FCC油浆富芳烃抽出油组成分析

冯祎; 孙昱东; 张帅

doi:10.1016/S1872-5813(21)60027-0

FCC油浆富芳烃抽出油组成分析

doi: 10.1016/S1872-5813(21)60027-0

中国石油大学（华东）化学工程学院山东青岛 266580

详细信息

作者简介:
冯祎：972684241@qq.com

通讯作者:
Tel：0532-86980605, E-mail：ydsun@upc.edu.cn

中图分类号: TE624.5
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- 被引次数: 0
出版历程
- 收稿日期: 2020-10-21
- 修回日期: 2020-12-30
- 网络出版日期: 2021-03-30
- 刊出日期: 2021-06-30

Composition analysis of aromatics-rich extraction oil from FCC slurry

College of Chemical Engineering, China University of Petroleum, Qingdao 266580, China

摘要

摘要: 以中间基属FCC油浆的抽出油为原料，采用实沸点减压蒸馏切割为每20 ℃一个窄馏分，测量其密度、残炭和运动黏度等基本物性，并结合元素分析、核磁共振波谱以及全二维气相色谱/飞行时间质谱等考察了窄馏分中芳烃组成和结构的变化。结果表明，随着沸点升高，窄馏分的密度、残炭、运动黏度均呈现递增趋势，沸点达420 ℃后变化尤为明显；440 ℃之前窄馏分中的芳烃主要以三、四环为主，其后五环芳烃含量急剧增加。FCC油浆中的芳烃具有较高的缩合度且芳环上仅含有少量较短的烷基侧链；油浆窄馏分中的杂原子化合物主要以硫化物和氧化物为主，氮化物和卤化物含量较低。
- FCC油浆 /
- 组成分析 /
- 窄馏分 /
- 物性 /
- 芳烃组成 /
- 杂原子化合物
Abstract: The extracted oil of intermediate base FCC slurry is split into eight narrow fractions with a boiling point interval of 20 °C by vacuum distillation. The aromatic composition and constitution of these narrow fractions were determined by measuring their density, carbon residue and kinematic viscosity as well as elemental analysis, ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy and comprehensive two-dimensional gas chromatography and time-of-flight mass spectrometry (GC×GC TOF MS). The results indicate that the density, carbon residue and kinematic viscosity of each narrow fraction increase with the increase of boiling point, in particular with a boiling point higher than 420 °C. The aromatics consist of mainly tricyclic and tetracyclic aryl hydrocarbons in the narrow fractions with a boiling point lower than 440 °C; the content of pentacyclic aromatics increases rapidly with the increace of boling point over 440 °C, though the pentacyclic aromatics are also present in the narrow fractions with a boiling point of 400–420 °C. The aromatics in the FCC slurry are highly-condensed and contain a small amount of short-alkyl groups. The heteratomic compounds in the narrow fractions include mainly sulfur- and oxygen-containing compounds, whereas the content of nitrogen- and halogen-containing compounds is very low.
- FCC slurry /
- composition analysis /
- narrow fraction /
- physical property /
- aromatic hydrocarbon composition /
- heteroatomic compound

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FIG. 719. FIG. 719.

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图 1 抽出油实沸点蒸馏曲线

Figure 1 True boiling point distillation curve of extracted oil

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图 2 抽出油窄馏分芳烃组成

Figure 2 Aromatic composition of different narrow fractions determined by GC×GC-TOFMS.

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图 3 抽出油窄馏分杂原子化合物分布

Figure 3 Distribution of heteroatomic compounds in various narrow fractions

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表 1 原料基本性质

Table 1 Primary properties of the FCC slurry

ρ²⁰/(kg·m⁻³)	M	w(carbon residue)/%	μ¹⁰⁰/(mm²·s⁻¹)	w(SARA)/%
ρ²⁰/(kg·m⁻³)	M	w(carbon residue)/%	μ¹⁰⁰/(mm²·s⁻¹)	saturates	aromatics	resins	asphaltenes
1120.20	343	8.43	14.08	18.77	72.37	6.06	2.80

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表 2 窄馏分收率分布

Table 2 Extraction yield of each narrow fraction from the FCC slurry

IBP−380 ℃	Yield w/%					480 ℃−FBP
IBP−380 ℃	380−400 ℃	400−420 ℃	420−440 ℃	440−460 ℃	460−480 ℃	480 ℃−FBP
5.67	27.59	20.25	15.07	8.89	6.69	15.08

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表 3 原料及产物性质检测方法

Table 3 Standards of testing methods of feedstock and products

Number	Analysis item	Method of analysis
1	ρ²⁰, density at 20 °C, (kg·m⁻³)	GB/T 2540—1981
2	M, average molecular weight	SH/T 0583—1994
3	w，carbon residue，%	GB/T 17144—1997
4	μ¹⁰⁰，kinematic viscosity, (mm²·s⁻¹)	GB/T 11137—1989

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表 4 窄馏分物性变化

Table 4 Physical properties of narrow fractions

Fraction	ρ²⁰/(kg·m⁻³)	w (carbon residue)/%	μ¹⁰⁰/(mm²·s⁻¹)
360−380 ℃	1.1008	0.12	3.63
380−400 ℃	1.1012	0.13	5.53
400−420 ℃	1.1066	0.25	8.07
420−440 ℃	1.1169	0.70	10.30
440−460 ℃	1.1268	2.65	18.10
460−480 ℃	1.1294	7.47	38.43
480−500 ℃	1.1850	16.01	81.44
500 ℃−FBP	1.2250	25.28	132.50

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表 5 C、H、S、N元素分析及VPO分子量

Table 5 Elemental composition and molecular weight of all narrow fractions

Fraction	n(H)/n(C)	w/%				M
Fraction	n(H)/n(C)	H	C	S	N	M
360−380 ℃	0.89	6.88	90.61	2.17	0.10	208
380−400 ℃	0.87	6.61	91.38	2.00	0.07	256
400−420 ℃	0.86	6.59	91.76	1.86	0.06	263
420−440 ℃	0.82	6.24	91.90	1.82	0.05	291
440−460 ℃	0.82	6.27	91.78	1.72	0.06	313
460−480 ℃	0.80	6.05	90.36	1.51	0.07	325
480−500 ℃	0.79	6.05	92.12	1.44	0.05	334
500 ℃−FBP	0.74	5.67	92.66	1.06	0.05	−

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表 6 窄馏分中不同化学位移氢的含量

Table 6 Content of hydrogen species (%) of different chemical shifts in each narrow fraction determined by ¹H-NMR

Fraction	w/%
Fraction	H_γ	H_β	H_α	H_A
IBP−380 ℃	0.73	11.35	43.63	44.28
380−400 ℃	0.89	10.98	43.30	44.83
400−420 ℃	0.82	10.12	43.22	45.84
420−440 ℃	0.64	9.48	43.83	46.05
440−460 ℃	0.61	9.34	43.64	46.41
460−480 ℃	0.71	9.58	41.61	48.11
480−500 ℃	0.53	8.84	41.59	49.04

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表 7 窄馏分核磁共振H谱结构参数

Table 7 Structural parameters of narrow fractions derived by the improved B-L method based on the ¹H-NMR results

Fraction	C_T	H_T	R_A	R_T	R_N	f_a	f_N	f_P	σ	H_AU/C_A
IBP−380 ℃	15.69	14.20	2.57	3.74	1.17	0.75	0.22	0.03	0.33	0.80
380−400 ℃	19.48	16.79	3.60	4.68	1.07	0.76	0.17	0.07	0.33	0.75
400−420 ℃	20.08	17.20	3.80	4.79	0.99	0.77	0.15	0.09	0.32	0.75
420−440 ℃	22.27	18.02	4.46	5.57	1.12	0.78	0.15	0.07	0.32	0.70
440−460 ℃	23.90	19.47	4.88	5.84	0.96	0.78	0.12	0.10	0.32	0.71
460−480 ℃	24.45	19.51	5.12	6.02	0.90	0.79	0.11	0.10	0.30	0.69
480−500 ℃	25.62	20.02	5.49	6.36	0.87	0.80	0.10	0.10	0.30	0.68

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表 8 窄馏分中不同化学位移碳的含量

Table 8 Fractions of carbon species (%) of different chemical shifts in each narrow fraction determined by ¹³C-NMR

Fraction	$ f_{{\rm{a}}} $/%	$ f^{{\rm{H}}}_{{\rm{a}}} $/%	$f^{{\rm{B}}}_{{\rm{a}}} $/%	$f^{{\rm{C}}}_{{\rm{a}}} $/%	$f^{{\rm{O}}}_{{\rm{a}}}$/%	$ f^{{\rm{C}}}_{{\rm{a}}} $/%	$ f_{{\rm{al}}} $/%	$ f^{{\rm{A}}}_{{\rm{al}}} $/%	$ f^{{\rm{B}}}_{{\rm{al}}} $/%	$ f^{{\rm{H}}}_{{\rm{al}}} $/%	$ f^{{\rm{O}}}_{{\rm{al}}} $/%
360−380 ℃	80.24	61.25	15.48	3.51	0	0	19.76	11.76	2.33	5.59	0.08
380−400 ℃	80.05	57.61	17.66	4.79	0	0	19.95	12.31	2.44	5.20	0
400−420 ℃	81.84	56.30	18.68	5.91	0.67	0.29	18.15	11.45	2.14	4.52	0.03
420−440 ℃	80.85	55.05	19.58	5.88	0.34	0	19.15	11.98	2.45	4.72	0
440−460 ℃	80.85	57.06	18.77	4.67	0.13	0.21	19.15	11.59	2.43	5.13	0
460−480 ℃	84.37	56.14	20.37	6.69	1.18	0	15.63	10.60	2.23	2.80	0
480−500 ℃	83.44	73.45	7.69	0	0	2.31	16.56	7.18	0.86	8.47	0
note: f_a, aromatic carbon; $ f^{{\rm{H}}}_{{\rm{a}}} $, proton aromatic carbon; $ f^{{\rm{B}}}_{{\rm{a}}} $, bridgehead aromatic carbon; $ f^{{\rm{S}}}_{{\rm{a}}} $, lateral aromatic carbon; $ f^{{\rm{O}}}_{{\rm{a}}} $ oxygen-bonded aromatic carbon; $ f^{{\rm{C}}}_{{\rm{a}}} $, carbonyl aromatic carbon; $ f_{{\rm{al}}} $, saturated carbon; $f^ {\rm{A} }_{ {\rm{al} } }$, lipomethyl carbon; $ f^{B}_{{\rm{al}}} $, aromatic ring methyl carbon; $ f^{{\rm{H}}}_{{\rm{al}}} $, methylene and methine carbon; $ f^{{\rm{O}}}_{{\rm{al}}} $, oxygen connected saturated carbon

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