沥青岩中界面活性沥青质分子结构及其在矿物表面吸附特征

doi:10.16085/j.issn.1000-6613.2021-0633

摘要/Abstract

摘要：

重质油固体系（如油砂、沥青岩、油页岩、重质油、油泥等）中因油-水-固三相复杂作用，导致分离困难。本文以印尼沥青岩重质油为例，针对重质组分中界面活性最强的界面活性沥青质的结构及其在矿物质表面吸附特性问题进行研究。通过凝胶渗透色谱、红外光谱仪、XPS等对界面活性沥青质的结构进行分析，提出其初步结构。以SiO₂为矿物固体模型，在甲苯溶剂环境中，采用QCM-D和AFM研究界面活性沥青质在固体表面的吸附特征，发现该类沥青质分子在SiO₂表面的吸附与普通沥青质分子存在较大差异，呈现多层吸附特征，符合Freundlich吸附模型。吸附膜存在较多高分散性团聚体，黏弹性较大，易于形成具有三维结构的强机械性界面膜。该结构和界面吸附特性可为揭示其在油水乳液稳定过程中的机理提供有利基础。

关键词: 界面, 吸附, 二氧化硅, 界面活性沥青质

Abstract:

Separation is difficult due to the complex interaction of oil-water-solid three phases in heavy oil solids (such as oil sands, bituminous rocks, oil shale, heavy oil, oil sludge, etc.). This article takes Indonesian bituminous heavy oil as an example to study the structure of the interfacially active asphaltene which has the strongest interfacial activity among the heavy components and its adsorption characteristics on the surface of minerals. The structure of interfacially active asphaltene was analyzed by gel permeation chromatography, infrared spectrometer, XPS, etc., and its preliminary structure was proposed. Taking SiO₂ as the mineral solid model, using QCM-D and AFM to study the adsorption characteristics of interfacially active asphaltenes on the solid surface in a toluene solvent environment, it is found that the adsorption of this subfraction of asphaltene molecules on the SiO₂ surface is larger than that of ordinary asphaltene molecules. The difference shows the characteristics of multilayer adsorption, which is in line with the Freundlich adsorption model. The adsorption film has more high-dispersion agglomerates and greater viscoelasticity, and is easy to form a strong mechanical interface film with three-dimensional structure. The structure and interface adsorption characteristics can provide a favorable basis for revealing its mechanism in the oil-water emulsion stabilization process.

Key words: interface, adsorption, silica, interfacially active asphaltene

中图分类号:

TE622

章雪莹, 马俊, 何林, 隋红, 李鑫钢. 沥青岩中界面活性沥青质分子结构及其在矿物表面吸附特征[J]. 化工进展, 2022, 41(2): 628-636.

ZHANG Xueying, MA Jun, HE Lin, SUI Hong, LI Xingang. Molecular structure of interfacially active asphaltene in asphalt rock and its adsorption characteristics on mineral surface[J]. Chemical Industry and Engineering Progress, 2022, 41(2): 628-636.

图/表 11

图1 IAA提取过程

图2 IAA及沥青质凝胶渗透色谱测试结果

表1 IAA的元素分析

样品	元素（质量分数）/%						H/C
样品	C	H	N	S	O	总计	H/C
IAA	73.01	7.64	0.98	9.83	4.60	96.06	—
IAA（归一化）	76.00	7.95	1.02	10.23	4.80	100.00	1.26

图3 IAA、残余沥青质、沥青质的红外光谱图

图4 IAA分子中不同原子（C、S、N、O）的XPS分析结果

表2 核磁共振氢谱中不同位置的氢的相对含量

氢的类型	化学位移/mg·L^-1	相对含量
H_aro	10.0~6.0	0.0647
H_ali	4.0~0.4	0.9353
H_α	4.0~2.0	0.1707
H_β	2.0~1.0	0.6014
H_γ	1.0~0.4	0.1632

表3 由改进B-L法计算得到IAA的结构参数

符号	结构参数	公式	结果
f_A	芳碳率	$f A = C / H - (H α + H β + H γ) / 2 H T C / H$	0.4128
H_AU/C_A	芳香环系缩合度	$H A U C A = H A / H T + H α / 2 H T C / H - (H α + H β + H γ) / 2 H T$	0.4564
σ	芳香环系周边氢取代率	$σ = H α / 2 H A + H α / 2$	0.5688
C_A	芳香碳数	$C A = C T f A$	56.83
C_S	饱和碳数	$C s = C T - C A$	80.85
R_A	芳香环数	$R A = (C A - 4) / 3$	17.61
R_T	总环数	$R T = C T + 1 - H T / 2 - C A / 2$	23.82
R_N	环烷烃环数	$R N = R T - R A$	6.21
C_N	环烷烃碳数	$C N = 3 R N$	18.63
n	结构单元数	$n = C A / 2.503 H A U / C A 2$	1.89
R_S	芳香环系烷基取代基数	$R S = σ [H T (H A + H α / 2)]$	7.81

表3 由改进B-L法计算得到IAA的结构参数

符号	结构参数	公式	结果
f_A	芳碳率	$f A = C / H - (H α + H β + H γ) / 2 H T C / H$	0.4128
H_AU/C_A	芳香环系缩合度	$H A U C A = H A / H T + H α / 2 H T C / H - (H α + H β + H γ) / 2 H T$	0.4564
σ	芳香环系周边氢取代率	$σ = H α / 2 H A + H α / 2$	0.5688
C_A	芳香碳数	$C A = C T f A$	56.83
C_S	饱和碳数	$C s = C T - C A$	80.85
R_A	芳香环数	$R A = (C A - 4) / 3$	17.61
R_T	总环数	$R T = C T + 1 - H T / 2 - C A / 2$	23.82
R_N	环烷烃环数	$R N = R T - R A$	6.21
C_N	环烷烃碳数	$C N = 3 R N$	18.63
n	结构单元数	$n = C A / 2.503 H A U / C A 2$	1.89
R_S	芳香环系烷基取代基数	$R S = σ [H T (H A + H α / 2)]$	7.81

图5 IAA及沥青质QCM-D吸附实验数据

表4 IAA及沥青质在二氧化硅表面的吸附动力学

浓度/mg·L^-1	IAA			沥青质
浓度/mg·L^-1	k₁	k₂	R²	k₁	k₂	R²
2	0.00156	2.03E-08	0.99	0.003844	0.000968	0.99
5	0.00667	0.000966	0.99	0.005468	0.000967	0.99
10	0.00786	0.000383	0.99	0.009055	0.001402	0.99
20	0.00815	0.000823	0.98	0.012364	0.002053	0.99
50	0.00846	0.000743	0.98	0.021559	0.004414	0.99
100	0.02210	0.000689	0.99	0.033569	0.006589	0.99

图6 甲苯中沥青质、IAA和二氧化硅表面之间的相互作用力曲线

图7 吸附前后二氧化硅表面形貌分析

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