典型表活剂与稠油在蒙脱石表面吸附行为的分子动力学模拟

doi:10.19596/j.cnki.1001-246x.8647

摘要/Abstract

摘要：

为探究蒸汽与表面活性剂复合驱对稠油与黏土矿物表面吸附稳定性的影响, 建立表活剂溶液、稠油和蒙脱石的三元吸附体系, 采用分子动力学方法阐释稠油与表活剂在蒙脱石表面的微观竞争吸附机理。计算结果表明: 非离子型表活剂难以与蒙脱石表面接触, 但在高温吸附质环境中具有较强的扩散能力; 阳离子型表活剂在较低温度下占据蒙脱石表面吸附位点并使稠油分子脱离蒙脱石; 而阴离子表活剂在高温条件下容易使稠油分子远离蒙脱石。高温促使沥青质聚集核离散, 从而促进稠油的流动, 但会导致部分表活剂更加亲附蒙脱石而造成非必要的损失。本研究为合理调整温度与表活剂的匹配性, 为敏感性稠油油藏的开发提供了良好的应用前景及推广意义。

关键词: 分子动力学, 表面活性剂, 蒙脱石, 稠油, 吸附行为

Abstract:

To investigate the adsorption mechanism of heavy oil on clay mineral surface during surfactant flooding, the microscopic mechanism of heavy oil and surfactant on montmorillonite surface under different temperatures can be explained by molecular dynamics simulation. Based on the four components (SARA) of heavy oil and sodium montmorillonite, the molecular dynamics simulation of the adsorption process is carried out after the water phase adsorbent containing surfactant molecules is added into the adsorption system. It shows that cationic surfactant tends to adsorb on the surface of montmorillonite and occupy more adsorption area, which makes the heavy oil molecules tend to separate from the surface of montmorillonite. The non-ionic surfactant does not show a tendency to adsorb towards the surface of montmorillonite during the relaxation process. Non-ionic surfactant has a high self-diffusion coefficient and thus diffuses in the adsorbent environment. High temperature disperses asphaltene aggregation nuclei in heavy oil, which facilitates heavy oil to flow away from the montmorillonite surface. However, high temperatures can also cause some surfactants more adhesion to the montmorillonite surface, resulting in surfactant loss. This study provides theoretical support for adjusting temperature and surfactant types during surfactant development and enhancing oil recovery of sensitive heavy oil reservoirs.

Key words: molecular dynamics simulation, surfactant, montmorillonite, heavy oil, adsorption behavior

李禹, 刘慧卿, 冯亚斌, 东晓虎, 王庆, 张波. 典型表活剂与稠油在蒙脱石表面吸附行为的分子动力学模拟[J]. 计算物理, 2023, 40(5): 583-596.

Yu LI, Huiqing LIU, Yabin FENG, Xiaohu DONG, Qing WANG, Bo ZHANG. Adsorption Behavior of Heavy Oil on Montmorillonite Surface by Typical Surfactant: Molecular Dynamics Simulation[J]. Chinese Journal of Computational Physics, 2023, 40(5): 583-596.

图/表 16

图1 钠基蒙脱石分子球棍模型(黄，红，粉，绿，紫和白色分别为硅，氧，铝，镁，钠和氢原子。)

Fig.1 Ball-and-stick model of sodium-montmorillonite molecules (Yellow, red, pink, green, purple, and white are silicon, oxygen, aluminum, magnesium, sodium, and hydrogen, respectively.)

图2 4组分球棍模型(灰色，白色，蓝色和黄色分别代表碳原子，氢原子，氮原子和硫原子。) (a) 饱和烃(C12H26); (b) 芳香烃(C30H46); (c) 胶质(C50H80S); (d) 沥青质(C56H71N)

Fig.2 Ball-and-stick models of the four components in heavy oil (Gray, white, blue and yellow represent carbon, hydrogen, nitrogen and sulfur atoms respectively.) (a) saturate (C12H26); (b) aromatic (C30H46); (c) resin (C50H80S); (d) asphaltene (C56H71N)

图3 含有不同表活剂的三元吸附体系 (a) SDBS; (b) DTAB; (c) OP-10

Fig.3 Ternary adsorption system with different surfactant (a) SDBS; (b) DTAB; (c) OP-10

图4 吸附体系的弛豫过程(温度为333 K) (a) SDBS; (b) DTAB; (c) OP-10

Fig.4 Relaxation process of adsorption system (temperature 333 K) (a) SDBS; (b) DTAB; (c) OP-10

表1 不同条件下沥青质分子的质心与蒙脱石表面的平均距离das-mo(nm)

Table 1 Average distance das-mo (nm) between the centroid of asphaltene molecules and montmorillonite at different temperatures and surfactant concentrations

表活剂种类	数量	温度
表活剂种类	数量	333 K	363 K	393 K
SDBS	5	1.826	2.284	2.512
	10	2.115	2.442	2.667
	20	2.229	2.552	2.732
DTAB	5	1.812	2.244	2.417
	10	2.076	2.375	2.636
	20	2.334	2.791	2.914
OP-10	5	1.823	2.063	2.227
	10	1.778	2.015	2.294
	20	1.928	2.284	2.352

图5 三元吸附体系在吸附过程中释放的吸附热 (a)SDBS体系吸附热；(b)DTAB体系吸附热；(c)OP-10体系吸附热

Fig.5 Adsorption heat of ternary adsorption system on the surface of montmorillonite (a)adsorption heat of SDBS system; (b)adsorption heat of DTAB system; (b)adsorption heat of OP-10 system

图6 升温过程中沥青质组分在蒙脱石表面的相对密度分布(表活剂分子数为10) (a)SDBS；(b)DTAB；(C)0P-10

Fig.6 Relative concentration of asphaltenes on montmorillonite surface during heating (number of surfactant molecules 10) (a)SDBS; (b)DTAB; (c)OP-10

图7 表活剂浓度升高过程中沥青质组分在蒙脱石表面的相对密度分布(温度为333 K) (a)SDBS；(b)DTAB

Fig.7 Relative concentration of asphaltenes on montmorillonite surface during increase concentration (temperature 333 K) (a)SDBS; (b)DTAB

图8 三种表活剂分子不同温度下的均方位移曲线及平衡态表活剂分子分布

Fig.8 Mean square displacement of three types of surfactant molecules at different temperatures

表2 表活剂自扩散系数，D(10-8 m2 ·s-1)

Table 2 Self-diffusivity of different types of surfactant, D(10-8 m2·s-1)

表活剂类型	333 K	363 K	393 K
SDBS	0.092 9	0.104 0	0.116 1
DTAB	0.086 5	0.084 9	0.085 5
OP-10	0.273 2	0.311 4	0.342 5

图9 不同类型表活剂分子在蒙脱石表面垂向上的相对浓度分布(表活剂分子数为10) (a)SDBS；(b)DTAB；(C)0P-10

Fig.9 Relative concentrations of different types of surfactant molecules on montmorillonite surface (number of surfactant molecules 10) (a)SDBS; (b)DTAB; (c)OP-10

图10 平衡状态下的沥青质分子堆积构型(DTAB表活剂分子数为5) (a)错位面对面堆积作用(F型)；(b)边对面堆积作用(T型)

Fig.10 The accumulative configuration of asphaltene molecules at equilibrium (number of DTAB surfactant molecules 5) (a) staggered face-to-face stacking (F-shaped); (b) side to side stacking (T-shape)

表3 不同条件下沥青质分子的质心平均距离din(nm)

Table 3 Average distance din (nm) between the center of mass of asphaltene molecules at different temperatures and surfactant concentrations

表活剂类型	分子个数	温度
表活剂类型	分子个数	333 K	363 K	393 K
SDBS	5	0.896	1.045	1.232
	10	0.935	1.127	1.288
	20	0.976	1.195	1.372
DTAB	5	0.903	1.011	1.247
	10	1.017	1.178	1.294
	20	1.252	1.367	1.433
OP-10	5	0.861	1.084	1.135
	10	0.861	1.084	1.135
	20	0.861	1.084	1.135

表4 沥青质、表活剂在蒙脱石表面的范德华能和静电作用势能

Table 4 Van der Waal energy and electrostatic potential energy of asphaltenes and surfactants on montmorillonite surface

表活剂类型	温度/K	沥青质吸附质-蒙脱石吸附剂		表活剂吸附质-蒙脱石吸附剂
表活剂类型	温度/K	静电势能/(kcal·mol^-1)	范德华势能/(kcal·mol^-1)	静电势能/(kcal·mol^-1)	范德华势能/(kcal·mol^-1)
SDBS	333	-265	-420	-6 000	82
	363	-255	-380	-6 035	85
	393	-223	-329	-6 001	86
DTAB	333	-259	-442	-5 661	16
	363	-242	-377	-5 760	33
	393	-217	-280	-5 804	47
OP-10	333	-366	-553	0	0
	363	-356	-333	0	0
	393	-344	-273	0	0

图11 蒙脱石表面的氢键分布(温度为333 K，分子数为5) (a)SDBS；(b)DTAB；(C)0P-10

Fig.11 Hydrogen bond distribution on the montmorillonite surface (The temperature is 333 K, number of molecules is 5) (a)SDBS; (b)DTAB; (c)OP-10

表5 水分子与蒙脱石之间存在的氢键数量

Table 5 The number of hydrogen bonds between water molecules and montmorillonite

表活剂类型	分子个数	温度
表活剂类型	分子个数	333 K	363 K	393 K
SDBS	5	198	207	214
	10	220	227	233
	20	267	276	281
DTAB	5	226	220	218
	10	254	247	242
	20	288	271	263
OP-10	5	187	195	208
	10	185	196	210
	20	184	196	211

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