Analysis of composition and chemical structure of Indonesian oil sands bitumen

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

Abstract

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

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

CLC Number:

O 657

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.

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.

Figures/Tables 15

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

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

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	—	—	—	—

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

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

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

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

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

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