Study on the Adsorption of Asphaltenes and Their Sub⁃Components by Mg⁃Al⁃LDH in Tahe

doi:10.3969/j.issn.1006-396X.2022.03.002

Abstract

Abstract:

Mg?Al?LDH was synthesized by the constant pH co?precipitation method,and the micro?structure and composition of the layered bimetallic hydroxides were characterized by X?ray diffraction (XRD),scanning electron microscopy (SEM),energy dispersive spectroscopy (EDS) and BET.The results show that LDHs were successfully prepared with a layered structure,a high degree of order,and mesopores.The toluene?n?heptane method was used to separate the asphaltenes in Tahe into heavy component A₁ and light component A₂.The elemental analysis indicates that A₁ had the highest polarity,followed by the Tahe asphaltenes and A₂.This paper further investigated the adsorption properties of Mg?Al?LDH for asphaltenes and their sub?components A₁ and A₂ in Tahe and found that the adsorption equilibrium can be reached within 2~3 h.The experimental data fitted well with the pseudo?second?order kinetics,and the adsorption isotherms followed the Langmuir model. The adsorption capacity of Mg?Al?LDH was 71.38,140.65 and 39.31 mg/g for asphaltenes in Tahe and their sub?components A₁ and A₂,respectively.

Key words: Bimetallic hydroxide, Asphaltenes, Sub?components, Adsorption

摘要：

采用pH恒定共沉淀法合成了双金属氢氧化物Mg?Al?LDH，采用X射线衍射(XRD)、扫描电镜(SEM)、能谱(EDS)及BET等手段对其微观形貌、结构和组成进行表征。结果表明，成功制备出具有层状结构且有序程度较高的LDHs，其孔径属于介孔范畴。采用甲苯?正庚烷法将塔河沥青质（T_A）分离成重组分(A₁)和轻组分(A₂)，并对其进行元素分析，得知A₁的极性最大，其次依次为T_A和A₂。进一步考察了Mg?Al?LDH对塔河沥青质及其亚组分A₁、A₂的吸附性能，研究发现Mg?Al?LDH对T_A及其亚组分A₁、A₂的吸附可在2~3 h达到平衡，实验数据与准二级动力学拟合较好，所得吸附等温线符合Langmuir模型，Mg?Al?LDH对T_A及其亚组分A₁、A₂的吸附量分别为71.38、140.65、39.31 mg/g。

关键词: 双金属氢氧化物, 沥青质, 亚组分, 吸附

CLC Number:

TQ110.9

Mengshuang Zhu, Genxiang Luo, Lingzi Xu, Donghao Lin, Jin Huang, Mingyu Qi. Study on the Adsorption of Asphaltenes and Their Sub⁃Components by Mg⁃Al⁃LDH in Tahe[J]. Journal of Petrochemical Universities, 2022, 35(3): 10-15.

朱孟爽, 罗根祥, 许凌子, 林东浩, 黄金, 齐明玉. Mg⁃Al⁃LDH对塔河沥青质及其亚组分的吸附研究[J]. 石油化工高等学校学报, 2022, 35(3): 10-15.

Figures/Tables 11

Fig.1 X?ray diffraction pattern of Mg?Al?LDH

Table 1 XRD structural parameters of Mg?Al?LDH

2θ_(003）/（°）	d_(003）/nm	D_(003）/nm	2θ_(006）/（°）	d_(006）/nm	D_(006）/nm	a/nm	c/nm
11.580	0.767 5	18.643 6	23.300	0.383 1	17.025 7	30.051 0	230.032 0

Fig.2 SEM image of Mg?Al?LDH

Table 2 EDS analysis of Mg?Al?LDH

质量分数/%			原子分数/%
O	Mg	Al	O	Mg	Al
55.64	29.78	14.58	66.32	23.37	10.31

Table 3 Elemental analysis of TA and its subcomponents A1 and A2

样品	w（元素）/%
样品	N	C	H	S	O
T_A	1.697	85.976	7.052	4.267	1.008
A₁	1.555	85.422	6.741	4.136	2.146
A₂	1.608	85.422	8.104	3.863	1.003

Table 4 Mass ratio of heteroatoms and C+H atoms of asphaltene and its subcomponents A1 and A2

样品	m_(O+N+S)/m_(C+H)
T_A	0.074 7
A₁	0.085 0
A₂	0.069 3

Fig.3 Fitting curve of Langmuir model(a) and Freundlich model(b)

Table 5 Fitting adsorption data of Mg?Al?LDH by Langmuir and Freundlich models

样品	Langmuir模型						Freundlich模型
样品	q_m/(mg $⋅$ g^-1)	K_L/(L $⋅$ mg^-1)			R²	1/n	K_F/(mg $⋅$ g^-1)	R²
T_A	71.38		0.018	0.997		0.592	3.12	0.982
A₁	140.65		0.006	0.999		0.800	1.25	0.983
A₂	39.31		0.007	0.996		0.575	0.95	0.947

Table 5 Fitting adsorption data of Mg?Al?LDH by Langmuir and Freundlich models

样品	Langmuir模型						Freundlich模型
样品	q_m/(mg $⋅$ g^-1)	K_L/(L $⋅$ mg^-1)			R²	1/n	K_F/(mg $⋅$ g^-1)	R²
T_A	71.38		0.018	0.997		0.592	3.12	0.982
A₁	140.65		0.006	0.999		0.800	1.25	0.983
A₂	39.31		0.007	0.996		0.575	0.95	0.947

Fig.4 Adsorption kinetics curve of Mg?Al?LDH to TA and its subcomponents A1 and A2

Fig.5 Curve fitted by quasi?first?order kinetics and quasi?second kinetics models

Table 6 Adsorption kinetic fitting parameters

样品	C₀/(mg·L^-1)	准一级动力学		准二级动力学
样品	C₀/(mg·L^-1)	k₁/（min^-1)	R²	k₂/(g·mg^-1·min^-1)	R²
T_A	180	0.385	0.958	0.007	0.999
A₁	180	0.337	0.843	0.017	0.999
A₂	180	0.392	0.913	0.006	0.997

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