印尼油砂沥青组成及化学结构分析
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摘要
利用FTIR和~(13)C NMR对印尼油砂沥青中的脂肪烃结构、芳香烃结构、含氧官能团以及碳骨架进行研究,并就印尼油砂样品中较高的硫含量进行XPS分析。结果表明:4个印尼油砂样品沥青中脂肪碳含量均占到了70%左右,脂肪烃主要由亚甲基构成,甲基与次甲基次之,样品中有大量的烷基侧链。FTIR无法准确分辨芳香烃部分的苯环取代结构,通过~(13)C NMR发现芳香烃中质子化芳碳的含量较高,桥头芳碳与侧枝芳碳为主要非质子化芳碳,由带质子化芳碳的比例大小可以推断样品芳香环上的取代度为2～4。样品含氧官能团部分以C-O形式存在于醇和醚中,部分以羧基形式存在。样品中硫主要为有机硫,芳香族硫化物含量最高,其次为脂肪族硫化物,存在一定比例亚砜。无机硫以黄铁矿硫与硫酸盐硫形式存在,由于油砂表面被有机质包裹,无机物裸露较少,XPS没有测得硫酸盐硫,黄铁矿硫的检测值也偏低。
The FTIR and ~(13)C NMR were used to study the aliphatic hydrocarbon structure, aromatic hydrocarbon structure, oxygen-containing functional groups and carbon skeleton in Indonesian oil sands bitumen. The sulfur content was subjected to XPS analysis. The results showed that the content of aliphatic carbon in the bitumen of the four Indonesian oil sand samples accounted for about 70%. The aliphatic hydrocarbons were mainly composed of methylene groups, followed by methyl and methine groups, and there were a large number of alkyl side chains in the samples. FTIR could not accurately distinguish the benzene ring substitution structure of aromatic hydrocarbons. The content of protonated aromatic carbon in aromatic hydrocarbons was found by ~(13)C NMR. The bridgehead aromatic carbon and side branch aromatic carbon were the main non-protonated aromatic carbons, which were protonated aromatic carbon. The ratio can be inferred to have a degree of substitution of 2 to 4 on the aromatic ring of the sample. The oxygen-containing functional moiety of the sample was present in the alcohol and ether in the form of C—O and partially in the form of a carboxyl group. The sulfur in the sample was mainly organic sulfur, and the aromatic sulfide content was the highest, followed by the aliphatic sulfide with a certain proportion of sulfoxide exists. Inorganic sulfur existed in the form of pyrite sulfur and sulfate sulfur. Since the surface of the oil sand was encapsulated by organic matter, the inorganic matter was less exposed. XPS analysis did not detect sulfate sulfur and the detection value of pyrite sulfur was also low.
The FTIR and ~(13)C NMR were used to study the aliphatic hydrocarbon structure, aromatic hydrocarbon structure, oxygen-containing functional groups and carbon skeleton in Indonesian oil sands bitumen. The sulfur content was subjected to XPS analysis. The results showed that the content of aliphatic carbon in the bitumen of the four Indonesian oil sand samples accounted for about 70%. The aliphatic hydrocarbons were mainly composed of methylene groups, followed by methyl and methine groups, and there were a large number of alkyl side chains in the samples. FTIR could not accurately distinguish the benzene ring substitution structure of aromatic hydrocarbons. The content of protonated aromatic carbon in aromatic hydrocarbons was found by ~(13)C NMR. The bridgehead aromatic carbon and side branch aromatic carbon were the main non-protonated aromatic carbons, which were protonated aromatic carbon. The ratio can be inferred to have a degree of substitution of 2 to 4 on the aromatic ring of the sample. The oxygen-containing functional moiety of the sample was present in the alcohol and ether in the form of C—O and partially in the form of a carboxyl group. The sulfur in the sample was mainly organic sulfur, and the aromatic sulfide content was the highest, followed by the aliphatic sulfide with a certain proportion of sulfoxide exists. Inorganic sulfur existed in the form of pyrite sulfur and sulfate sulfur. Since the surface of the oil sand was encapsulated by organic matter, the inorganic matter was less exposed. XPS analysis did not detect sulfate sulfur and the detection value of pyrite sulfur was also low.
引文
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[14]王擎,许祥成,迟铭书,等.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 Xiangcheng, CHI Mingshu, et al. FTIR study on the composition and structure of kerogen and its pyrolysis oil generation characteristics[J]. Journal of Fuel Chemistry and Technology, 2015, 43(10):1158-1166.
[15] KELEMEN S R, GEORGE G N, GORBATY M L. Direct determination and quantification of sulphur forms in heavy petroleum and coals:1.The X-ray photoelectron spectroscopy(XPS)approach[J]. Fuel, 1990,69(8):939-944.
[16]葛涛,张明旭,马祥梅.新阳炼焦煤结构的FTIR和XPS谱学表征[J].光谱学与光谱分析, 2017, 37(8):2406-2411.GE Tao, ZHANG Mingxu, MA Xiangmei. FTIR and XPS spectroscopic characterization of coking coal structure in Xinyang[J]. Spectroscopy and Spectral Analysis, 2017, 37(8):2406-2411.
[17]朱子彬,朱宏斌,吴勇强,等.烟煤快速加氢热解的研究[J].燃料化学学报, 2001, 29(1):44-48.ZHU Zibin, ZHU Hongbin, WU Yongqiang, et al. Study on the rapid hydropyrolysis of bituminous coal[J]. Journal of Fuel Chemistry and Technology, 2001, 29(1):44-48.
[18]李梅,杨俊和,张启锋,等.用XPS研究新西兰高硫煤热解过程中氮、硫官能团的转变规律[J].燃料化学学报, 2013, 41(11):1287-1293.LI Mei, YANG Junhe, ZHANG Qifeng, et al. XPS was used to study the transformation of nitrogen and sulfur functional groups during pyrolysis of high sulfur coal in New Zealand[J]. Journal of Fuel Chemistry and Technology, 2013, 41(11):1287-1293.
[19]罗宽勇,韩冬云,李福起,等.印尼油砂沥青的净化工艺[J].化工进展, 2016, 35(12):3885-3890.LUO Kuanyong, HAN Dongyun, LI Fuqi, et al. Purification process of oil sand asphalt in Indonesia[J]. Chemical Industry and Engineering Progress, 2016, 35(12):3885-3890.
[20]韩峰,张衍国,蒙爱红,等.云南褐煤结构的FTIR分析[J].煤炭学报, 2014, 39(11):2293-2299.HAN Feng, ZHANG Yanguo, MENG Aihong, et al. FTIR analysis of lignite structure in Yunnan[J]. Journal of China Coal Society, 2014, 39(11):2293-2299.
[21]刘粉荣,李文,郭慧卿,等. XPS法研究煤表面碳官能团的变化及硫迁移行为[J].燃料化学学报, 2011, 39(2):81-84.LIU Fanrong, LI Wen, GUO Huiqing, et al. XPS study on the changes of carbon functional groups and sulfur migration behavior on coal surface[J]. Journal of Fuel Chemistry and Technology, 2011, 39(2):81-84.
[22]陈丽诗,王岚岚,潘铁英,等.固体核磁碳结构参数的修正及其在煤结构分析中的应用[J].燃料化学学报, 2017, 45(10):1153-1163.CHEN Lishi, WANG Lanlan, PAN Tieying, et al. Modification of structural parameters of solid nuclear magnetic carbon and its application in coal structural analysis[J]. Journal of Fuel Chemistry and Technology, 2017, 45(10):1153-1163.
[23]马玲玲,秦志宏,张露,等.煤有机硫分析中XPS分峰拟合方法及参数设置[J].燃料化学学报, 2014, 42(3):277-283.MA Lingling, QIN Zhihong, ZHANG Lu, et al. XPS peak fitting method and parameter setting for coal organic sulfur analysis[J].Journal of Fuel Chemistry and Technology, 2014, 42(3):277-283.
[24] WANG Qing, LIU Qi, WANG Zhichao, et al. Characterization of organic nitrogen and sulfur in the oil shale kerogens[J]. Fuel Processing Technology, 2017, 160(3):170-177.
[2]何林,孙文郡,李鑫钢.溶剂萃取在油砂分离中的应用及发展[J].化工进展, 2011, 30(s2):186-189.HE Lin, SUN Wenjun, LI Xingang. Application and development of solvent extraction in oil sand separation[J]. Chemical Industry and Engineering Progress, 2011, 30(s2):186-189.
[3]韦石.我国成为第二大石油消费国[J].复杂油气藏, 2012, 5(4):8.WEI Shi. China became the second largest consumer of oil[J].Complex Hydrocarbon Reservoirs, 2012, 5(4):8.
[4]刘增洁.未来20年世界能源供需预测[J].中国能源, 2002(5):33-35.LIU Zengjie. Forecast of world energy supply and demand over the next 20 years[J]. Energy of China, 2002(5):33-35.
[5]王擎,王引,贾春霞.三种印尼油砂燃烧特性研究[J].中国电机工程学报, 2012, 32(26):23-30.WANG Qing, WANG Yin, JIA Chunxia. Study on the combustion characteristics of three Indonesian oil sands[J]. Proceedings of the CSEE, 2012, 32(26):23-30.
[6]李莉.油砂——一种新的替代能源[J].当代石油石化, 2005, 13(12):28-30.LI Li. Oil sands—a new alternative energy source[J]. Petroleum&Petrochemical Today, 2005, 13(12):28-30.
[7]王擎,戈建新,贾春霞,等.干馏终温对油砂油化学结构的影响[J].化工学报, 2013, 64(11):4216-4222.WANG Qing, GE Jianxin, JIA Chunxia, et al. Effect of final retorting temperature on chemical structure of oil sands[J]. CIESC Journal,2013, 64(11):4216-4222.
[8] TONG Jianhui, HAN Xiangxin, WANG Sha, et al. Evaluation of structural characteristics of Huadian oil shale kerogen using direct techniques(solid-state13C NMR, XPS, FT-IR, and XRD)[J]. Energy&Fuels, 2011, 25(25):4006-4013.
[9] CHEN Yanyan, FURMANN A, MASTALERZ M, et al. Quantitative analysis of shales by KBr-FTIR and micro-FTIR[J]. Fuel, 2014, 116(1):538-549.
[10] QIAN Lin, ZHAO Yijun, SUN Shaozeng, et al. Chemical/physical properties of char during devolatilization in inert and reducing conditions[J]. Fuel Processing Technology, 2014, 118(2):327-334.
[11]张安贵,王刚,毕研涛,等.内蒙古油砂沥青热转化前后化学结构的变化规律[J].石油学报(石油加工), 2011, 27(3):434-440.ZHANG Angui, WANG Gang, BI Yantao, et al. Variation of chemical structure of asphalt from oil sands in Inner Mongolia before and after thermal conversion[J]. Acta Petrolei Sinica, 2011, 27(3):434-440.
[12]王擎,王智超,贾春霞,等.基于固体13C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. Research on asphaltene structure of oil sands based on solid13C NMR technology[J]. Chemical Industry and Engineering Progress, 2014, 33(6):1392-1396.
[13]刘洪鹏,巩时尚,贾春霞,等.基于TG和FTIR的印尼油砂微观结构及热解特性实验[J].科学技术与工程, 2017, 17(18):1-8.LIU Hongpeng, GONG Shishang, JIA Chunxia, et al. Microstructure and pyrolysis characteristics of Indonesian oil sands based on TG and FTIR[J]. Science Technology and Engineering, 2017, 17(18):1-8.
[14]王擎,许祥成,迟铭书,等.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 Xiangcheng, CHI Mingshu, et al. FTIR study on the composition and structure of kerogen and its pyrolysis oil generation characteristics[J]. Journal of Fuel Chemistry and Technology, 2015, 43(10):1158-1166.
[15] KELEMEN S R, GEORGE G N, GORBATY M L. Direct determination and quantification of sulphur forms in heavy petroleum and coals:1.The X-ray photoelectron spectroscopy(XPS)approach[J]. Fuel, 1990,69(8):939-944.
[16]葛涛,张明旭,马祥梅.新阳炼焦煤结构的FTIR和XPS谱学表征[J].光谱学与光谱分析, 2017, 37(8):2406-2411.GE Tao, ZHANG Mingxu, MA Xiangmei. FTIR and XPS spectroscopic characterization of coking coal structure in Xinyang[J]. Spectroscopy and Spectral Analysis, 2017, 37(8):2406-2411.
[17]朱子彬,朱宏斌,吴勇强,等.烟煤快速加氢热解的研究[J].燃料化学学报, 2001, 29(1):44-48.ZHU Zibin, ZHU Hongbin, WU Yongqiang, et al. Study on the rapid hydropyrolysis of bituminous coal[J]. Journal of Fuel Chemistry and Technology, 2001, 29(1):44-48.
[18]李梅,杨俊和,张启锋,等.用XPS研究新西兰高硫煤热解过程中氮、硫官能团的转变规律[J].燃料化学学报, 2013, 41(11):1287-1293.LI Mei, YANG Junhe, ZHANG Qifeng, et al. XPS was used to study the transformation of nitrogen and sulfur functional groups during pyrolysis of high sulfur coal in New Zealand[J]. Journal of Fuel Chemistry and Technology, 2013, 41(11):1287-1293.
[19]罗宽勇,韩冬云,李福起,等.印尼油砂沥青的净化工艺[J].化工进展, 2016, 35(12):3885-3890.LUO Kuanyong, HAN Dongyun, LI Fuqi, et al. Purification process of oil sand asphalt in Indonesia[J]. Chemical Industry and Engineering Progress, 2016, 35(12):3885-3890.
[20]韩峰,张衍国,蒙爱红,等.云南褐煤结构的FTIR分析[J].煤炭学报, 2014, 39(11):2293-2299.HAN Feng, ZHANG Yanguo, MENG Aihong, et al. FTIR analysis of lignite structure in Yunnan[J]. Journal of China Coal Society, 2014, 39(11):2293-2299.
[21]刘粉荣,李文,郭慧卿,等. XPS法研究煤表面碳官能团的变化及硫迁移行为[J].燃料化学学报, 2011, 39(2):81-84.LIU Fanrong, LI Wen, GUO Huiqing, et al. XPS study on the changes of carbon functional groups and sulfur migration behavior on coal surface[J]. Journal of Fuel Chemistry and Technology, 2011, 39(2):81-84.
[22]陈丽诗,王岚岚,潘铁英,等.固体核磁碳结构参数的修正及其在煤结构分析中的应用[J].燃料化学学报, 2017, 45(10):1153-1163.CHEN Lishi, WANG Lanlan, PAN Tieying, et al. Modification of structural parameters of solid nuclear magnetic carbon and its application in coal structural analysis[J]. Journal of Fuel Chemistry and Technology, 2017, 45(10):1153-1163.
[23]马玲玲,秦志宏,张露,等.煤有机硫分析中XPS分峰拟合方法及参数设置[J].燃料化学学报, 2014, 42(3):277-283.MA Lingling, QIN Zhihong, ZHANG Lu, et al. XPS peak fitting method and parameter setting for coal organic sulfur analysis[J].Journal of Fuel Chemistry and Technology, 2014, 42(3):277-283.
[24] WANG Qing, LIU Qi, WANG Zhichao, et al. Characterization of organic nitrogen and sulfur in the oil shale kerogens[J]. Fuel Processing Technology, 2017, 160(3):170-177.