氯化亚铬脱除黄铁矿对桦甸油页岩有机质结构的影响
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摘要
采用元素分析、~(13)C NMR、XPS和TG-MS技术考察了氯化亚铬(CrCl_2)脱除黄铁矿对桦甸油页岩有机质结构的影响。结果表明,CrCl_2可有效脱除有机质中的黄铁矿,脱除率为96.19%。CrCl_2对有机质的碳骨架结构影响较小,脱除黄铁矿前后有机质中脂碳、芳碳和羧基/羰基碳的相对含量以及有机质的热解特征温度基本保持不变,但CrCl_2可破坏有机质中的C-O键,使C-O/C-OH和O=C-O的含量减少,造成0.98%的有机碳损失和12.54%的有机质损失。CrCl_2处理后,有机质的C含量显著增加,H含量稍有增加,O含量显著降低,使得H/C略微降低,O/C明显降低。另外,CrCl_2处理后,单位质量有机质中脂碳的含量增加了5.28%,使其热解过程中产生了更多的挥发分,残留的氧化铬对有机质的热分解可能也具有促进作用。
Influence of pyrite removal by chromous chloride( CrCl_2) on structure of organic matter in Huadian oil shale was examined using ultimate analysis,13 C NMR,XPS and TG-MS technology. The results showthat CrCl_2 treatment leads to 96.19% removal of pyrite from oil shale. The relative contents of aliphatic,aromatic,and carboxyl/carbonyl carbons of organic matter remain about the same level after pyrite removal by CrCl_2,so does the pyrolysis characteristic temperature,indicating the carbon skeleton of organic matter is less affected by CrCl_2. However,the CrCl_2 treatment can break C-O bond in organic matter and reduce content of C-O/C-OH and O = C-O,leading to about 0.98% and 12.54% loss for organic carbon and organic matter,respectively. In addition,carbon content of organic matter significantly increases,hydrogen content slightly increases,and oxygen content is markedly reduced after pyrite removal by CrCl_2,resulting in a slight decrease of H/C but a marked decrease of O/C in organic matter. The mass loss of organic matter treated by CrCl_2 increases during pyrolysis because aliphatic carbon content of unit mass of organic matter increases 5.28%. Besides,the residual chromium oxide may also promote decomposition of organic matter during pyrolysis.
Influence of pyrite removal by chromous chloride( CrCl_2) on structure of organic matter in Huadian oil shale was examined using ultimate analysis,13 C NMR,XPS and TG-MS technology. The results showthat CrCl_2 treatment leads to 96.19% removal of pyrite from oil shale. The relative contents of aliphatic,aromatic,and carboxyl/carbonyl carbons of organic matter remain about the same level after pyrite removal by CrCl_2,so does the pyrolysis characteristic temperature,indicating the carbon skeleton of organic matter is less affected by CrCl_2. However,the CrCl_2 treatment can break C-O bond in organic matter and reduce content of C-O/C-OH and O = C-O,leading to about 0.98% and 12.54% loss for organic carbon and organic matter,respectively. In addition,carbon content of organic matter significantly increases,hydrogen content slightly increases,and oxygen content is markedly reduced after pyrite removal by CrCl_2,resulting in a slight decrease of H/C but a marked decrease of O/C in organic matter. The mass loss of organic matter treated by CrCl_2 increases during pyrolysis because aliphatic carbon content of unit mass of organic matter increases 5.28%. Besides,the residual chromium oxide may also promote decomposition of organic matter during pyrolysis.
引文
[1]王擎,孙斌,刘洪鹏,柏静儒,肖冠华.油页岩热解过程矿物质行为分析[J].燃料化学学报,2013,41(2):163-168.(WANG Qing,SUN Bin,LIU Hong-peng,BAI Jing-ru,XIAO Guan-hua. Analysis of mineral behavior during pyrolysis of oil shale[J]. J Fuel Chem Technol,2013,41(2):163-168.)
[2]畅志兵,初茉,张超,白书霞,林浩.桦甸油页岩热解过程中热沥青的组成变化规律[J].燃料化学学报,2016,44(11):1310-1317.(CHANG Zhi-bing,CHU Mo,ZHANG Chao,BAI Shu-xia,LIN Hao. Variation of chemical composition of thermal bitumen during Huadian oil shale pyrolysis[J]. J Fuel Chem Technol,2016,44(11):1310-1317.)
[3] ORENDT A M,PIMIENTA I S,BADU S R,SOLUM M S,PUGMIRE R J,FACELLI J C,WINANS R E. Three-dimensional structure of the Siskin Green River Oil Shale Kerogen M odel:A comparison betw een calculated and observed properties[J]. Energy Fuels,2013,27(2):702-710.
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[5]王擎,许祥成,迟铭书,张宏喜,崔达,柏静儒.干酪根组成结构及其热解生油特性的红外光谱研究[J].燃料化学学报,2015,43(10):1158-1166.(WANG Qing,XU Xiang-cheng,CHI Ming-shu,ZHANG Hong-xi,CUI Da,BAI Jing-ru. FT-IR study on composition of oil shale kerogen and its pyrolysis oil generation characteristics[J]. J Fuel Chem Technol,2015,43(10):1158-1166.)
[6] TONG J H,HAN X X,WANG S,JIANG X M. Evaluation of structural characteristics of Huadian oil shale kerogen using direct techniques(solid-state13C NM R,XPS,FT-IR,and XRD)[J]. Energy Fuels,2011,25(9):4006-4013.
[7] WANG Q,HOU Y C,WU W Z,YU Z,REN S H,LIU Q Y,LIU Z Y. A study on the structure of Yilan oil shale kerogen based on its alkali-oxygen oxidation yields of benzene carboxylic acids,13C NM R and XPS[J]. Fuel Process Technol,2017,166:30-40.
[8]畅志兵,初茉,张超,白书霞,林浩,马良博.固有碳酸盐和硅酸盐对太姥油页岩热解产物的影响[J].化工学报,2017,68(4):1582-1589.(CHANG Zhi-bing,CHU Mo,ZHANG Chao,BAI Shu-xia,LIN Hao,MA Liang-bo. Influence of inherent carbonates and silicates on pyrolytic products of Tailao oil shale[J]. J Chem Ind Eng(China),2017,68(4):1582-1589.)
[9] BALLICE L. Effect of demineralization on yield and composition of the volatile products evolved from temperature-programmed pyrolysis of Beypazari(Turkey)oil shale[J]. Fuel Process Technol,2005,86(6):673-690.
[10] ZHAO X S,ZHANG X L,LIU Z Y,LU Z H,LIU Q Y. Organic matter in Yilan oil shale:Characterization and pyrolysis with or without inorganic minerals[J]. Energy Fuels,2017,31(4):3784-3792.
[11] YRM Y,DROR Y,LEVY M. Effect of acid dissolution on the mineral matrix and organic matter of Zefa Efe oil shale[J]. Fuel Process Technol,1985,11(1):71-86.
[12]迟铭书,王擎,李松阳,刘奇,查伯宇.酸洗对桦甸油页岩矿物质以及有机结构的影响[J].燃料化学学报,2017,45(12):1424-1433.(CHI Ming-shu,WANG Qing,LI Song-yang,LIU Qi,CHA Bo-yu. Influence of demineralization on minerals and organic structure in Huadian oil shale[J]. J Fuel Chem Technol,2017,45(12):1424-1433.)
[13] LARSEN J W,PAN C S,SHAWVER S. Effect of demineralization on the macromolecular structure of coals[J]. Energy Fuels,1989,3(5):557-561.
[14] GAI R H,JIN L J,ZHANG J B,WANG J Y,HU H Q. Effect of inherent and additional pyrite on the pyrolysis behavior of oil shale[J]. J Anal Appl Pyrolysis,2014,105:342-347.
[15] NEWTON R J,BOTTRELL S H,DEAN S P,HATFIELD D,RAISWELL R. An evaluation of the use of the chromous chloride reduction method for isotopic analyses of pyrite in rocks and sediment[J]. Chem Geol,1995,125(3/4):317-320.
[16] CANFIELD D E,RAISWELL R,WESTRICH J T,REAVES C M,BERNER R A. The use of chromium reduction in the analysis of reduced inorganic sulfur in sediments and shales[J]. Chem Geol,1986,54(1/2):149-155.
[17] ACHOLLA F V,ORR W L. Pyrite removal from kerogen without altering organic matter:The chromous chloride method[J]. Energy Fuels,1993,7(3):406-410.
[18] GALUKHIN A,GERASIMOV A,NIKOLAEV I,NOSOV R,OSIN Y. Pyrolysis of Kerogen of Bazhenov Shale:Kinetics and influence of inherent pyrite[J]. Energy Fuels,2017,31(7):6777-6781.
[19]周扬.依兰油页岩分级萃取物的结构研究[D].黑龙江:黑龙江科技学院,2011.(ZHOU Yang. Study on the structures of sequential extraction of Yi-lan oil-shale[D]. Heilongjiang:Heilongjiang University of Science and Technology,2011.)
[20] LIU Q,HOU Y C,WU W Z,WANG Q,REN S H,LIU Q Y. New insight into the chemical structures of Huadian kerogen with supercritical ethanolysis:Cleavage of w eak bonds to small molecular compounds[J]. Fuel Process Technol,2018,176:138-145.
[21]柏静儒,王擎,魏艳珍,关晓辉.桦甸油页岩的酸洗脱灰[J].中国石油大学学报(自然科学版),2010,34(2):150-153.(BAI Jing-ru,WANG Qing,WEI Yan-zhen,GUAN Xiao-hui. Acid treatment de-ashing of Huadian oilshal[J]. J China Univ Pet(Nat Sci Ed),2010,34(2):150-153.)
[22] CHANG Z B,CHU M,ZHANG C,BAI S X,LIN H,MA L B. Influence of inherent mineral matrix on the product yield and characterization from Huadian oil shale pyrolysis[J]. J Anal Appl Pyrolysis,2018,130:269-276.
[23] VANDENBROUCKE M,LARGEAU C. Kerogen origin,evolution and structure[J]. Org Geochem,2007,38(5):719-833.
[24]张晓亮.油页岩有机质结构组成及其热断裂行为研究[D].北京:北京化工大学,2015.(ZHANG Xiao-liang. Study on sturcture composition and thermal fracture behavior of oil shale organic matter[D]. Beijing:Beijing University of Chemical Technology,2015.)
[25] ABOULKAS A,EL HARFI K. Effects of acid treatments on Moroccan Tarfaya oil shale and pyrolysis of oil shale and their kerogen[J]. J Fuel Chem Technol,2009,37(6):659-667.
[26]刘建忠,齐庆杰,周俊虎,曹欣玉,岑可法.煤中氟化物在燃烧产物中的分布特征[J].环境科学,2003,24(4):127-130.(LIU Jian-zhong,QI Qing-jie,ZHOU Jun-hu,CAO Xin-yu,CEN Ke-fa. Distribution of fluoride in the combustion products of coal[J].Environ Sci,2003,24(4):127-130.)
[27]蒋旭光,徐旭,严建华,何杰,池涌,岑可法.煤燃烧过程中氯析出特性的试验研究[J].煤炭学报,2002,27(4):398-401.(JIANG Xu-guang,XU Xu,YAN Jian-hua,HE Jie,CHI Yong,CEN Ke-fa. Experimental study on the release characteristic of chlorine in coal combustion process[J]. J China Coal Soc,2002,27(4):398-401.)
[28] GELINAS Y,BALDOCK J A,HEDGES J I. Demineralization of marine and freshwater sediments for CP/MAS 13C NMR analysis[J]. Org Geochem,2001,32(5):677-693.
[29] ZHAO X S,LIU Z Y,LU Z H,SHI L,LIU Q Y. A study on average molecular structure of eight oil shale organic matters and radical information during pyrolysis[J]. Fuel,2018,219:399-405.
[30] HILLIER J L,FLETCHER T H,SOLUM M S,PUGMIRE R J. Characterization of macromolecular structure of pyrolysis products from a Colorado Green River oil shale[J]. Ind Eng Chem Res,2013,52(44):15522-15532.
[31] KOSATEVA A,STEFANOVA M,MARINOV S,CZECH J,CARLEER R,YPERMAN J. Characterization of organic components in leachables from Bulgarian lignites by spectroscopy,chromatography and reductive pyrolysis[J]. Int J Coal Geol,2017,183:100-109.
[32] LI Q Y,HAN X X,LIU Q Q,JIANG X M. Thermal decomposition of Huadian oil shale. Part 1. Critical organic intermediates[J]. Fuel,2014,121:109-116.
[33]石剑,李术元,马跃.爱沙尼亚油页岩及其热解产物的电子顺磁共振研究[J].燃料化学学报,2018,46(1):1-7.(SHI Jian,LI Shu-yuan,MA Yue. Electron paramagnetic resonance(EPR)properties of Estonia oil shale and its pyrolysates[J]. J Fuel Chem Technol,2018,46(1):1-7.)
[34] PAN L W,DAI F Q,HUANG J N,LIU S,LI G Q. Study of the effect of mineral matters on the thermal decomposition of Jimsar oil shale using TG-M S[J]. Thermochim Acta,2016,627:31-38.
[35] TORRENTE M C,GALAN M A. Kinetics of the thermal decomposition of oil shale from Puertollano(Spain)[J]. Fuel,2001,80(3):327-334.
[2]畅志兵,初茉,张超,白书霞,林浩.桦甸油页岩热解过程中热沥青的组成变化规律[J].燃料化学学报,2016,44(11):1310-1317.(CHANG Zhi-bing,CHU Mo,ZHANG Chao,BAI Shu-xia,LIN Hao. Variation of chemical composition of thermal bitumen during Huadian oil shale pyrolysis[J]. J Fuel Chem Technol,2016,44(11):1310-1317.)
[3] ORENDT A M,PIMIENTA I S,BADU S R,SOLUM M S,PUGMIRE R J,FACELLI J C,WINANS R E. Three-dimensional structure of the Siskin Green River Oil Shale Kerogen M odel:A comparison betw een calculated and observed properties[J]. Energy Fuels,2013,27(2):702-710.
[4] GUAN X H,LIU Y,WANG D,WANG Q,CHI M S,LIU S,LIU C G. Three-dimensional structure of a huadian oil shale kerogen model:An experimental and theoretical study[J]. Energy Fuels,2015,29(7):4122-4136.
[5]王擎,许祥成,迟铭书,张宏喜,崔达,柏静儒.干酪根组成结构及其热解生油特性的红外光谱研究[J].燃料化学学报,2015,43(10):1158-1166.(WANG Qing,XU Xiang-cheng,CHI Ming-shu,ZHANG Hong-xi,CUI Da,BAI Jing-ru. FT-IR study on composition of oil shale kerogen and its pyrolysis oil generation characteristics[J]. J Fuel Chem Technol,2015,43(10):1158-1166.)
[6] TONG J H,HAN X X,WANG S,JIANG X M. Evaluation of structural characteristics of Huadian oil shale kerogen using direct techniques(solid-state13C NM R,XPS,FT-IR,and XRD)[J]. Energy Fuels,2011,25(9):4006-4013.
[7] WANG Q,HOU Y C,WU W Z,YU Z,REN S H,LIU Q Y,LIU Z Y. A study on the structure of Yilan oil shale kerogen based on its alkali-oxygen oxidation yields of benzene carboxylic acids,13C NM R and XPS[J]. Fuel Process Technol,2017,166:30-40.
[8]畅志兵,初茉,张超,白书霞,林浩,马良博.固有碳酸盐和硅酸盐对太姥油页岩热解产物的影响[J].化工学报,2017,68(4):1582-1589.(CHANG Zhi-bing,CHU Mo,ZHANG Chao,BAI Shu-xia,LIN Hao,MA Liang-bo. Influence of inherent carbonates and silicates on pyrolytic products of Tailao oil shale[J]. J Chem Ind Eng(China),2017,68(4):1582-1589.)
[9] BALLICE L. Effect of demineralization on yield and composition of the volatile products evolved from temperature-programmed pyrolysis of Beypazari(Turkey)oil shale[J]. Fuel Process Technol,2005,86(6):673-690.
[10] ZHAO X S,ZHANG X L,LIU Z Y,LU Z H,LIU Q Y. Organic matter in Yilan oil shale:Characterization and pyrolysis with or without inorganic minerals[J]. Energy Fuels,2017,31(4):3784-3792.
[11] YRM Y,DROR Y,LEVY M. Effect of acid dissolution on the mineral matrix and organic matter of Zefa Efe oil shale[J]. Fuel Process Technol,1985,11(1):71-86.
[12]迟铭书,王擎,李松阳,刘奇,查伯宇.酸洗对桦甸油页岩矿物质以及有机结构的影响[J].燃料化学学报,2017,45(12):1424-1433.(CHI Ming-shu,WANG Qing,LI Song-yang,LIU Qi,CHA Bo-yu. Influence of demineralization on minerals and organic structure in Huadian oil shale[J]. J Fuel Chem Technol,2017,45(12):1424-1433.)
[13] LARSEN J W,PAN C S,SHAWVER S. Effect of demineralization on the macromolecular structure of coals[J]. Energy Fuels,1989,3(5):557-561.
[14] GAI R H,JIN L J,ZHANG J B,WANG J Y,HU H Q. Effect of inherent and additional pyrite on the pyrolysis behavior of oil shale[J]. J Anal Appl Pyrolysis,2014,105:342-347.
[15] NEWTON R J,BOTTRELL S H,DEAN S P,HATFIELD D,RAISWELL R. An evaluation of the use of the chromous chloride reduction method for isotopic analyses of pyrite in rocks and sediment[J]. Chem Geol,1995,125(3/4):317-320.
[16] CANFIELD D E,RAISWELL R,WESTRICH J T,REAVES C M,BERNER R A. The use of chromium reduction in the analysis of reduced inorganic sulfur in sediments and shales[J]. Chem Geol,1986,54(1/2):149-155.
[17] ACHOLLA F V,ORR W L. Pyrite removal from kerogen without altering organic matter:The chromous chloride method[J]. Energy Fuels,1993,7(3):406-410.
[18] GALUKHIN A,GERASIMOV A,NIKOLAEV I,NOSOV R,OSIN Y. Pyrolysis of Kerogen of Bazhenov Shale:Kinetics and influence of inherent pyrite[J]. Energy Fuels,2017,31(7):6777-6781.
[19]周扬.依兰油页岩分级萃取物的结构研究[D].黑龙江:黑龙江科技学院,2011.(ZHOU Yang. Study on the structures of sequential extraction of Yi-lan oil-shale[D]. Heilongjiang:Heilongjiang University of Science and Technology,2011.)
[20] LIU Q,HOU Y C,WU W Z,WANG Q,REN S H,LIU Q Y. New insight into the chemical structures of Huadian kerogen with supercritical ethanolysis:Cleavage of w eak bonds to small molecular compounds[J]. Fuel Process Technol,2018,176:138-145.
[21]柏静儒,王擎,魏艳珍,关晓辉.桦甸油页岩的酸洗脱灰[J].中国石油大学学报(自然科学版),2010,34(2):150-153.(BAI Jing-ru,WANG Qing,WEI Yan-zhen,GUAN Xiao-hui. Acid treatment de-ashing of Huadian oilshal[J]. J China Univ Pet(Nat Sci Ed),2010,34(2):150-153.)
[22] CHANG Z B,CHU M,ZHANG C,BAI S X,LIN H,MA L B. Influence of inherent mineral matrix on the product yield and characterization from Huadian oil shale pyrolysis[J]. J Anal Appl Pyrolysis,2018,130:269-276.
[23] VANDENBROUCKE M,LARGEAU C. Kerogen origin,evolution and structure[J]. Org Geochem,2007,38(5):719-833.
[24]张晓亮.油页岩有机质结构组成及其热断裂行为研究[D].北京:北京化工大学,2015.(ZHANG Xiao-liang. Study on sturcture composition and thermal fracture behavior of oil shale organic matter[D]. Beijing:Beijing University of Chemical Technology,2015.)
[25] ABOULKAS A,EL HARFI K. Effects of acid treatments on Moroccan Tarfaya oil shale and pyrolysis of oil shale and their kerogen[J]. J Fuel Chem Technol,2009,37(6):659-667.
[26]刘建忠,齐庆杰,周俊虎,曹欣玉,岑可法.煤中氟化物在燃烧产物中的分布特征[J].环境科学,2003,24(4):127-130.(LIU Jian-zhong,QI Qing-jie,ZHOU Jun-hu,CAO Xin-yu,CEN Ke-fa. Distribution of fluoride in the combustion products of coal[J].Environ Sci,2003,24(4):127-130.)
[27]蒋旭光,徐旭,严建华,何杰,池涌,岑可法.煤燃烧过程中氯析出特性的试验研究[J].煤炭学报,2002,27(4):398-401.(JIANG Xu-guang,XU Xu,YAN Jian-hua,HE Jie,CHI Yong,CEN Ke-fa. Experimental study on the release characteristic of chlorine in coal combustion process[J]. J China Coal Soc,2002,27(4):398-401.)
[28] GELINAS Y,BALDOCK J A,HEDGES J I. Demineralization of marine and freshwater sediments for CP/MAS 13C NMR analysis[J]. Org Geochem,2001,32(5):677-693.
[29] ZHAO X S,LIU Z Y,LU Z H,SHI L,LIU Q Y. A study on average molecular structure of eight oil shale organic matters and radical information during pyrolysis[J]. Fuel,2018,219:399-405.
[30] HILLIER J L,FLETCHER T H,SOLUM M S,PUGMIRE R J. Characterization of macromolecular structure of pyrolysis products from a Colorado Green River oil shale[J]. Ind Eng Chem Res,2013,52(44):15522-15532.
[31] KOSATEVA A,STEFANOVA M,MARINOV S,CZECH J,CARLEER R,YPERMAN J. Characterization of organic components in leachables from Bulgarian lignites by spectroscopy,chromatography and reductive pyrolysis[J]. Int J Coal Geol,2017,183:100-109.
[32] LI Q Y,HAN X X,LIU Q Q,JIANG X M. Thermal decomposition of Huadian oil shale. Part 1. Critical organic intermediates[J]. Fuel,2014,121:109-116.
[33]石剑,李术元,马跃.爱沙尼亚油页岩及其热解产物的电子顺磁共振研究[J].燃料化学学报,2018,46(1):1-7.(SHI Jian,LI Shu-yuan,MA Yue. Electron paramagnetic resonance(EPR)properties of Estonia oil shale and its pyrolysates[J]. J Fuel Chem Technol,2018,46(1):1-7.)
[34] PAN L W,DAI F Q,HUANG J N,LIU S,LI G Q. Study of the effect of mineral matters on the thermal decomposition of Jimsar oil shale using TG-M S[J]. Thermochim Acta,2016,627:31-38.
[35] TORRENTE M C,GALAN M A. Kinetics of the thermal decomposition of oil shale from Puertollano(Spain)[J]. Fuel,2001,80(3):327-334.