Thermal dissolution of Shengli and Xiaolongtan lignites in methanol and analysis of the soluble portions
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摘要: 研究了胜利褐煤(SL) 和小龙潭褐煤(XLT) 在甲醇中的热溶行为, 并利用傅里叶变换红外光谱、气相色谱/质谱(GC/MS) 和大气压固体分析探针/飞行时间质谱(ASAP/TOF-MS) 对320 ℃热溶物的组成和结构特征进行了分析。两种褐煤热溶物产率均随温度升高而增加, 但240 ℃后XLT热溶物(SPXLT) 产率明显高于SL热溶物(SPSL)。GC/MS分析表明, 两种褐煤热溶物以含氧化合物为主, 尤其酚类的相对含量超过49%;与SPXLT相比, SPSL中烯烃、芳烃、醚类、羧酸、酯类和有机硫化合物(OSCs) 含量较高, 而烷烃、酚类、酮类和有机氮化合物含量较低; SPSL中的OSCs以噻吩为主, 而SPXLT中的OSCs以硫醇为主。ASAP/TOF-MS可检测出热溶物中大量GC/MS无法检测出的较强极性和难挥发化合物; 与SPXLT相比, SPSL中CHO和CHS族分含量较低, 而CHN、CHNO、CHOS、CHNS和CHNOS族分含量较高; 两种褐煤热溶物中化合物的碳数和双键数(double bond equivalent, DBE) 主要分布在3-15和0-10, SPXLT中化合物的碳数和DBE分布相对集中。
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关键词:
- 褐煤 /
- 热溶 /
- 气相色谱/质谱 /
- 大气压固体分析探针/飞行时间质谱
Abstract: Thermal dissolution behaviors of Shengli (SL) and Xiaolongtan (XLT) lignite in methanol were investigated. The composition and structural characteristics of soluble portions (SPs) obtained at 320 ℃ were characterized with Fourier transform infrared spectroscopy, gas chromatograph /mass spectrometer (GC/MS) and atmospheric solid analysis probe/time of flight mass spectrometer (ASAP/TOF-MS). For the two lignites, the yield of SPs increase with temperature increasing, while the yield of SPs from XLT (SPXLT) is obvious higher than that from SL (SPSL) above 240 ℃. GC/MS analysis results show that compounds in the SPs are dominated in oxygen-containing organic species, especially the relative content of phenols is higher than 49%. The relative contents of alkenes, arenes, ethers, carboxylic acids, esters, organosulfur compounds (OSCs) in SPSL are higher, while the relative contents of alkanes, phenols, ketones and organonitrogen compounds in SPSL are lower than those in SPXLT. Additionally, the OSCs in SPSL and SPXLT are mainly composed of thiophenes and mercaptan, respectively. Many compounds with high polarity and low volatility which could not be identified by GC/MS were identified using ASAP/TOF-MS. The relative contents of CHO and CHS class species in SPSL are higher, but the relative contents of CHN, CHNO, CHOS, CHNS and CHNOS in SPSL are lower than those in SPXLT. The carbon number and double bond equivalent (DBE) of the compounds in SPSL and SPXLT mainly distribute in 0-10 and 3-15, respectively, while the distribution of carbon number and DBE of the compound in SPXLT are more concentrated than those in SPSL.-
Key words:
- lignite /
- thermal dissolution /
- GC/MS /
- ASAP/TOF-MS
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表 1 褐煤的工业分析和元素分析
Table 1 Proximate and ultimate analyses of coal samples
Sample Proximate analysis w/% Ultimate analysis wdaf/% Mad Ad Vdaf C H N S Oa SL 13.14 11.07 42.56 69.87 5.54 1.03 1.29 22.27 XLT 20.40 7.55 41.64 59.94 5.24 1.82 2.27 30.73 a: by difference 表 2 SPSL和SPXLT中GC/MS可检测到烃类化合物
Table 2 Hydrocarbons identified in SPSLand SPXLT by GC/MS
Compound RC /% Compound RC /% SPSL SPXLT SPSL SPXLT Alkanes arenes 2, 6, 10, 14-tetramethylhexadecane 0.28 - 4-isopropyl-1, 2-dimethylbenzene 0.22 - Pentadecane 0.55 0.16 2-methylnaphthalene 0.24 - Tetradecane 0.44 - 1, 2, 4-trimethyl-5-(prop-1-en-2-yl) benzene 0.12 - Heptadecane - 0.25 2, 3-dihydro-1, 1, 3-trimethyl-1 H-indene 0.12 - Octadecane 0.33 0.32 trimethyl-1 H-indene 0.40 - Nonadecane - 0.63 1, 3-dimethylnaphthalene 0.62 - Eicosane 0.27 0.59 1, 2, 3, 4-tetrahydro-1, 5, 0.20 - 7-trimethylnaphthalene Heneicosane 0.28 0.80 1, 2, 3, 4, 5, 6-hexamethylbenzene 0.49 0.38 Docosane - 0.64 1, 2, 4, 5-tetraethylbenzene 1.15 - Tricosane - 0.66 1-ethyl-3, 5-diisopropylbenzene 0.51 - Tetracosane 0.11 0.36 trimethylnaphthalene 0.29 0.29 Alkenes 9-ethylphenanthrene 0.40 - 1, 2, 3, 4, 5, 6-hexamethylcyclohexa-1, 0.42 - (1 S, 4 S)-4-isopropyl-1, 6-dimethyl-1, 2, 3, 0.83 - 3-diene 4-tetrahydronaphthalene 5, 5-dimethyl-1, 2-dipropylcyclopenta-1, 3-diene 1.08 0.40 4-isopropyl-1, 6-dimethylnaphthalene 0.64 0.80 Octadec-1-ene - 0.11 1, 2, 3, 4-tetramethylnaphthalene 0.40 - (E)-henicos-10-ene 0.12 - 5, 6, 7, 8-tetramethyl-1, 2, 3, 0.77 0.19 4-tetrahydronaphthalene 1, 4-di-tert-butylbenzene 0.26 - 表 3 SPSL和SPXLT中GC/MS可检测醇、酚和醚类化合物
Table 3 Alcohols, phenols and ethers identified in SPSL and SPXLT by GC/MS
Compound RC /% Compound RC /% SPSL SPXLT SPSL SPXLT Alcohols 4-sec-butylphenol 0.22 - 3, 3-dimethyl-2, 3-dihydro-1 H-inden-1-ol 0.56 - 2-methyl-6-propylphenol 0.31 - (4-tert-butylphenyl) methanol 1.18 - diethylphenol 0.61 - 3, 7, 11-trimethyldodecan-1-ol - 0.80 tetramethylphenol 12.20 6.73 Henicosan-1-ol - 0.15 2-methoxy-4-propylphenol 0.27 - Docosan-1-ol - 0.19 tert-butylmethylphenol 4.94 2.14 Phenols 2-ethyl-4, 5-dimethylphenol 1.90 Phenol 0.24 - 2, 3, 5-trimethylbenzene-1, 4-diol - 4.22 o-cresol 1.09 1.00 2-tert-butyl-4, 6-dimethylphenol 0.59 0.40 2-methoxyphenol 0.43 0.76 2, 6-diisopropylphenol - 2.05 Dimethylphenol 3.91 7.57 2-tert-butylbenzene-1, 4-diol - 0.82 3-isopropylphenol 0.72 0.34 (3 S, 3a S)-3a-methyl-3, 3a, 4, 5-tetrahydro 0.36 - -2 H-cyclopenta[a]naphthalen-3-ol Ethylphenol 0.64 - (R)-2, 5, 7, 8-tetramethyl-2-((4R, 8R)-4, 8, - 0.50 12-trimethyltridecyl) chroman-6-ol Methoxymethylphenol 1.44 1.30 ethers Ethylmethylphenol 1.34 0.78 dimethoxybenzene 0.32 - 4, 5-dimethylbenzene-1, 3-diol 0.26 - methoxytrimethylbenzene 0.16 0.09 Trimethylphenol 11.14 16.97 dimethoxymethylbenzene 0.59 0.43 2-propylphenol 0.26 - 1-tert-butyl-4-methoxybenzene 0.80 - 2-ethyl-4, 5-dimethylphenol - 1.92 5-propylbenzo[ d][1, 3]dioxole 0.95 - Isopropylmethylphenol 5.15 3.47 1-sec-butyl-4-methoxybenzene 0.74 - 3-tert-butylphenol - 2.55 1-isopropyl-2-methoxy-4-methylbenzene 2.78 - 2, 3, 5-trimethylbenzene-1, 4-diol 0.47 0.53 1, 2, 3-trimethoxy-5-methylbenzene 0.91 0.76 Methoxytrimethylphenol 0.99 1.41 2, 3-dihydro-2, 2, 5, 6-tetramethylbenzofuran - 1.17 表 4 SPSL和SPXLT中GC/MS可检测醛和酮类化合物
Table 4 Aldehydes and ketones identified in SPSL and SPXLT by GC/MS
Compound RC /% SPSL SPXLT Aldehydes 2-(2-methoxy-5-methylphenyl) propanal 0.60 - Ketones Trimethylcyclopent-2-enone 0.92 4.17 2, 3, 4, 5-tetramethylcyclopent-2-enone 0.69 1.04 3, 5, 5-trimethylcyclohex-2-enone - 0.63 1-(2, 6-dihydroxy-3-methylphenyl) ethanone 0.25 - 2, 3, 5, 6-tetramethylcyclohexa-2, 5-diene-1, 4-dione 0.35 0.43 1-(4-hydroxy-3-methoxyphenyl) ethanone 1.66 4.57 1-(2-hydroxy-4, 5-dimethylphenyl) ethanone 0.34 - 1-(2, 5-dimethoxyphenyl) ethanone - 0.18 Octahydro-2-(propan-2-ylidene) inden-4-one 0.56 0.49 1-(4-methoxyphenyl) butan-1-one 0.35 - 1-(5-hydroxy-2, 3, 4-trimethylphenyl) ethanone 1.26 - 2, 3-dihydro-3, 3, 5, 7-tetramethylinden-1-one 1.54 - 1-(3, 4-dichlorophenyl) ethanone 0.27 - 1-(2, 4, 5-triethylphenyl) ethanone 0.38 - 4, 4, 7, 8-tetramethylchroman-2-one - 0.37 表 5 SPSL和SPXLT中GC/MS可检测CAs和酯类化合物
Table 5 CAs and esters identified in SPSL和SPXLT by GC/MS
Compound RC /% Compound RC /% SPSL SPXLT SPSL SPXLT CAs methyl tetradecanoate - 0.25 2-methoxybenzoic acid 0.49 - methyl 2, 3-dihydro-1, 1-dimethyl-1 H- 1.08 - indene-4-carboxylate 4-isopropylbenzoic acid 0.57 0.49 methyl 9-methyltetradecanoate 0.48 - 4-acetylbenzoic acid 1.05 - methyl palmitate - 0.55 Esters methyl heptadecanoate - 0.19 Dimethyl succinate 0.15 - methyl stearate 0.15 0.67 Dimethyl glutarate 0.22 - methyl nonadecanoate - 0.19 2-isopropyl-5-methylphenyl acetate 0.36 - methyl 12-methyltetradecanoate 0.19 - Methyl decanoate 0.17 - methyl icosanoate - 0.30 Methyl 3-methoxybenzoate 0.24 - methyl 18-methylnonadecanoate 0.14 - Methyl undecanoate 0.23 - methyl henicosanoate - 0.31 Methyl 4-(1-hydroxyethyl) benzoate 0.30 - methyl docosanoate - 0.59 Methyl 4-methoxy-3-methylbenzoate 0.61 - methyl tricosanoate - 0.36 Methyl dodecanoate - 0.31 methyl tetracosanoate 0.18 0.70 Dimethyl nonanedioate 0.51 - methyl pentacosanoate - 0.17 Dimethyl decanedioate 0.26 - methyl hexacosanoate 0.32 0.58 Methyl 7-methylcyclopenta[c] 0.40 - methyl octacosanoate 0.21 0.34 pyran-4-carboxylate 表 6 SPSL和SPXLT中GC/MS可检测OSCs和ONCs
Table 6 OSCs and ONCs identified in SPSL和SPXLT by GC/MS
Compound RC /% SPSL SPXLT OSCs Isopropylbenzenethiol 0.19 1.48 2-ethyl-7-methylbenzo[ b]thiophene 0.75 - 2-ethyl-5, 7-dimethylbenzo[ b]thiophene 1.71 - Diethylbenzo[ b]thiophene 0.57 0.46 1-(dimethylbenzo[ b]thiophen-2-yl) ethanone 1.25 - ONCs N1-ethyl-N4, N4-dimethylbenzene-1, 4-diamine - 0.33 N1, N1-diethylbenzene-1, 4-diamine - 0.55 5-methyl-5, 6, 7, 8-tetrahydroquinazoline-2, 0.53 - 4(1 H, 3 H)-dione N1, N1, N4, N4-tetramethylbenzene-1, 7.15 10.50 4-diamine (E)-4-((isopropylimino) methyl)-N, - 2.84 N-dimethylaniline 2-benzyl-1-methyl-3-nitrobenzene 0.23 - (E)-N, N-diethyl-4-(4-nitrostyryl) aniline - 0.24 表 7 SPSL和SPXLT中ASAP/TOF-MS可检测化合物族分及其分布
Table 7 Compound classes and their distribution in SPSL and SPXLT identified by ASAP/TOF-MS
Compound class SPSL SPXLT relative peak intensity /% peak number relative peak intensity /% peak number CHO 7.17 11 34.29 17 CHN 13.64 18 7.33 19 CHNO 56.88 116 54.32 64 CHS 0.1 1 0.27 1 CHOS 2.01 4 0.05 1 CHNS 9.71 20 2.57 11 CHNOS 10.49 35 1.17 7 Total 100 205 100 120 -
[1] LI XH, XUE Y L, FENG J, YI Q, LI W Y, GUO X F, LIU K. Co-pyrolysis of lignite and shendong coal direct liquefaction residue[J]. Fuel, 2015, 144(15): 345-348. https://www.researchgate.net/publication/270517436_Co-pyrolysis_of_lignite_and_Shendong_coal_direct_liquefaction_residue [2] ASHIDA R, MORIMOTO M, MAKINO Y, UMEMOTO S, NAKAGAWA H, MIURA K, SAITO K, KATO K. Fractional of brown coal by sequential high temperature solvent extraction[J]. Fuel, 2009, 88(8): 1485-1490. doi: 10.1016/j.fuel.2008.12.003 [3] MAE K, SHINDO H, MIURA K. A new two-step oxidation degradation method for produceing valuable chemicals from low rank coals under mild conditions[J]. Energy Fuels, 2001, 15(3): 611-617. doi: 10.1021/ef000177e [4] 王知彩, 李良, 水恒福, 雷智平, 任世彪, 康士刚, 潘春秀.先锋褐煤热溶及热溶物红外光谱表征[J].燃料化学学报, 2011, 39(6): 401-406. doi: 10.1016/S1872-5813(11)60027-3WANG Zhi-cai, LI Liang, SHUI Heng-fu, LEI Zhi-ping, REN Shi-biao, KANG Shi-gang, PAN Chun-xiu. High temperature thermal extraction Xianfeng lignite and FT-IR characterization of its extracts and residues[J]. J Fuel Chem Technol, 2011, 39(6): 401-406. doi: 10.1016/S1872-5813(11)60027-3 [5] 潘春秀, 刘华龙, 祝婉婉, 李海平, 刘锦润, 魏贤勇, 水恒福, 王知彩.神府次烟煤在不同温度下的热溶产物表征[J].燃料化学学报, 2015, 43(4): 416-421. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18604.shtmlPAN Chun-xiu, LIU Hua-long, ZHU Wan-wan, LI Hai-ping, LIU Jin-run, WEI Xian-yong, SHUI Heng-fu, WANG Zhi-cai. Characterization of thermal dissolution products of a subbituminous coal at different temperatures[J]. J Fuel Chem Technol, 2015, 43(4): 416-421. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18604.shtml [6] DING M, ZHAO Y P, DOU Y Q, WEI X Y, FAN X, CAO J P, WANG Y L, ZONG Z M. Sequential extraction of thermal dissolution of shengli lignite[J]. Fuel Process Technol, 2015, 135(7): 20-24. https://www.researchgate.net/publication/276078810_Sequential_extraction_and_thermal_dissolution_of_Shengli_lignite [7] LU H Y, WEI X Y, YU R, PENG Y L, QI X Z, QIE L M. Sequential thermal dissolution of Huolinguole lignite in methanol and ethanol[J]. Energy Fuels, 2011, 25(6): 2741-2745. doi: 10.1021/ef101734f [8] CHEN B, WEI X Y, ZONG Z M, YANG Z S, QING Y, LIU C. Difference in chemical composition of supercritical methanolysis products between two lignites[J]. Appl Energy, 2011, 88(12): 4570-4576. doi: 10.1016/j.apenergy.2011.05.052 [9] GIVEN P H, MARZEC A, BARTON W A, LYNCH L J, GERSTEIN B C. The concept of a mobile or molecular phase within the macromolecular network of coal: A debate[J]. Fuel, 1986, 65(2): 155-163. doi: 10.1016/0016-2361(86)90001-3 [10] ZHAO Y P, HU H Q, JIN L J, WU B, ZHU S W. Pyrolysis behavior of weakly reductive coals from Northwest China[J]. Energy Fuels 2009, 23(2): 870-875. doi: 10.1021/ef800831y [11] 潘春秀, 魏贤勇, 李汉青, 水恒福, 王知彩, 祝婉婉, 赵智军, 宗志敏.先锋褐煤及其热溶残渣的过氧化氢氧解[J].燃料化学学报, 2013, 41(12): 1415-1421. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18306.shtmlPAN Chun-xiu, WEI Xian-yong, LI Han-qing, SHUI Heng-fu, WANG Zhi-cai, ZHU Wan-wan, ZHAO Zhi-jun, ZONG Zhi-min. H2O2 oxidation of Xianfeng lignite and its thermal extraction residue[J]. J Fuel Chem Technol, 2013, 41(12): 1415-1421. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18306.shtml [12] HODEK W, KIRSCHSTEIN J, VAN HEEK K H. Reactions of oxygen containing structures in coal pyrolysis[J]. Fuel, 1991, 70(3): 424-428. doi: 10.1016/0016-2361(91)90133-U [13] LI D, ZHANG C, XIA J, TAN P, YANG L, CHEN G. Evolution of organic sulfur in the thermal upgrading process of Shengli lignite[J]. Energy Fuels, 2013, 27(7): 3446-3453. https://www.researchgate.net/publication/263943704_Evolution_of_Organic_Sulfur_in_the_Thermal_Upgrading_Process_of_Shengli_Lignite [14] LI P, ZONG Z M, LIU F J, WANG Y G, WEI X Y, FAN X, ZHAO Y P, ZHAO W. Sequential extraction and characterization of liquefaction residue from Shenmu-Fugu subbituminous coal[J]. Fuel Process Technol, 2015, 136(8): 1-7. https://www.researchgate.net/publication/270872295_Sequential_extraction_and_characterization_of_liquefaction_residue_from_Shenmu-Fugu_subbituminous_coal [15] LIU F J, WEI X Y, LI W T, GUI J, LI P, WANG Y G, XIE R L, ZONG Z M. Methanolysis of extraction residue from Xianfeng lignite with NaOH and product characterizations with different spectrometries[J]. Fuel Process Technol, 2015, 136(8): 8-16. https://www.researchgate.net/publication/275167942_Methanolysis_of_extraction_residue_from_Xianfeng_lignite_with_NaOH_and_product_characterizations_with_different_spectrometries [16] HOURANI N, MULLER H, ADAM F M, PANA S K, WITT M, AL-HAJJJ A A, SARATHY S M. Structural level characterization of base oils using advanced analytical techniques[J]. Energy Fuels, 2015, 29(5): 2962-2970. doi: 10.1021/acs.energyfuels.5b00038