不同基属渣油正戊烷及正庚烷沥青质结构组成研究

孙昱东; 王泽州; 李茂林; 肖胜玉

doi:10.19906/j.cnki.JFCT.2022018

不同基属渣油正戊烷及正庚烷沥青质结构组成研究

doi: 10.19906/j.cnki.JFCT.2022018

1.
中国石油大学(华东)化学工程学院山东青岛 266580
2.
中石化青岛炼油化工有限公司炼油三部山东青岛 266500

详细信息

通讯作者:
Tel：15066836878/0532-86980605， E-mail：ydsun@upc.edu.cn

中图分类号: TE624.5
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出版历程
- 收稿日期: 2022-01-10
- 修回日期: 2022-03-11
- 录用日期: 2022-03-21
- 网络出版日期: 2022-03-24
- 刊出日期: 2022-10-21

Structure and composition of n-pentane and n-heptane asphaltene from different properties crude

1.
College of Chemical Engineering, China University of Petroleum, Qingdao 266580, China
2.
SINOPEC Qingdao Refining & Chemical CO., LTD, Qingdao 266500, China

摘要

摘要: 采用SARA四组分分离方法得到石蜡基玉门常压渣油和环烷基马瑞常压渣油的C₅和C₇沥青质，结合 ¹H-NMR、FT-IR、VPO及元素分析等方法，对沥青质的结构组成和官能团形态进行表征，考察不同基属渣油沥青质以及不同沉淀剂所得沥青质的结构组成差异。结果表明，四种沥青质的官能团类型基本一致，但分子结构单元存在一定差异，相比于环烷基马瑞沥青质，石蜡基玉门沥青质的分子结构单元更大，芳碳分率较小，但H_AU/C_A值也较小，分子缩合程度更高；随沉淀剂碳链增长，沥青质收率减少(相同原料的正庚烷沥青质收率约为正戊烷沥青质的80%左右)，H/C降低，平均相对分子量升高，C₇沥青质具有更高的芳碳率$ f $_A和更多的结构单元数。各类沥青质中均存在较多的饱和结构，饱和碳分率约为0.5。
- 沥青质 /
- 沉淀剂 /
- 原油基属 /
- 结构组成 /
- 官能团
Abstract: C5 and C7 asphaltene were separated from paraffin base Yumen atmospheric residue and naphthene base Merey atmospheric residue by n-pentane and n-heptane respectively using the method of SARA. The structure parameters and functional groups analyzed and characterized systematically by VPO, ¹H-NMR, FT-IR and elemental analysis, in order to comparative studied the differences in asphaltene structure of different residues and asphaltene obtained by different precipitants. The results showed that there was consistent in the functional groups of different asphaltenes basically, but there was some differences in the unit structure of different asphaltene. Yumen paraffinic asphaltenes had significantly higher molecular weight, smaller H_AU/C_A value and higher condensation degree than Merey naphthenic asphaltenes. With the increase of carbon chain of precipitants, the yield (the yield of n-heptane asphaltene was about 80% of n-pentane for the some feedstook) and the H/C of asphaltene decreased, the molecular weight of asphaltene increased. C₇ asphaltenes had higher aromatic carbon ratio ($ f $_A) and more structure units than C₅ asphaltene. More saturated structure existed in various asphaltenes and the saturate carbon fraction was about 0.5.
- asphaltene /
- precipitants /
- crude properties /
- structure & composition /
- functional group

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FIG. 1878. FIG. 1878.

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图 1 沥青质的核磁共振氢谱谱图

Figure 1 ¹H-NMR spectrogram of asphaltene

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图 2 马瑞沥青质的红外光谱谱图

Figure 2 FT-IR specta of MR asphaltene

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图 3 玉门沥青质的红外光谱谱图

Figure 3 FT-IR specta of YM asphaltene

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表 1 原料性质

Table 1 Properties of residue

Item	YMAR	MRAR
Density (20℃)/(kg·m⁻³)	898.5	986.2
Viscosity (100℃)/(mm²·s⁻¹)	10.13	130.70
Carbon residue w/%	5.21	13.40
SARA w/%
Saturate	49.62	38.04
Aromatic	24.07	29.80
Resin	15.56	19.34
Asphaltene	10.75	12.81
Elemental w/%
C	86.30	84.76
H	12.60	10.84
S	0.77	3.74
N	0.28	0.51
H/C(mol ratio)	1.75	1.53

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表 2 沥青质收率

Table 2 Yield of asphaltenes

Asphaltene	C5YM	C7YM	C5MR	C7MR
Yield w/%	13.58	10.75	16.11	13.23
Note: C5: n-pentane asphaltene; C7: n-heptane asphaltene; YM: Yumen atmospheric residue; MR: Merey atmospheric residue

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表 3 沥青质的元素组成及平均相对分子质量

Table 3 Element composition and molecular weight of asphaltene

Asphaltene	Vitimate analysis w/%				H/C (mol ratio)	M
Asphaltene	C	H	S	N	H/C (mol ratio)	M
C5YM	85.58	8.54	2.10	1.13	1.20	4468
C7YM	86.41	7.99	2.42	1.93	1.11	4735
C5MR	83.40	8.08	4.70	1.53	1.16	3561
C7MR	82.94	7.71	4.81	1.73	1.12	4612

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表 4 沥青质中不同化学位移的氢含量

Table 4 Different H content of asphaltene

Item	C5YM	C7YM	C5MR	C7MR
H_γ w/%	30.22	17.08	29.43	32.31
H_β w/%	52.85	59.77	49.49	42.75
H_α w/%	4.86	14.97	6.01	9.82
H_A w/%	12.08	8.17	15.07	15.11

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表 5 沥青质结构参数

Table 5 Structural parameters of asphaltene

Structural parameter	C5YM	C7YM	C5MR	C7MR
C_T	318.38	340.68	177.84	318.5
H_T	378.58	375.36	205.31	352.8
C_A	151.94	168.35	90.66	168.77
R_A	49.31	54.78	28.89	54.92
R_T	54.12	69.82	30.86	58.72
R_N	4.81	15.04	1.97	3.79
R_A/R_N	10.25	3.64	14.64	14.49
C_N	14.43	45.12	5.92	11.37
C_P	152.01	127.21	81.26	138.36
H_AU/C_A	0.36	0.35	0.41	0.42
$ f $_A	0.48	0.49	0.51	0.53
$ f $_N	0.05	0.13	0.03	0.04
$ f $_p	0.48	0.37	0.46	0.43
σ	0.17	0.48	0.17	0.25
n	3.17	3.27	2.42	4.72
Usw	1409.47	1446.25	1056.29	977.54
C_A^*	47.93	51.42	37.39	35.77
C_T^*	100.43	104.06	73.35	67.51
H_T^*	119.42	114.65	84.68	74.78
R_T^*	17.07	21.33	12.73	12.44
R_A^*	15.56	16.73	11.91	11.64
R_N^*	1.52	4.59	0.81	0.80

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