(1):108-117
14 YU Ya-Ru,FAN Xing,ZHAO Yun-Peng,WEI Xian-Yong.Chinese J.Anal.Chem.,2017,45(7):1005-1011于亚如,樊星,赵云鹏,魏贤勇.分析化学,2017,45(7):1005-1011
15 Wang M,Fan X,Wei X Y,Cao J P,Zhao Y P,Wang S Z,You C Y.Fuel,2016,183:115-122
16 Fan X,Wei X Y,Zong Z M.Fuel,2013,109:28-32
17 Rodgers R P,Marshall A G.Asphaltenes,Heavy Oils,and Petroleomics,New York:Springer,2007:63-93
18 Marshall A G,Hendrickson C L.Int.J.Mass Spectrom.,2002,215(1):59-75
19 Zhang L Z,Hou Z,Horton S R,Klein M T,Shi Q,Zhao S Q,Xu C M.Energy Fuels,2014,28(3):1736-1749
20 Corilo Y E,Vaz B G,Simas R C,Nascimento H D,Klitzke C F,Pereira R L,Bastos W L,Neto E V S,Rodgers R P,Eberlin M N.Anal.Chem.,2010,82(10):3990-3996
21 Smith E A,Park S,Klein A T,Lee Y J.Energy Fuels,2012,26(6):3796-3802
22 Chiaberge S,Leonardis I,Fiorani T,Cesti P,Reale S,Angelis F D.Energy Fuels,2014,28(3):2019-2026
23 Yan H L,Zong Z M,Li Z K,Wei X Y.Fuel,2015,160:596-604
24 Koolen H F,Swarthout R F,Nelson R K,Chen H,Krajewski L C,Aeppli C,McKenna A M,Rodgers R P,Reddy C M.Energy Fuels,2015,29(2):641-648
25 Shi Q,Yan Y,Wu X J,Li S Y,Chung K H,Zhao S Q,Xu C M.Energy Fuels,2010,24(1):5533-5538
26 Pan N,Cui D C,Li R L,Shi Q,Chung K H,Long H Y,Li Y Y,Zhang Y H,Zhao S Q,Xu C M.Energy Fuels,2012,26(9):5719-5728
27 Robb D B,Smith D R,Blades M W.J.Am.Soc.Mass Spectrom.,2008,19(7):955-963
28 Bae E,Na J G,Chung S H,Kim H S,Kim S.Energy Fuels,2010,24(4):2563-2569
29 Schaub T M,Rodgers R P,Marshal A G.Energy Fuels,2005,19(4):1566-1573
30 Shaw G J,Franich R A,Eglinton G,Allan J,Douglas A G.Phys.Chem.Earth,1980,12:281-286