催化裂化油浆组成分布对中间相沥青光学织构的影响

doi:10.11949/0438-1157.20200237

摘要/Abstract

摘要：

以SLO-LH、SLO-SH和SLO-YN催化裂化油浆为原料，利用热缩聚法制备中间相沥青，系统分析了油浆的烃组成分布、沸点分布以及核磁结构特征，关联了中间相沥青光学织构与原料性质组成关系。结果表明，SLO-SH和SLO-YN油浆中的分子量和组成分布较窄，在给定反应条件(430℃、0.7 MPa)下制备中间相沥青的光学织构指数(OTI)值分别为45和50，中间相织构主要由大面积的域及流域组成，镶嵌结构较少。相对于SLO-SH与SLO-YN，SLO-LH样品的烃组成与沸点分布明显疏散，得到的中间相主要由镶嵌组织与小域构成。结果表明集中分布且芳烃含量高有利于得到高收率与高OTI值的优质中间相沥青，对油浆组分进行分离是制备高品质中间相沥青和针状焦的必要途径。

关键词: 催化裂化油浆, 组成, 分离, 分布, 中间相沥青, 显微结构

Abstract:

Using SLO-LH, SLO-SH and SLO-YN catalytic cracking oil slurry as raw materials, mesophase pitch was prepared by thermal polycondensation method. The hydrocarbon composition distribution, boiling point distribution and nuclear magnetic structure characteristics of the oil slurry were systematically analyzed and related to mesophase pitch. The results show that the molecular weight and composition distribution of SLO-SH and SLO-YN are relatively narrow. The mesophase pitch was prepared under the given reaction conditions at 430 ℃ and 0.7 MPa. The obtained mesophase texture is mainly composed of domain and flow domain, and with less mosaic structure. The SLO-SH and SLO-YN optical texture index (OTI) are 45 and 50, respectively. Compared with SLO-SH and SLO-YN, the hydrocarbon composition and boiling point distribution of SLO-LH samples are significantly evacuated. The mesophase obtained from SLO-LH is mainly composed of a mosaic structure and a small domain. The results show that concentrated distribution and high aromatics content are conducive to high-quality mesophase pitch with high yield and high OTI value. Separation of oil slurry components is a necessary way to prepare high-quality mesophase pitch and needle coke.

Key words: catalytic slurry oil, composition, separation, distribution, mesophase pitch, microstructure

中图分类号:

TE 624

代晓玉, 马远恩, 许志明, 张霖宙, 赵锁奇, 徐春明. 催化裂化油浆组成分布对中间相沥青光学织构的影响[J]. 化工学报, 2020, 71(6): 2678-2687.

Xiaoyu DAI, Yuan en MA, Zhiming XU, Linzhou ZHANG, Suoqi ZHAO, Chunming XU. Effects of composition distribution of catalytic slurry oils on optical texture of mesophase pitch[J]. CIESC Journal, 2020, 71(6): 2678-2687.

图/表 11

表1 催化油浆的基本性质

Table 1 Basic properties of three slurry oils

Properties	SLO-LH	SLO-YN	SLO-SH
carbon residue/%(mass)	8.16	10.83	16.08
ash/%(mass)	0.16	0.23	0.32
density/(cm³/g)	0.99	1.07	1.09
SARA/%(mass)
saturate	31.29	14.41	14.64
aromatic	45.49	71.78	59.39
resin	17.85	9.54	16.17
asphaltene	1.16	1.55	2.69
element/%(mass)
C	88.97	91.56	91.17
H	10.67	7.89	7.81
O	0.59	0.40	0.45
N	0.33	0.15	0.48
S	0.30	0.71	0.51
metal content/(μg/g)
Ni	5.20	2.40	11.30
V	<0.1	4.60	0.60
Al	76.00	279.00	638.00
Ca	3.10	3.30	12.60
Fe	14.30	6.80	34.50
Na	4.50	2.40	52.10

图1 微型反应釜简图

Fig.1 Brief depiction of micro-reactor

表2 中间相沥青及针状焦微观织构类型的命名与光学织构指数

Table 2 Nomenclature and optical texture index of microstructure types of mesophase asphalt and needle coke

Type	Size/shape	Index(OTI)
mosaic	<10 μm	1
small domain	10—60 μm	5
domain	>60 μm	50
flow domain	>60 μm long,>10 μm wide	100

表3 油浆的分子量数据

Table 3 Molecular weight of catalytic slurry

Sample	M_n	M_w	Dispersion coefficient
SLO-LH	574	2188.66	3.81
SLO-YN	263	333.74	1.27
SLO-SH	276	384.22	1.39

图2 催化油浆的分子量分布

Fig.2 Molecular weight distribution of catalytic slurry oils

图3 催化油浆的沸点分布

Fig.3 The boiling point distribution of SLO

图4 催化油浆的烃组成分布结果

Fig.4 Distribution of hydrocarbon composition of catalytic oil slurry

表4 3种催化油浆的1H NMR的分析结果

Table 4 1H NMR data of three kinds of slurry oil

Sample	h_a	h_α	h_β	h_γ	f_A	H_AU/C_A	C_T	H_T	σ
SLO-LH	0.10	0.12	0.65	0.13	0.35	0.65	42.52	60.76	0.36
SLO-YN	0.31	0.31	0.30	0.08	0.64	0.75	20.05	20.59	0.33
SLO-SH	0.31	0.28	0.33	0.08	0.64	0.72	20.95	21.39	0.31
Sample	C_A	R_T	R_A	R_N	C_N	C_S	C_P	L	n
SLO-LH	15.06	5.61	3.27	2.34	9.37	27.46	18.09	6.69	0.77
SLO-YN	12.89	4.31	2.72	1.59	6.37	7.17	0.79	1.39	1.06
SLO-SH	13.50	4.51	2.87	1.63	6.54	7.45	0.92	1.58	0.97

图5 中间相沥青的光学结构织构(放大200倍)

Fig.5 Typical optical structure of mesophase pitches(200×)

图6 中间相沥青的光学织构分布

Fig.6 Optical texture distribution of mesophase pitch

图7 不同中间相沥青的收率与OTI的对比

Fig.7 The comparison of yield and OTI of different mesophase pitches

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