固态~(13)C-NMR法表征渣油沥青质的结构组成
|
摘要
以长庆常压渣油、胜利减压渣油和加拿大减压渣油为原料,研究了正庚烷沥青质的结构及组成,根据固态~(13)C-NMR分析结果,计算了沥青质分子的平均结构单元参数,并模拟出了沥青质的结构单元模型。结果表明,沥青质分子由4个左右的结构单元组成,每个结构单元包括5～7个缩合芳香环。沥青质中的饱和碳以环烷碳为主,并包含少量的短烷基侧链,沥青质的n(HS)/n(CS)在1.6左右。对于平均相对分子质量较大、具有较短烷基侧链和较少取代基的沥青质分子,由核磁共振氢谱计算其结构参数时,采用重油计算过程的假设——芳香环烷基侧链上α位及β位和β位以远的氢/碳比为2(x=y=2)是不合理的,可能会导致计算结果与沥青质的真实结构存在较大的误差。
The structure and composition of n-heptane asphaltenes from Changqing atmospheric residue,Shengli vacuum residue and Canadian vacuum residue were studied with using solid-state ~(13)C-NMR.Based on solid-state ~(13)C-NMR characterization results,the average structure unit parameters of asphaltenes were calculated,and asphaltene structure unit model was simulated.Experimental and calculation results indicate that asphaltene molecules consist of about 4 structure units,each containing 5 to 7 ploy-aromatic rings.For saturated carbons in asphaltenes,there are mainly naphthenic carbons with a few short alkyl side chains.For asphaltenes with large average relative molecular mass,short alkyl side chains and less substituents,n(HS)/n(CS)of asphaltene is about 1.6.This indicates that there is a large error in the calculation of asphaltene structure parameters by following heavy oil calculation procedures,which assumes that n(H)/n(C)ofα,βand other alkyl side chains in aromatic rings is 2.
The structure and composition of n-heptane asphaltenes from Changqing atmospheric residue,Shengli vacuum residue and Canadian vacuum residue were studied with using solid-state ~(13)C-NMR.Based on solid-state ~(13)C-NMR characterization results,the average structure unit parameters of asphaltenes were calculated,and asphaltene structure unit model was simulated.Experimental and calculation results indicate that asphaltene molecules consist of about 4 structure units,each containing 5 to 7 ploy-aromatic rings.For saturated carbons in asphaltenes,there are mainly naphthenic carbons with a few short alkyl side chains.For asphaltenes with large average relative molecular mass,short alkyl side chains and less substituents,n(HS)/n(CS)of asphaltene is about 1.6.This indicates that there is a large error in the calculation of asphaltene structure parameters by following heavy oil calculation procedures,which assumes that n(H)/n(C)ofα,βand other alkyl side chains in aromatic rings is 2.
引文
[1]王子军,阙国和.减压渣油中胶状沥青状物质的化学结构研究[J].石油学报(石油加工),1999,15(6):39-46.(WANG Zijun, QUE Guohe.Investigation on chemical structure of resins and pentane asphaltenes in vacuum residue[J].Acta Petrolei Sinica(Petroleum Processing Section),1999,15(6):39-46.)
[2]张庆,邓文安,李传,等.稠油沥青质的基本化学组成结构与缔合性研究[J].石油炼制与化工,2014,45(6):20-25.(ZHANG Qing, DENG Wenan,LI Chuan,et al.Study on basic chemical structure and association of asphaltene in heavy oil[J].Petroleum Processing and Petrochemicals,2014,45(6):20-25.)
[3]CHEN C,GAO J,YAN Y.Observation of the type of hydrogen bonds in coal by FTIR[J].Energy&Fuels,1998,12(3):446-449.
[4]商红岩,韩哲茵,冀勇.中间相沥青显微结构的研究[J].石油沥青,1998,12(2):25-28.(SHANG Hongyan,HAN Zheyin,JI Yong,et al.Research on the micro-structures of mesophase pitch[J].Asphal,1998,12(2):25-28.)
[5]王逗.核磁共振原理及其应用[J].现代物理知识,2005,17(5):50-51.(WANG Dou.Principle and application of nuclear magnetic resonance[J].Modern Physical Knowledge,2005,17(5):50-51.)
[6]张会成,马波,孟雪松,等.NMR波谱解析渣油组分的化学结构[J].石油学报(石油加工),2011,27(6):941-945.(ZHANGHuicheng, MABo, MENG Xuesong,et al.Analysis for chemical structures of residue by NMR[J].Acta Petrolei Sinica(Petroleum Processing Section),2011,27(6):941-945.)
[7]张强,孙昱东,杨朝合,等.超声波处理对加氢反应前后沥青质单元分子结构的影响[J].燃料化学学报,2014,42(1):48-54.(ZHANG Qiang,SUN Yudong,YANG Chaohe,et al.Effect of ultrasonic treatment on the unit structure ofpre-andpost-hydrotreating asphaltene[J]. Journal of Fuel Chemistry and Technology,2014,42(1):48-54.)
[8]ESCALIER J C, BOULETt R, COLIN J M.Characterization of heavy crude oils and petroleum residues[C]//195th Amer Chem Soc Nat Mtg 3rd Amer Chem Congr,1988.
[9]李红,原雯,郑焕云.VPO法测定石油产品中分子量[J].化学工程师,2011,25(12):29-30.(LI Hong,YUAN Wen,ZHENG Huanyun. Determination of molecular weight in petroleum products by VPO method[J].Chemical Engineer,2011,25(12):29-30.)
[10]Poveda J C,Molina D R.Average molecular parameters of heavy crude oils and their fractions using NMR spectroscopy[J].Journal of Petroleum Science and Engineering,2012,84:1-7.
[11]王擎,王智超,贾春霞,等.基于固体13 C核磁共振技术对油砂沥青质结构的研究[J].化工进展,2014,33(6):1392-1396.(WANG Qing,WANG Zhichao,JIA Chunxia,et al.Study on structural features of oil sand with solid state 13 C NMR[J].Chemical Induetry and Engineering Process,2014,33(6):1392-1396.)
[12]董喜贵,雷群芳,俞庆森.石油沥青质的NMR测定及其模型分子推测[J].燃料化学学报,2004,32(6):668-672.(DONG Xigun,LEI Qunfang,YU Qingsen.NMR determination of petroleum asphaltenes and their model molecules evaluation[J]. Journal of Fuel Chemistry and Technology,2004,32(6):668-672.)
[13]王子军,梁文杰.减压渣油组分中芳环数分布的同步荧光光谱研究[J].石油学报(石油加工),1999,15(4):67-71.(WANG Zijun,LIANG Wenjie.Studies on contributions of aromatic rings of vacuum residue fractions by synchronous fluorescence spectroscopy[J].Acta Petrolei Sinica(Petroleum Processing Section),1999,15(4):67-71.)
[14]CLUTTER D R,PETRAKIS L,STENGER J R R L,et al. Nuclear magnetic resonance spectrometry of petroleum fractions. Carbon-13 and proton nuclear magnetic resonance characterizations in terms of average molecule parameters[J].Analytical Chemistry,1972,44(8):1395-1405.
[15]水恒福,沈本贤,高晋生,等.1 H-NMR和IR对道路沥青老化过程的研究[J].华东理工大学学报:自然科学版,1998,24(4):405-409.(SHUI Hengfu,SHEN Benxian,GAO Jinsheng,et al.Study on the aging process of paving asphalt with 1 H-NMR an IR[J].Journal of East China university of Science and Technology,1998,24(4):405-409.)
[16]孙昱东,杨朝合,山红红,等.渣油加氢转化过程中沥青质结构单元的变化[J].石油学报(石油加工),2010,26(S):191-197.(SUN Yudong,YANG Chaohe,SHAN Honghong, et al. Structure changes of asphaltene units in residue hydrotreating[J]. Acta Petrolei Sinica(Petroleum Processing Section),2010,26(S):191-197.)
[2]张庆,邓文安,李传,等.稠油沥青质的基本化学组成结构与缔合性研究[J].石油炼制与化工,2014,45(6):20-25.(ZHANG Qing, DENG Wenan,LI Chuan,et al.Study on basic chemical structure and association of asphaltene in heavy oil[J].Petroleum Processing and Petrochemicals,2014,45(6):20-25.)
[3]CHEN C,GAO J,YAN Y.Observation of the type of hydrogen bonds in coal by FTIR[J].Energy&Fuels,1998,12(3):446-449.
[4]商红岩,韩哲茵,冀勇.中间相沥青显微结构的研究[J].石油沥青,1998,12(2):25-28.(SHANG Hongyan,HAN Zheyin,JI Yong,et al.Research on the micro-structures of mesophase pitch[J].Asphal,1998,12(2):25-28.)
[5]王逗.核磁共振原理及其应用[J].现代物理知识,2005,17(5):50-51.(WANG Dou.Principle and application of nuclear magnetic resonance[J].Modern Physical Knowledge,2005,17(5):50-51.)
[6]张会成,马波,孟雪松,等.NMR波谱解析渣油组分的化学结构[J].石油学报(石油加工),2011,27(6):941-945.(ZHANGHuicheng, MABo, MENG Xuesong,et al.Analysis for chemical structures of residue by NMR[J].Acta Petrolei Sinica(Petroleum Processing Section),2011,27(6):941-945.)
[7]张强,孙昱东,杨朝合,等.超声波处理对加氢反应前后沥青质单元分子结构的影响[J].燃料化学学报,2014,42(1):48-54.(ZHANG Qiang,SUN Yudong,YANG Chaohe,et al.Effect of ultrasonic treatment on the unit structure ofpre-andpost-hydrotreating asphaltene[J]. Journal of Fuel Chemistry and Technology,2014,42(1):48-54.)
[8]ESCALIER J C, BOULETt R, COLIN J M.Characterization of heavy crude oils and petroleum residues[C]//195th Amer Chem Soc Nat Mtg 3rd Amer Chem Congr,1988.
[9]李红,原雯,郑焕云.VPO法测定石油产品中分子量[J].化学工程师,2011,25(12):29-30.(LI Hong,YUAN Wen,ZHENG Huanyun. Determination of molecular weight in petroleum products by VPO method[J].Chemical Engineer,2011,25(12):29-30.)
[10]Poveda J C,Molina D R.Average molecular parameters of heavy crude oils and their fractions using NMR spectroscopy[J].Journal of Petroleum Science and Engineering,2012,84:1-7.
[11]王擎,王智超,贾春霞,等.基于固体13 C核磁共振技术对油砂沥青质结构的研究[J].化工进展,2014,33(6):1392-1396.(WANG Qing,WANG Zhichao,JIA Chunxia,et al.Study on structural features of oil sand with solid state 13 C NMR[J].Chemical Induetry and Engineering Process,2014,33(6):1392-1396.)
[12]董喜贵,雷群芳,俞庆森.石油沥青质的NMR测定及其模型分子推测[J].燃料化学学报,2004,32(6):668-672.(DONG Xigun,LEI Qunfang,YU Qingsen.NMR determination of petroleum asphaltenes and their model molecules evaluation[J]. Journal of Fuel Chemistry and Technology,2004,32(6):668-672.)
[13]王子军,梁文杰.减压渣油组分中芳环数分布的同步荧光光谱研究[J].石油学报(石油加工),1999,15(4):67-71.(WANG Zijun,LIANG Wenjie.Studies on contributions of aromatic rings of vacuum residue fractions by synchronous fluorescence spectroscopy[J].Acta Petrolei Sinica(Petroleum Processing Section),1999,15(4):67-71.)
[14]CLUTTER D R,PETRAKIS L,STENGER J R R L,et al. Nuclear magnetic resonance spectrometry of petroleum fractions. Carbon-13 and proton nuclear magnetic resonance characterizations in terms of average molecule parameters[J].Analytical Chemistry,1972,44(8):1395-1405.
[15]水恒福,沈本贤,高晋生,等.1 H-NMR和IR对道路沥青老化过程的研究[J].华东理工大学学报:自然科学版,1998,24(4):405-409.(SHUI Hengfu,SHEN Benxian,GAO Jinsheng,et al.Study on the aging process of paving asphalt with 1 H-NMR an IR[J].Journal of East China university of Science and Technology,1998,24(4):405-409.)
[16]孙昱东,杨朝合,山红红,等.渣油加氢转化过程中沥青质结构单元的变化[J].石油学报(石油加工),2010,26(S):191-197.(SUN Yudong,YANG Chaohe,SHAN Honghong, et al. Structure changes of asphaltene units in residue hydrotreating[J]. Acta Petrolei Sinica(Petroleum Processing Section),2010,26(S):191-197.)