印尼油砂沥青组成及化学结构分析

doi:10.16085/j.issn.1000-6613.2018-2186

摘要/Abstract

摘要：

利用FTIR和¹³C 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¹³C 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。

关键词: 油砂, 傅里叶变换红外光谱, X射线光电子能谱分析, 核磁共振, 燃料, 化学分析

Abstract:

The FTIR and ¹³C 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 ¹³C 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.

Key words: oil sands, FTIR, XPS, NMR, fuel, chemical analysis

中图分类号:

O 657

柏静儒, 陈嘉彬, 李坤, 王智超, 蒋凌志, 王擎. 印尼油砂沥青组成及化学结构分析[J]. 化工进展, 2019, 38(07): 3117-3125.

Jingru BAI, Jiabin CHEN, Kun LI, Zhichao WANG, Lingzhi JIANG, Qing WANG. Analysis of composition and chemical structure of Indonesian oil sands bitumen[J]. Chemical Industry and Engineering Progress, 2019, 38(07): 3117-3125.

图/表 15

表1 油砂样品铝甄实验及抽提实验结果分析

样品	铝甄实验结果				索氏抽提实验结果
样品	半焦产率 /%	气体+损失质量分数/%	焦油产率/%	水产率/%	沥青产率 /%	砂砾产率 /%
DL	74.54	3.56	20.69	1.21	32.32	66.58
KAI	74,48	3.43	20.82	1.27	30.28	67.34
WK	73.75	3.66	21.36	1.23	30.23	67.47
WINTO	72.96	4.61	21.03	1.4	29.34	69.26

表2 油砂样品的工业分析与元素分析

样品	工业分析（质量分数）/%					元素分析（质量分数）/%
样品	M _ad	A _ad	V _ad	FC _ad	CO₂	N	C	H	O	S_t
DL	0.80	47.32	25.87	0.69	25.32	0.76	80.52	9.38	1.52	3.85
WK	0.86	46.15	26.51	0.51	25.97	1.01	79.07	9.14	1.41	3.66
KAI	0.87	45.08	29.45	0.82	23.78	0.92	79.16	9.21	1.72	3.72
WINTO	0.77	47.26	27.22	0.43	24.32	1.15	79.82	8.99	1.21	5.79

表3 沥青与砂砾的形态硫分析

硫形态	沥青形态硫分析（质量分数）/%				砂砾形态硫分析（质量分数）/%
硫形态	DL	KAI	WK	WINTO	DL	KAI	WK	WINTO
全硫	3.85	3.66	3.72	5.79	0.68	0.58	0.58	0.4
硫酸盐硫	—	—	—	—	0.36	0.26	0.27	0.31
黄铁矿硫	—	—	—	—	0.32	0.32	0.31	0.33
有机硫	3.85	3.66	3.72	5.79	—	—	—	—

图1 油砂样品的沥青红外光谱谱图

图2 沥青中脂肪烃FTIR拟合图

表4 沥青中脂肪烃FTIR吸收峰及归属

峰位置/cm^-1	吸收峰归属	相对含量/%
峰位置/cm^-1	吸收峰归属	DL	WK	KAI	WINTO
2840～2860	syn.R₂CH₂	24.94	24.86	25.03	24.78
2890～2910	－R₃CH	16.41	16.39	16.54	16.51
2920～2930	asym.R₂CH₂	39.59	39.62	39.56	40.2
2955～2965	asym.RCH₃	19.06	19.13	18.87	18.51

图3 沥青中芳香烃FTIR拟合图

表5 沥青中芳香烃FTIR吸收峰及归属

峰位置/cm^-1	吸收峰归属	相对含量/%
峰位置/cm^-1	吸收峰归属	DL	WK	KAI	WINTO
710～730	脂肪族亚甲基链(链长大于4)	—	—	—	—
740～800	苯环二取代芳烃苯环三取代芳烃	6.71	11.03	11.83	4.82
850～900	苯环二取代芳烃苯环三取代芳烃苯环四取代芳烃苯环五取代芳烃	93.29	88.97	88.17	95.18

图4 沥青中含氧官能团FTIR拟合图

表6 沥青中含氧官能团FTIR吸收峰及归属

峰位置/cm^-1	吸收峰归属	相对含量/%
峰位置/cm^-1	吸收峰归属	DL	WK	KAI	WINTO
1100~1260	C－O	51.93	39.96	49.11	42.43
1300~1350	R－COOH	45.16	54.73	49.3	49.46
1350~1500	－CH₂－，－CH₃	—	—	—	—
1690~1800	－C $? ?$ O	2.91	5.31	1.59	8.11

表6 沥青中含氧官能团FTIR吸收峰及归属

峰位置/cm^-1	吸收峰归属	相对含量/%
峰位置/cm^-1	吸收峰归属	DL	WK	KAI	WINTO
1100~1260	C－O	51.93	39.96	49.11	42.43
1300~1350	R－COOH	45.16	54.73	49.3	49.46
1350~1500	－CH₂－，－CH₃	—	—	—	—
1690~1800	－C $? ?$ O	2.91	5.31	1.59	8.11

图5 印尼油砂13C NMR波谱图

图6 印尼油砂13C NMR波谱分峰图

表7 印尼油砂脂肪烃与芳香烃部分化学位移及归属

化学位移δ	归属	结构	相对含量/%
化学位移δ	归属	结构	DL	WK	KAI	WINTO
14~16	甲基碳	R—CH₃	10.37	8.37	12.41	16.87
22~36	亚甲基碳	—CH₂	49.1	47.91	46.75	45.98
36~50	次甲基碳、季碳	—CH —C	10.13	9.83	9.97	8.73
100~129	质子化芳碳		18.95	15.25	16.81	18.24
129~137	桥头芳碳		6.85	4.22	5.32	4.66
137~148	侧枝芳香碳		3.54	12.15	7.72	4.31
165~188	羧基碳	R－COOH	1.06	2.27	1.02	1.21

图7 印尼油砂XPS谱图

图8 印尼油砂S2p拟合谱图

参考文献 24

1	贾春霞, 刘洪鹏, 柏静儒, 等 . 油砂燃烧过程的TG-DSC分析[J]. 化工进展, 2013, 32(6): 1273-1277.
	JIA Chunxia , LIU Hongpeng , BAI Jingru , et al . TG-DSC analysis of oil sands combustion process [J]. Chemical Industry and Engineering Progress, 2013, 32(6): 1273-1277.
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-state ¹³C 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 solid ¹³C 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 , Xiangmei MA . 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.
	Lingling MA , 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.

[1]	陈匡胤, 李蕊兰, 童杨, 沈建华. 质子交换膜燃料电池气体扩散层结构与设计研究进展[J]. 化工进展, 2023, 42(S1): 246-259.
[2]	许家珩, 李永胜, 罗春欢, 苏庆泉. 甲醇水蒸气重整工艺的优化[J]. 化工进展, 2023, 42(S1): 41-46.
[3]	赖诗妮, 江丽霞, 李军, 黄宏宇, 小林敬幸. 含碳掺氨燃料的研究进展[J]. 化工进展, 2023, 42(9): 4603-4615.
[4]	张启, 赵红, 荣峻峰. 质子交换膜燃料电池中氧还原反应抗毒性电催化剂研究进展[J]. 化工进展, 2023, 42(9): 4677-4691.
[5]	蒋博龙, 崔艳艳, 史顺杰, 常嘉城, 姜楠, 谭伟强. 过渡金属Co₃O₄/ZnO-ZIF氧还原催化剂Co/Zn-ZIF模板法制备及其产电性能[J]. 化工进展, 2023, 42(6): 3066-3076.
[6]	李栋先, 王佳, 蒋剑春. 皂脚热解-催化气态加氢制备生物燃料[J]. 化工进展, 2023, 42(6): 2874-2883.
[7]	马哲杰, 张文励, 赵炫凯, 李平. PEMFC阴极催化层氧传质阻力影响的研究进展[J]. 化工进展, 2023, 42(6): 2860-2873.
[8]	陈昊, 张传浩, 于峰, 范彬彬, 李瑞丰. Y型沸石在异丁醇齐聚反应中的催化性能[J]. 化工进展, 2023, 42(2): 794-802.
[9]	于海强, 郭泉忠, 杜克勤, 汪川. 脉冲电沉积PbO₂涂层在PEMFC不锈钢双极板上的应用[J]. 化工进展, 2023, 42(2): 917-924.
[10]	范思强, 彭绍忠, 彭冲, 胡永康. 废塑料高附加值利用技术研究进展[J]. 化工进展, 2023, 42(2): 1020-1027.
[11]	沈天绪, 沈来宏. 基于3kW塔式串行流化床差异燃料的化学链燃烧解析[J]. 化工进展, 2023, 42(1): 138-147.
[12]	薛马晨, 杨伯伦, 夏春谷, 朱刚利. 乙醇缩合制高碳醇（C₆₊醇）多相催化剂研究进展[J]. 化工进展, 2023, 42(1): 194-203.
[13]	寇佳伟, 程淑艳, 程芳琴. 类水滑石基催化剂光催化二氧化碳还原研究进展[J]. 化工进展, 2022, 41(S1): 190-198.
[14]	高帷韬, 殷屺男, 涂自强, 龚繁, 李阳, 徐宏, 王诚, 毛宗强. 金属有机框架材料中的质子传导及其在质子交换膜中的应用[J]. 化工进展, 2022, 41(S1): 260-268.
[15]	肖周荣, 李国柱, 王涖, 张香文, 谷建民, 王德松. 液体碳氢燃料蒸汽重整制氢催化剂研究进展[J]. 化工进展, 2022, 41(S1): 97-107.