白石湖煤THF萃取物中硫、氮化合物赋存形态
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摘要
采用四氢呋喃(THF)对白石湖煤进行索氏萃取,萃取液在四氟硼酸银存在下与碘甲烷反应,转化成甲基磺酸盐。采用电喷雾电离(ESI)傅里叶变换离子回旋共振质谱(FT-ICR MS)对甲基硫盐和含氮化合物进行了表征,结合硫、氮化学发光检测器(GC-SCD和GC-NCD)分析,研究THF萃取物中硫、氮化合物形态。结果表明,THF萃取物中主要是S_1、S_2、N_1、N_1O_1类化合物,含量较高的硫、氮化合物分别是二苯并噻吩类化合物及咔唑类化合物。
Baishihu lignite was subjected to Soxhlet extraction by tetrahydrofuran(THF). The extract was reacted with iodomethane in the presence of silver tetrafluoroborate and converted to methylsulfonium salts. The methylsulfonium salts and nitrogen compounds were characterized by electrospray ionization(ESI) and Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS). Combined with sulfur and nitrogen chemiluminescence detectors(GC-SCD and GC-NCD),the forms of sulfur and nitrogen compounds in THF extracts were studied. The results showed that S_1, S_2, N_1 and N_1O_1 class species were identified in THF extract. The sulfur and nitrogen compounds were mostly dibenzothiophene and carbazole compounds.
Baishihu lignite was subjected to Soxhlet extraction by tetrahydrofuran(THF). The extract was reacted with iodomethane in the presence of silver tetrafluoroborate and converted to methylsulfonium salts. The methylsulfonium salts and nitrogen compounds were characterized by electrospray ionization(ESI) and Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS). Combined with sulfur and nitrogen chemiluminescence detectors(GC-SCD and GC-NCD),the forms of sulfur and nitrogen compounds in THF extracts were studied. The results showed that S_1, S_2, N_1 and N_1O_1 class species were identified in THF extract. The sulfur and nitrogen compounds were mostly dibenzothiophene and carbazole compounds.
引文
[1] 舒歌平, 史士东, 李克健. 煤炭液化技术[M]. 北京: 煤炭工业出版社, 2003.(SHU Ge-ping, SHI Shi-dong, LI Ke-jian. Direct Coal Liquefaction[M]. Beijing: Coal Industry Press, 2003.)
[2] 史士东. 煤加氢液化工程学基础[M]. 北京: 化学工业出版社, 2012.(SHI Shi-dong. Engineering Basis of Coal Hydro-Liquefaction[M]. Beijing: Chemical Industry Press, 2003.)
[3] HAENEL M W. Recent progress in coal structure research[J]. Fuel, 1992, 71(11): 1211-1223.
[4] 刘敏, 史士东, 曲思建, 刘立麟, 盛明, 毛学锋. 煤炭直接液化反应机理理论研究进展[J]. 洁净煤技术, 2015, 21(4): 49-54.(LIU Min, SHI Shi-dong, QU Si-Jian, LIU Li-lin, SHENG Ming, MAO Xue-feng. Progress in theoretical research on reaction mechanism of coal direct liquefaction[J]. Clean Coal Technol, 2015, 21(4): 49-54.)
[5] NEAVEL R. Liquefaction of coal in hydrogen-donor and non-donor vehicles[J]. Fuel, 1976, 55(3): 237-242.
[6] 贾伟. 煤中小分子化合物对煤高温快速液化的影响[D]. 山西: 太原理工大学, 2010.(JIA Wei. Effect of small molecular compounds in coal on rapid liquefaction of coal at high temperature[D]. Shanxi: Taiyuan University of Technology, 2010.)
[7] NI H X, YAN L L, MA C, SHI Q. Molecular composition of soxhlet n-methyl-2-pyrrolidinone extracts from a lignite[J]. Energy Fuels, 2016, 30(11): 9285-9292.
[8] IION M, TAKANOHASHI T, OHSUGA H. Extraction of coals with CS2-N-methyl-2-pyrrolidinone mixed solvent at room temperature[J]. Fuel, 1988, 67(12): 1639-1647.
[9] MATHEWS J P, BURGESS C, PAINTER P. Interactions of illinois No.6 bituminous coal with solvents: A review of solvent swelling and extraction literature[J]. Energy Fuels, 2015, 29(3): 1279-1294.
[10] FACRIS L, FLORES J. Sorption of heavy metals on a coal beneficiation tailing material: II.Adsorptive particulate flotation[J]. Coal Prep, 2002, 22(5): 234-248.
[11] TAKANOHASHI T, OHKAW T, YANAGIDA T. Effect of maceral composition on the extraction of bituminous coals with carbon disulphide-n-methyl-2-pyrridinone mixed solvent at room temperature[J]. Fuel, 1993, 72(1): 51-55.
[12] CAI M, SMART R. Quantitative analysis of N-methyl-2-pyroolidinone in coal extracts by TGA-FTIR[J]. Energy Fuels, 1993, 7(1): 52-56.
[13] GAO H, NOMURA M, SATORU M A. Statistical distribution characteristics of pyridine transport in coal particles and a series of new phenomenological models for overshoot and nonovershoot solvent swelling of coal particles[J]. Energy Fuel, 1999, 13(2): 518-528.
[14] 陈茺, 高晋生, 颜捷. 环己酮抽提煤的研究[J]. 燃料化学学报, 1997, 25(1): 60-64.(CHEN Chong, GAO Jin-sheng, YAN Jie. Study on Extraction of coal with cyclohexanone[J]. J Fuel Chem Technol, 1997, 25(1): 60-64.)
[15] LIY F, WEI X Y, GUI J, WANG Y G, LI P, ZONG Z M. Characterization of biomarkers and structural features of condensed aromatics in xianfeng lignite[J]. Energy Fuels, 2013, 27(12): 7369-7378.
[16] RANMAN M, SAMANTA A, GUPTA R. Production and characterization of ash-free coal from low-Rank canadian coal by solvent extraction[J]. Fuel Process Technol, 2013, 115(11): 88-98.
[17] STOCK L M, OBENG M. Oxidation and carboxylation: a reaction sequence for the study of aromatic structural elements in pocahontas no.3 coal[J]. Energy Fuels, 1997, 11(5): 987-997.
[18] 史权, 赵锁奇, 徐春明, 侯读杰. 傅立叶变换离子回旋共振质谱仪在石油组成分析中的应用[J]. 质谱学报, 2008, 29(6): 367-378.(SHI Quan, ZHAO Suo-qi, XU Chun-ming, Hou Du-jie. Application of fourier transform ion cyclotron resonance mass spectrometer in petroleum composition analysis[J]. J Mass Spectr, 2008, 29(6): 367-378.)
[19] WU Z, RODEGERS R P, MARSHALL A G. Compositional determination of acidic species in illinois no. 6 coal extracts by electrospray ionization fourier transform ion cyclotron resonance mass spectrometry[J]. Energy Fuels, 2004, 18(5): 1424-1428.
[20] WU Z, RODGERS R P, MARSHALL A G. Two-and three-dimensional van krevelen diagrams: A graphical analysis complementary to the kendrick mass plot for sorting elemental compositions of complex organic mixtures based on ultrahigh-resolution broadband fourier transform ion cyclotron resonance mass measurements[J]. Anal Chem, 2004, 76(9): 2511-2516.
[21] SHI Q, PAN N, LONG H, CUI D, GUO X, LONG Y, CHUNG K H, ZHAO S, XU C, HSU C S. Characterization of middle-temperature gasification coal tar. part 3: Molecular composition of acidic compounds[J]. Energy Fuels, 2013, 27(1): 108-117.
[22] KONG J, WEI X Y, YA H L, LI Z K, ZHAO M X, LI Y, ZONG Z M. Analysis of extractable basic nitrogen compounds in buliangou subbituminous coal by positive-ion ESI FT-ICR MS[J]. Fuel, 2015, 159: 385-391.
[23] SHI Q, HOU D, CHUNG K H, XU C, ZHAO S, ZHANG Y. Characterization of heteroatom compounds in a crude oil and its saturates,aromatics,resins and asphaltenes (sara) and non-basic nitrogen fractions analyzed by negative-ion electrospray ionization fourier transform ion cyclotron resonance mass spectrometry[J]. Energy Fuels, 2010, 24(4): 2545-2553.
[24] BRADLEY C, SCHILLER D J. Determination of sulfur compound distribution in petroleum by gas chromatography with a flame photometric detector[J]. Anal Chem, 1986, 58(14): 3017-3021.
[25] GARCIA C L, BECCHI M, GRENIER M F, PAISSE O, SZYMANSKIT R. Analysis of aromatic sulfur compounds in gas oils using gc with sulfur chemiluminescence detection and high-resolution ms[J]. Anal Chem, 2002, 74(15): 3849 -3857.
[26] CHAWLA B, SANZO F D. Determination of sulfur components in light petroleum streams by high-resolution gas chromatography with chemiluminescence detection[J]. J Chromatography, 1992, 589(1/2): 271-279.
[27] SHI Q, XU C, ZHAO S, CHUNG K H, ZHANG Y. Characterization of basic nitrogen species in coker gas oils by positive-ion electrospray ionization fourier transform ion cyclotron resonance mass spectrom[J]. Energy Fuels, 2009, 24 (1): 563.569.
[28] LIU P, SHI Q, CHUNG K H, ZHANG Y, PAN N. Molecular characterization of sulfur compounds in venezuela crude oil and its sara fractions by electrospray ionization fourier transform ion cyclotron resonance mass spectrom[J]. Energy Fuels, 2010, 24(9): 5089-5096.
[29] 吴梅, 史军歌, 田松柏. 汽油中元素硫的GC-SCD分析方法[J]. 石油学报(石油加工), 2008, 33(2): 320-325.(WU Mei, SHI Jun-ge, TIAN Song-bai. Analysis of elemental sulfur in gasoline by GC-SCD[J]. Acta Pet Sin(Pet Process Sect), 2008, 33(2): 320-325.)
[30] 黄澎, 张晓静, 毛学锋, 李伟林. 神府煤液化油加氢精制过程中硫氮化合物分布的变化[J]. 燃料化学学报, 2015, 43(12): 37-43.(HUANG Peng, ZHANG Xiao-jing, MAO Xue-feng, LI Wei-ling. Distribution of sulfur and nitrogen compounds in shenfu coal liquefied oil hydrorefining process[J]. J Fuel Chem Technol, 2015, 43(12): 37-43.)
[31] 李延红. 煤液化油中含氮化合物存在形式及分布的研究[D]. 上海: 华东理工大学, 2014.(LI Yan-hong. Study on the existence and distribution of nitrogen-containing compounds in coal liquefied oil[D]. Shanghai: East China University of Science and Technology, 2014.)
[2] 史士东. 煤加氢液化工程学基础[M]. 北京: 化学工业出版社, 2012.(SHI Shi-dong. Engineering Basis of Coal Hydro-Liquefaction[M]. Beijing: Chemical Industry Press, 2003.)
[3] HAENEL M W. Recent progress in coal structure research[J]. Fuel, 1992, 71(11): 1211-1223.
[4] 刘敏, 史士东, 曲思建, 刘立麟, 盛明, 毛学锋. 煤炭直接液化反应机理理论研究进展[J]. 洁净煤技术, 2015, 21(4): 49-54.(LIU Min, SHI Shi-dong, QU Si-Jian, LIU Li-lin, SHENG Ming, MAO Xue-feng. Progress in theoretical research on reaction mechanism of coal direct liquefaction[J]. Clean Coal Technol, 2015, 21(4): 49-54.)
[5] NEAVEL R. Liquefaction of coal in hydrogen-donor and non-donor vehicles[J]. Fuel, 1976, 55(3): 237-242.
[6] 贾伟. 煤中小分子化合物对煤高温快速液化的影响[D]. 山西: 太原理工大学, 2010.(JIA Wei. Effect of small molecular compounds in coal on rapid liquefaction of coal at high temperature[D]. Shanxi: Taiyuan University of Technology, 2010.)
[7] NI H X, YAN L L, MA C, SHI Q. Molecular composition of soxhlet n-methyl-2-pyrrolidinone extracts from a lignite[J]. Energy Fuels, 2016, 30(11): 9285-9292.
[8] IION M, TAKANOHASHI T, OHSUGA H. Extraction of coals with CS2-N-methyl-2-pyrrolidinone mixed solvent at room temperature[J]. Fuel, 1988, 67(12): 1639-1647.
[9] MATHEWS J P, BURGESS C, PAINTER P. Interactions of illinois No.6 bituminous coal with solvents: A review of solvent swelling and extraction literature[J]. Energy Fuels, 2015, 29(3): 1279-1294.
[10] FACRIS L, FLORES J. Sorption of heavy metals on a coal beneficiation tailing material: II.Adsorptive particulate flotation[J]. Coal Prep, 2002, 22(5): 234-248.
[11] TAKANOHASHI T, OHKAW T, YANAGIDA T. Effect of maceral composition on the extraction of bituminous coals with carbon disulphide-n-methyl-2-pyrridinone mixed solvent at room temperature[J]. Fuel, 1993, 72(1): 51-55.
[12] CAI M, SMART R. Quantitative analysis of N-methyl-2-pyroolidinone in coal extracts by TGA-FTIR[J]. Energy Fuels, 1993, 7(1): 52-56.
[13] GAO H, NOMURA M, SATORU M A. Statistical distribution characteristics of pyridine transport in coal particles and a series of new phenomenological models for overshoot and nonovershoot solvent swelling of coal particles[J]. Energy Fuel, 1999, 13(2): 518-528.
[14] 陈茺, 高晋生, 颜捷. 环己酮抽提煤的研究[J]. 燃料化学学报, 1997, 25(1): 60-64.(CHEN Chong, GAO Jin-sheng, YAN Jie. Study on Extraction of coal with cyclohexanone[J]. J Fuel Chem Technol, 1997, 25(1): 60-64.)
[15] LIY F, WEI X Y, GUI J, WANG Y G, LI P, ZONG Z M. Characterization of biomarkers and structural features of condensed aromatics in xianfeng lignite[J]. Energy Fuels, 2013, 27(12): 7369-7378.
[16] RANMAN M, SAMANTA A, GUPTA R. Production and characterization of ash-free coal from low-Rank canadian coal by solvent extraction[J]. Fuel Process Technol, 2013, 115(11): 88-98.
[17] STOCK L M, OBENG M. Oxidation and carboxylation: a reaction sequence for the study of aromatic structural elements in pocahontas no.3 coal[J]. Energy Fuels, 1997, 11(5): 987-997.
[18] 史权, 赵锁奇, 徐春明, 侯读杰. 傅立叶变换离子回旋共振质谱仪在石油组成分析中的应用[J]. 质谱学报, 2008, 29(6): 367-378.(SHI Quan, ZHAO Suo-qi, XU Chun-ming, Hou Du-jie. Application of fourier transform ion cyclotron resonance mass spectrometer in petroleum composition analysis[J]. J Mass Spectr, 2008, 29(6): 367-378.)
[19] WU Z, RODEGERS R P, MARSHALL A G. Compositional determination of acidic species in illinois no. 6 coal extracts by electrospray ionization fourier transform ion cyclotron resonance mass spectrometry[J]. Energy Fuels, 2004, 18(5): 1424-1428.
[20] WU Z, RODGERS R P, MARSHALL A G. Two-and three-dimensional van krevelen diagrams: A graphical analysis complementary to the kendrick mass plot for sorting elemental compositions of complex organic mixtures based on ultrahigh-resolution broadband fourier transform ion cyclotron resonance mass measurements[J]. Anal Chem, 2004, 76(9): 2511-2516.
[21] SHI Q, PAN N, LONG H, CUI D, GUO X, LONG Y, CHUNG K H, ZHAO S, XU C, HSU C S. Characterization of middle-temperature gasification coal tar. part 3: Molecular composition of acidic compounds[J]. Energy Fuels, 2013, 27(1): 108-117.
[22] KONG J, WEI X Y, YA H L, LI Z K, ZHAO M X, LI Y, ZONG Z M. Analysis of extractable basic nitrogen compounds in buliangou subbituminous coal by positive-ion ESI FT-ICR MS[J]. Fuel, 2015, 159: 385-391.
[23] SHI Q, HOU D, CHUNG K H, XU C, ZHAO S, ZHANG Y. Characterization of heteroatom compounds in a crude oil and its saturates,aromatics,resins and asphaltenes (sara) and non-basic nitrogen fractions analyzed by negative-ion electrospray ionization fourier transform ion cyclotron resonance mass spectrometry[J]. Energy Fuels, 2010, 24(4): 2545-2553.
[24] BRADLEY C, SCHILLER D J. Determination of sulfur compound distribution in petroleum by gas chromatography with a flame photometric detector[J]. Anal Chem, 1986, 58(14): 3017-3021.
[25] GARCIA C L, BECCHI M, GRENIER M F, PAISSE O, SZYMANSKIT R. Analysis of aromatic sulfur compounds in gas oils using gc with sulfur chemiluminescence detection and high-resolution ms[J]. Anal Chem, 2002, 74(15): 3849 -3857.
[26] CHAWLA B, SANZO F D. Determination of sulfur components in light petroleum streams by high-resolution gas chromatography with chemiluminescence detection[J]. J Chromatography, 1992, 589(1/2): 271-279.
[27] SHI Q, XU C, ZHAO S, CHUNG K H, ZHANG Y. Characterization of basic nitrogen species in coker gas oils by positive-ion electrospray ionization fourier transform ion cyclotron resonance mass spectrom[J]. Energy Fuels, 2009, 24 (1): 563.569.
[28] LIU P, SHI Q, CHUNG K H, ZHANG Y, PAN N. Molecular characterization of sulfur compounds in venezuela crude oil and its sara fractions by electrospray ionization fourier transform ion cyclotron resonance mass spectrom[J]. Energy Fuels, 2010, 24(9): 5089-5096.
[29] 吴梅, 史军歌, 田松柏. 汽油中元素硫的GC-SCD分析方法[J]. 石油学报(石油加工), 2008, 33(2): 320-325.(WU Mei, SHI Jun-ge, TIAN Song-bai. Analysis of elemental sulfur in gasoline by GC-SCD[J]. Acta Pet Sin(Pet Process Sect), 2008, 33(2): 320-325.)
[30] 黄澎, 张晓静, 毛学锋, 李伟林. 神府煤液化油加氢精制过程中硫氮化合物分布的变化[J]. 燃料化学学报, 2015, 43(12): 37-43.(HUANG Peng, ZHANG Xiao-jing, MAO Xue-feng, LI Wei-ling. Distribution of sulfur and nitrogen compounds in shenfu coal liquefied oil hydrorefining process[J]. J Fuel Chem Technol, 2015, 43(12): 37-43.)
[31] 李延红. 煤液化油中含氮化合物存在形式及分布的研究[D]. 上海: 华东理工大学, 2014.(LI Yan-hong. Study on the existence and distribution of nitrogen-containing compounds in coal liquefied oil[D]. Shanghai: East China University of Science and Technology, 2014.)