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

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Tel：0532-86980605；E-mail：ydsun@upc.edu.cn

中图分类号: TE624.5
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出版历程
- 网络出版日期: 2021-03-30

Analysis of aromatics-rich extraction oil composition of 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，采用密度、残炭、运动黏度等基本物性分析结果，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、运动黏度呈现递增趋势，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 /
- 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 divided into eight narrow fractions with boiling point range of 20 ℃ by vacuum distillation. The aromatic composition of narrow fractions were obtained by means of density, carbon residue, kinematic viscosity, elemental analysis, ¹H-NMR、¹³C-NMR, and GC × GC TOF MS. The results showed that the density, carbon residue and kinematic viscosity of the narrow fractions increased with the increase of boiling point, especially after 420 ℃. The aromatics mainly consisted of tricyclic and tetracyclic in narrow fractions before 440 ℃. The pentacyclic aromatics present in narrow fraction of 400−420 ℃and increased rapidly after 440 ℃. The aromatics in FCC slurry are highly-condensed and contain a small amount of short-alkyl groups. The heteratomic compounds in the narrow fraction are mainly sulfide and oxide, and the content of nitride and halide is very low.
- FCC slurry /
- narrow fraction /
- physical property /
- aromatic hydrocarbon composition /
- heteroatomic compound

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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 narrow fractions

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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 of narrow fractions

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表 1 原料基本性质

Table 1. Main properties of FCC slurry

ρ²⁰/(kg·m⁻³)	M	ω(carbon residue)/%	ν¹⁰⁰/(mm²·s⁻¹)	ω(SARA)/%
ρ²⁰/(kg·m⁻³)	M	ω(carbon residue)/%	ν¹⁰⁰/(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. Narrow fraction yield distribution

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/(kg·m^-3)	GB/T 2540-1981
2	M	SH/T 0583-1994
3	ω(carbon residue)/%	GB/T 17144-1997
4	ν¹⁰⁰/(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)	ω(carbon residue)/%	ν¹⁰⁰/(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. Element analysis of C、H、S、N and molecular weight

Fraction	n(H)/n(C)	ω(H)/%	ω(C)/%	ω(S)/%	ω(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. Hydrogen content of different chemical shift in narrow fractions

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 by ¹H-NMR

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. Carbon content of different chemical shift in narrow fractions

Fraction	fa/%	fa^H/%	fa^B/%	fa^S/%	fa^O/%	fa^C/%	fal/%	fal^A/%	fal^B/%	fal^H/%	fal^O/%
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
注：fa-芳碳分率；fa^H-质子芳碳分率；fa^B-桥头芳碳分率；fa^S-侧枝芳碳分率；fa^O-氧接芳碳分率；fa^C-羰基芳碳分率；fal-饱和碳分率；fal^A-脂甲基碳分率；fal^B-芳环甲基碳分率；fal^H-亚甲基、次甲基碳分率；fal^O-氧接饱和碳分率

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