Research on direct hydro-upgrading of crude oils and the dissociation of asphaltene supramolecules

doi:10.11949/0438-1157.20240977

Abstract

Abstract:

Hydrotreating is a crucial process for upgrading low-quality heavy oils. However, the presence of asphaltene supramolecules severely impedes the efficiency of hydrogenation. Therefore, it is very important to improve the hydrogenation decomposition efficiency of asphaltene supramolecular in three main hierarchical structures (molecular unit, nanoaggregate and cluster). This study investigated the reaction performance of direct hydrogenation of crude oil and the change law of asphaltene supramolecular hierarchical structure, aiming to provide a new solution for improving the asphaltene supramolecular decomposition efficiency in petroleum. The results indicate that direct crude oil hydrogenation performs better in upgrading than heavy oil hydrogenation, achieving a removal rate of over 70% for non-hydrocarbon components and more than 80% for asphaltenes. During the crude oil hydrogenation, the apparent structural size of asphaltene decreased from a range of 2—4 μm to below 2 μm, resulting in a more uniform particle size. The hierarchical structure of asphaltene supramolecules has changed significantly. The size of supramolecular clusters has decreased by over 50% compared to their size before hydrogenation. Additionally, nearly 90% of the amorphous nanoaggregates in asphaltene supramolecular structures have been converted, and the conversion of difficult-to-convert crystalline nanoaggregates has exceeded 70%. Hydrogenating crude oils decrease the spatial shielding effect among molecular units, resulting in a more compact secondary structure. This study investigated a novel method for the direct hydrogenation of crude oils, aiming to enhance the dissociation of asphaltene supramolecules and facilitate the efficient conversion of low-quality crude oils.

Key words: crude oil, hydrogenation, asphaltene, polymerization, dissociation, hierarchical structure

摘要：

加氢处理是劣质重油提质升级的重要工艺，但是沥青质超分子的存在严重影响了加氢改质的效果。因此，针对沥青质超分子三个主要层级结构（分子单元、纳米聚集体和团簇），提高其加氢解缔效率至关重要。本研究考察了原油直接加氢的反应性能及沥青质超分子层级结构的变化规律，旨在为提高石油中沥青质超分子解缔效率提供新的解决方案。结果表明，与重油加氢相比，原油直接加氢表现出更优异的改质性能，其中非烃化合物的脱除率超过70%，而沥青质的脱除率则超过80%。在原油加氢过程中，沥青质的表观结构尺寸从原先的2~4 μm降低到2 μm以下，且颗粒尺寸变得更加均匀。沥青质超分子的层级结构也发生了显著变化，超分子团簇的尺寸相比加氢前减少了50%以上，沥青质超分子中90%的非晶纳米聚集体被转化，而难以转化的似晶纳米聚集体的转化率也超过了70%。原油加氢处理降低了分子单元之间的空间屏蔽效应，使其形成了更紧密的次级结构。本研究探索了原油直接加氢改质的新方法，以提高沥青质超分子解缔性能，促进劣质原油的高效利用。

关键词: 原油, 加氢, 沥青质, 聚合, 解缔, 层级结构

CLC Number:

TE 624

Shunnian XU, Xiao FENG, Dejun SHI, Zhiguo SUN, Chenwei ZHANG, Gang WANG, Jinsen GAO, Chunming XU. Research on direct hydro-upgrading of crude oils and the dissociation of asphaltene supramolecules[J]. CIESC Journal, 2025, 76(2): 812-824.

许顺年, 冯晓, 史得军, 孙志国, 张宸玮, 王刚, 高金森, 徐春明. 原油直接加氢改质及其沥青质超分子解缔反应的研究[J]. 化工学报, 2025, 76(2): 812-824.

Figures/Tables 15

Table 1 The properties of feedstocks

指标	BC	BH
ρ²⁰/(kg·m^-3)	881.5	921.8
残炭/%（质量）	7.92	13.75
元素组成/%（质量）
C	84.05	84.56
H	12.53	11.34
S	3.19	3.72
N	0.23	0.38
金属含量/(μg·g^-1)	66.5	92.5
胶质/%（质量）	7.81	21.72
沥青质/%（质量）	2.85	4.63
馏分段收率/%（质量）
IBP~180℃	10.2	—
180~350℃	24.5	2.2
350~500℃	20.0	31.2
>500℃	45.3	66.6

Fig.1 The loading conditions of the hydrogenation catalyst

Fig.2 Schematic diagram of high-pressure hydrogenation apparatus

Table 2 The properties of hydrogenation oils

指标	BH-HT	BC-HT1	BC-HT2
ρ²⁰/(kg·m^-3)	884.9	866.4	868.2
残炭/%（质量）	5.48	3.55	3.79
元素组成/%（质量）
C	86.44	86.33	86.49
H	12.38	13.40	13.18
S	0.93	0.20	0.30
N	0.25	0.07	0.03
金属含量/(μg·g^-1)	18.1	19.3	17.3
胶质/%（质量）	17.63	5.71	6.09
沥青质/%（质量）	2.70	0.27	0.41

Fig.3 Hydro-upgrading of crude oils

Fig.4 Hydro-upgrading of crude oils

Fig.5 SEM images of primary and secondary asphaltenes

Fig.6 The evolution of clusters before and after hydrotreatment

Table 3 Structural parameters of the amorphous nanoaggregates

指标	初始沥青质	BH-HT	BC-HT1	BC-HT2
f_A	0.50	0.55	0.59	0.58
f_P	0.39	0.33	0.24	0.25
R_A	61.8	55.4	46.6	49.0
R_N	13.5	12.4	13.8	14.7
H_AU/C_A	0.42	0.40	0.32	0.33

Fig.7 XRD patterns of the nanoaggregates and graphite

Fig.8 The content of nanoaggregates before and after hydrotreatment

Table 4 Structural parameters of the amorphous nanoaggregates

指标	初始沥青质	BH-HT	BC-HT1	BC-HT2
f_A^XRD	0.20	0.23	0.27	0.23
d_m/nm	0.36	0.36	0.35	0.36
d_γ/nm	0.57	0.56	0.56	0.56
L_a/nm	2.38	1.73	1.67	1.72
L_c/nm	1.75	1.67	1.60	1.64
N	5.97	5.73	5.47	5.61
N_ar	8.91	6.48	6.26	6.45

Fig.9 The evolution of crystalline nanoaggregates before and after hydrotreatment

Table 5 Structural parameters of the molecular units

指标	初始沥青质	BH-HT	BC-HT1	BC-HT2
n	5.3	4.4	2.4	2.7
f_A	0.50	0.55	0.59	0.58
f_P	0.39	0.33	0.24	0.25
$R_{A}^{*}$	11.6	12.6	19.8	18.3
$R_{N}^{*}$	2.5	2.8	5.9	5.5
H_AU/C_A	0.42	0.40	0.32	0.33

Table 5 Structural parameters of the molecular units

指标	初始沥青质	BH-HT	BC-HT1	BC-HT2
n	5.3	4.4	2.4	2.7
f_A	0.50	0.55	0.59	0.58
f_P	0.39	0.33	0.24	0.25
$R_{A}^{*}$	11.6	12.6	19.8	18.3
$R_{N}^{*}$	2.5	2.8	5.9	5.5
H_AU/C_A	0.42	0.40	0.32	0.33

Fig.10 The evolution of molecular units before and after hydrotreatment

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