沙特常压渣油超临界流体萃取分馏宽馏分中含硫化合物的分子表征

刘美; 赵海玲; 孙琦; 赵德智

沙特常压渣油超临界流体萃取分馏宽馏分中含硫化合物的分子表征

刘美^1, ,,
赵海玲¹,
孙琦²,
赵德智¹

基金项目:

中国海洋石油总公司 HL00FW (P)2014-0005

详细信息

中图分类号: TE624.4
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出版历程
- 收稿日期: 2015-09-17
- 修回日期: 2015-12-03

Molecular characterization of sulfur-containing compounds in the wide fractions of Saudi Arabia atmospheric residue by supercritical fluid extraction fractionation

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Corresponding author: Tel：13941330401，024-56863015；E-mail：liumeifushun@163.com

摘要

摘要: 采用超临界流体萃取分馏 (SFEF) 装置, 将沙特中质原油常压渣油 (SZAR) 按照分子大小和极性强弱进行多级萃取分馏, 得到四个宽馏分和一个萃余残渣。考察了四个宽馏分沸程分布、密度、残炭值、黏度、相对分子质量、硫和氮含量以及结构族组成等基本性质均随萃取压力的变化趋势。采用甲基衍生化作用使含硫化合物转化为含有极性的甲基硫盐, 结合正离子模式下的电喷雾 (ESI) 电离源的傅里叶变换离子回旋共振质谱 (FT-ICR MS) 分析各馏分中所包含的含硫化合物的分子组成。结果表明, 超临界萃取分馏技术可以将馏分按照分子大小进行分离, 且对于非烃类化合物具有富集作用。各个馏分中含量最高的均为包含一个硫原子的S₁类化合物, 且二苯并噻吩 (DBE=6) 类含量最高。馏分越重, S₁、S₂类化合物含量越高、种类越繁多、且缩合程度更高, 包含的更多的大分子含硫化合物。
- 超临界流体萃取分馏 /
- 甲基衍生化 /
- 电喷雾电离 /
- 傅里叶变换离子回旋共振质谱 /
- 含硫化合物
Abstract: Saudi Arabia atmospheric residue (SZAR) was subjected to supercritical fluid extraction fractionation (SFEF) and separated into four extractable fractions and an un-extractable end-cut.The SFEF subfractions were subjected to the simulated distillation analysis, gel permeation chromatography (GPC) for their molecular weight distributions, and open column liquid chromatography for their saturates, aromatics, resins, and asphaltenes (SARA) compositions, by high-temperature gas chromatography (GC).The density, carbon residue value, viscosity, and sulfur and nitrogen content along with the extraction pressure were determined.Sulfur compounds in wide fractions were converted to methylsulfonium salts, which were characterized by positive-ion electrospray ionization (ESI) and Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry (MS).The results indicated that the mass range and maximum peak intensity of the SFEF subfraction are increased as the SFEF subfraction becomes heavier.The molecules in various SFEF subfractions are separated by their polarity and molecular weight.The highest level in the various fractions is referred to S₁ class species and meanwhile, benzothiophene turns to be the dominant heteroatom compounds.Compared with the lighter fractions, heavier fractions have higher contents of S₁ and S₂ class species, wider range, higher molecular weight, and more aromatic cores.
- supercritical fluid extraction fractionation /
- methylation /
- electrospray ionization /
- Fourier transform ion cyclotron resonance mass spectrometry /
- sulfur-containing compounds

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图 1 宽馏分的烃类族组成

Figure 1. SARA compositions of SFEF fractions

: res. ;: aro. ;: sat.

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图 2 宽馏分的模拟蒸馏曲线

Figure 2. Simulated distillation curves of SFEF fractions

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图 3 宽馏分SFEF-1-SFEF-4的红外光谱谱图

Figure 3. FT-IR spectra of SFEF fractions

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图 4 SZAR宽馏分的正离子模式下FT ICR-MS质谱图 (a) 及局部放大图 (b)

Figure 4. Broadband (a) and expanded (b) mass spectra for wide fractions of SZAR from positive-ion ESI FT-ICR MS

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图 5 宽馏分中S₁、S₂类化合物DBE碳数分布

Figure 5. Plots of DBE as a function of the carbon number for S₁ and S₂ class species in wide fractions from positive-ion ESI FT-ICR MS

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表 1 原油常渣的主要性质

Table 1. Bulk properties of SZAR

Item	Value
Density (20℃) ρ/(g·cm^-3)	0.9682
Carbon residue w/%	10.99
Viscosity (100℃) μ/(mPa·s)	48.36
Molecular weight	512
Carbon w/%	84.91
Hydrogen w/%	11.15
H/C (atomic ratio)	0.64
Nitrogen w/%	0.27
Sulfur w/%	3.44
Nickel w/(μg·g^-1)	22.38
Vanadium w/(μg·g^-1)	69.95
Saturates w/%	45.88
Aromatics w/%	34.96
Resins w/%	17.36
C₇asphaltene w/%	1.80

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表 2 SZAR的萃取分馏条件

Table 2. Conditions for the supercritical fluid extraction fractionation (SFEF) of Saudi Arabia atmospheric residue (SZAR)

Solvent	Raw material quantity m/g	Flow q/(mL·min^-1)	Linearization applied pressure p/MPa	Rate of rise /(MPa·h^-1)	Temperature t/℃			Cut fraction w/%
Solvent	Raw material quantity m/g	Flow q/(mL·min^-1)	Linearization applied pressure p/MPa	Rate of rise /(MPa·h^-1)	tower top	middle	bottom	Cut fraction w/%
n-pentane	700	100	4-12	1.0	250	240	230	20

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表 3 SZAR各个宽馏分随压力变化的收率

Table 3. Extracted pressure and yield of each cut in SFEF of SZAR

Cut number	Extract pressure p/MPa	Yield w/%	Comment
SFEF-1	5.30	21.16	flowable
SFEF-2	5.85	20.95	flowable
SFEF-3	6.65	21.01	unflowable
SFEF-4	10.00	21.23	unflowable
End cut	N/A	15.62	solids

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表 4 宽馏分的基本性质

Table 4. Properties of SFEF subfractions

Cut number	ρ_20℃^a	μ_100℃^b /(mm²·s^-1)	CCR^c w/%	Elemental analysis w/%				C/H (atomic ratio)
Cut number	ρ_20℃^a	μ_100℃^b /(mm²·s^-1)	CCR^c w/%	C^d	H^d	S^e	N^f	C/H (atomic ratio)
SFEF-1	0.9089	4.43	0.46	85.60	12.27	1.86	0.11	0.59
SFEF-2	0.9402	10.27	1.96	85.32	12.01	2.44	0.15	0.60
SFEF-3	0.9487	16.91	2.90	85.11	11.76	2.73	0.19	0.61
SFEF-4	1.1256	59.51	9.37	84.49	11.34	3.46	0.27	0.63
^a: GB/T 13377-1992; ^b: GBT-11137; ^c: ASTM D189; ^d: ASTM D5291; ^e: ASTM D5453; ^f: ASTM D5762

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