油水膜分离中高黏度油滴行为研究和影响因素分析

doi:10.11949/0438-1157.20240088

摘要/Abstract

摘要：

膜法分离油田采出废水中的重油组分是膜污染的重要影响因素，且不同膜分离条件下膜面附近的复杂油滴行为直接影响膜分离效果，所以研究膜面附近的高黏度油滴行为十分必要。基于实际油田采出废水物性数据的实验测定结果，采用耗散粒子动力学（DPD）方法结合高黏度油滴轨迹和油滴间相互作用能结果对油滴行为进行细化分析。结果表明，双油滴呈现掠过和聚并两大类行为，又可各分为三个行为阶段：油滴间排液、油滴接触和油滴复稳；双油滴间距和油滴与膜面间距的减小有助于油滴聚并，从而有利于油水分离，且油滴与膜面间距的减小会导致油滴碰撞后的位置更远离膜面；表面活性剂的存在阻碍油滴聚并，不利于油水分离，且离子型表面活性剂因其亲水头间的强排斥力而阻碍作用更强；第3油滴的存在会促进双油滴聚并，有利于油水分离，其促聚并程度受油滴碰撞角的影响。研究结果可为后续的油滴与分离膜相互作用及油水分离效果的研究提供依据，也可为油水膜分离条件的设置和技术优化提供理论支持。

关键词: 膜分离, 耗散粒子动力学, 模拟, 油滴行为, 表面活性剂

Abstract:

Membrane separation of heavy oil components in oilfield produced wastewater is an important factor affecting membrane pollution, and the complex oil droplet behavior near the membrane surface directly affects the membrane separation effect under different membrane separation conditions. So it is necessary to study the behavior of high viscosity oil droplets near the membrane surface. Based on experimental results of the physical properties of actual oilfield produced wastewater, the dissipative particle dynamics (DPD) method was used to analyze the behavior of oil droplets by combining the trajectory of high viscosity oil droplets and the interaction energy between oil droplets. The results show that the double oil droplets exhibit two types of behaviors: passing and coalescing. Each can be divided into three behavioral stages: liquid drainage between oil droplets, oil droplet contact, and oil droplet stabilization. The decrease of the distance between double oil droplets and the distance between oil droplets and the membrane surface was conducive to the coalescence of oil droplets, which was conducive to oil-water separation, and the decrease of the distance between oil droplets and the membrane surface would cause the position of oil droplets after collision to be further away from the membrane surface. The presence of surfactants hindered the coalescence of oil droplets and was not conducive to oil-water separation, and ionic surfactants had a stronger hindering effect due to their strong repulsion between hydrophilic heads. The presence of the third oil droplet promoted the coalescence of the double oil droplets, and the degree of coalescence promotion was affected by the collision angle of oil droplets. The research results can provide a basis for the subsequent study of the interaction between oil droplets and separation membranes and the effectiveness of oil-water separation, as well as theoretical support for the setting and technical optimization of membrane oil-water separation conditions.

Key words: membrane separation, dissipative particle dynamics, simulation, oil droplet behavior, surfactants

中图分类号:

TQ 028.4

霍宗伟, 牛亚宾, 潘艳秋. 油水膜分离中高黏度油滴行为研究和影响因素分析[J]. 化工学报, 2024, 75(6): 2262-2273.

Zongwei HUO, Yabin NIU, Yanqiu PAN. Behavior of high viscosity oil droplets in oil-water membrane separation and its influencing factors[J]. CIESC Journal, 2024, 75(6): 2262-2273.

图/表 16

图1 油分子、金红石型TiO2晶胞和表面活性剂分子的构型

Fig.1 Configuration of oil molecule, rutile TiO2 cell and surfactant molecule

表1 物性参数实验测定结果

Table 1 Experimental results of physical property parameters

体系分类	自扩散系数/(m²/s)	动力黏度/(mPa·s)	界面张力/(mN/m)
水^[20-21]	2.30×10^-9	0.89	—
油	2.02×10^-11	136.14	—
油-水	—	—	8.9654
油-水-CTAB	—	—	0.2746
油-水-SDS	—	—	0.3261
油-水-SLS	—	—	1.7496
油-水-Tween-80	—	—	7.6272

图2 各分子的粗粒化模型

Fig.2 The coarse-grained model of each molecule

表2 DPD无量纲单位及对应实际值

Table 2 DPD dimensionless units and corresponding actual values

名称	DPD无量纲符号	DPD无量纲单位	实际值
质量	m	1	1.14×10^-24kg
长度	r_c、x、z、……	1	1.5066×10^-9m
温度	Θ	1 (k_BT)	298 K
能量	E	1 (k_BT)	4.1164×10^-21J
时间	t	1 (r_c(m/E)^1/2)	25.0266 ps
速度	v	1 (1/(m/E)^1/2)	60.1999 m/s
剪切速率	G	1 (1/t)	0.03996 ps^-1

表3 DPD模拟参数集结果

Table 3 Results of DPD simulation parameters

液相类型	N_{m_par}	s	γ	r_c
水相	4	0.25	20	1.0
油相	4	0.25	2650	1.0
油水相间	4	0.25	39.7	1.0

表4 包含珠子间静电相互作用的保守力参数

Table 4 Conservative force parameters including electrostatic interactions between beads

珠子类型	T-H	T	T-T	O	W	N	NA	S1	S2	BR	TIO
T-H	98.85
T	123.97	132.10
T-T	118.01	134.73	105.28
O	125.59	86.69	95.60	86.20
W	136.98	153.27	145.08	197.24	104.00
N	49.48	130.75	29.33	126.02	8.13	265.32
NA	33.78	160.55	35.40	131.10	55.69	261.00	276.54
S1	31.69	145.39	56.42	145.89	36.07	0	0	239.10
S2	41.82	150.08	63.15	166.39	65.43	0	0	246.92	259.00
BR	63.96	165.04	83.17	241.39	101.53	0	0	251.53	259.31	351.76
TIO	108.18	162.72	141.61	196.84	66.70	63.80	138.58	13.02	10.59	168.58	0

表5 界面张力实验值及模拟值

Table 5 Experimental and simulated results of interfacial tension

体系分类	实验值/ (mN/m)	模拟值/ (mN/m)	相对误差/%
油-水	8.9654	9.6743	7.91
油-水-CTAB	0.2746	0.2539	7.54
油-水-SDS	0.3261	0.3815	16.99
油-水-SLS	1.7496	1.6540	5.46
油-水-Tween-80	7.6272	6.7254	11.82

图3 膜面附近剪切流下双、三油滴体系物理模型示意图

Fig.3 Schematic diagram of the physical model of double and triple oil droplet system under shear flow near the membrane surface

图4 膜面附近双油滴行为分析

Fig.4 Behavior analysis of double oil droplets near the membrane surface

图5 Δz21_0对双油滴行为的影响

Fig.5 Influence of Δz21_0 on the behavior of double oil droplets

图6 Zd对双油滴行为的影响

Fig.6 Influence of Zd on the behavior of double oil droplets

图7 双油滴各自质心及总质心沿Z轴位移情况

Fig.7 Displacement of the double oil droplets' respective centroid and total centroid along the Z axis

图8 SAA对双油滴行为的影响

Fig.8 Influence of SAA on the behavior of double oil droplets

图9 膜面附近三油滴行为分析

Fig.9 Behavior analysis of triple oil droplets near the membrane surface

图10 OD3初始位置对双油滴行为的影响

Fig.10 Influence of OD3 initial position on the behavior of double oil droplets

表6 Δz32_0和Δx32_0改变时的油滴行为结果

Table 6 Oil droplet behavior results when Δz32_0 and Δx32_0 change

OD₃位置		θ₁₂/(°)	θ₂₃/(°)	中间行为	影响阶段	区域和易聚并程度^①
三油滴对照组		25.36	30.28	OD₂-OD₃先排液、先碰撞	油滴间排液阶段（Ⅰ）	A(++)
Δz_{32_0}改变	0.9R₁	30.34	27.74	OD₁-OD₂先排液，OD₂-OD₃先碰撞		A(+++)
	0.8R₁	30.68	20.97	OD₁-OD₂先排液，OD₂-OD₃先碰撞		B(+)
	0.7R₁	39.28	19.29	OD₁-OD₂碰撞前中程时OD₂-OD₃碰撞	油滴碰撞阶段（Ⅱ-1）	A(++)
Δx_{32_0}改变	-5.25R₁	39.01	28.59			A(++++)
	-5.50R₁	55.31	20.84			A(+++)
	-5.75R₁	81.14	18.87	OD₁-OD₂碰撞后程时OD₂-OD₃碰撞	油滴逃离阶段（Ⅱ-2）	B(+)
	-6.00R₁	93.82	18.35	OD₁-OD₂碰撞后程时OD₂-OD₃碰撞	油滴逃离阶段（Ⅱ-2）	B(+)

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