乳化热固性树脂体系构建及其封堵性能评价

doi:10.3969/j.issn.2097-2806.2023.06.006

Abstract

Abstract:

With the development of water flooding in fractured reservoirs with high temperature （reservoir temperature of 130 ℃）, the problem of fracture channeling by water injected becomes more and more prominent. Epoxy resin has the characteristics of high strength and aging resistance after curing at high temperature, which is a potential high-temperature plugging agent. Since epoxy resin is not easy to be injected and difficult to cure under wet conditions, the epoxy resin was emulsified by the phase inversion method. A variety of emulsifiers were selected to emulsify epoxy resin （E-44） with tap water and simulated formation water as the water phase, and the emulsifiers suitable for both kinds of water were screened out. Then single-factor experiments were carried out to study the effects of stirring speed, emulsifying temperature, water adding speed, mass fraction of emulsifier, and oil-water volume ratio on the phase inversion process of epoxy resin and the properties of emulsion. Finally, the orthogonal experiment was used to analyze the level of each factor and determine the optimal emulsifying process. The results of differential scanning calorimetry showed that the curing temperature of the system was 129.5 ℃, and it had good plugging effect after curing at reservoir temperature.

Key words: epoxy resin, emulsion, curing agent, thermal stability, plugging

CLC Number:

TQ423

Zhen Enlong, Zhang Wen, Qian Zhen, Du Ruotong, Wang Yang. Construction and plugging performance evaluation of emulsified thermosetting resin system[J].China Surfactant Detergent & Cosmetics, 2023, 53(6): 649-657.

Figures/Tables 17

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References 22

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实验号	实验因子				指标
实验号	A 搅拌速度/（r/min）	B 乳化温度/℃	C 加水速度/（mL/min）	D w（乳化剂）/%	离心稳定性/级	粒径/μm
1	A₁（600）	B₁（40）	C₁（1）	D₁（15）	1	4.2
2	A₁（600）	B₂（50）	C₂（1.5）	D₂（20）	4	2.0
3	A₁（600）	B₃（60）	C₃（2）	D₃（25）	3	2.6
4	A₂（800）	B₁（40）	C₂（1.5）	D₃（25）	5	1.7
5	A₂（800）	B₂（50）	C₃（2）	D₁（15）	2	3.1
6	A₂（800）	B₃（60）	C₁（1）	D₂（20）	4	2.1
7	A₃（1 000）	B₁（40）	C₃（2）	D₂（20）	5	1.6
8	A₃（1 000）	B₂（50）	C₁（1）	D₃（25）	6	1.5
9	A₃（1 000）	B₃（60）	C₂（1.5）	D₁（15）	2	3.3

实验项目	离心稳定性/级
实验项目	A	B	C	D
K₁	8	11	11	5
K₂	11	12	11	13
K₃	13	9	10	14
k₁	2.7	3.7	3.7	1.7
k₂	3.7	4	3.7	4.3
k₃	4.3	3	3.3	4.7
极差R	1.6	1	0.3	3
因素主次顺序	D>A>B>C
优水平	A₃	B₂	C₂	D₃
优组合	A₃B₂C₂D₃

实验项目	A	B	C	D
K_1j	8.8	7.5	7.8	10.6
K_2j	6.9	6.6	7	5.7
K_3j	6.4	8	7.3	5.8
K_1j²	77.44	56.25	60.84	112.36
K_2j²	47.61	43.56	49	32.49
K_3j²	40.96	64	53.29	33.64
偏差平方和	1.07	0.34	0.11	5.23
自由度	2	2	2	2
F比	9.81	3.08	1.00	47.97
F临界值	9	9	9	19
显著性	a=0.1	a=0.1	a=0.1	a=0.05

项目	现象
外观	乳白色、不透明
类型	O/W型
平均粒径/μm	1.5
离心稳定性/级	5
冻融稳定性/级	3
贮存稳定性（25 ℃）	>30 d

实验序号	固化剂型号	类型	Rf	粒径/μm	离心稳定性/级	贮存稳定性/（25 ℃/7 d）
1	MZL	O/W型	0.57	1.6	4	不分层
2	DDM	O/W型	0.69	1.5	4	不分层
3	QS1678	O/W型	0.67	1.7	4	不分层
4	BS-777	O/W型	0.62	1.7	4	轻微分层
5	Y-3155	O/W型	0.82	1.9	3	严重分层
6	Y-3388	O/W型	0.85	2.1	3	严重分层
7	WE-8318	O/W型	0.75	1.7	3	严重分层
8	MTHPA	O/W型	0.71	2.1	3	破乳、两相分离
9	ZY-S811	O/W型	0.76	2.2	3	破乳、两相分离
10	HS-122	O/W型	0.87	3.1	2	破乳、两相分离

Construction and plugging performance evaluation of emulsified thermosetting resin system

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实验序号	DDM+MZL	类型	外观	离心稳定性/级	贮存稳定性/(25 ℃/7 d)
1	5%+5%	O/W型	乳白色	4	不分层
2	5%+7.5%	O/W型	乳白色	4	不分层
3	5%+10%	O/W型	浅黄色	3	严重分层
4	7.5%+5%	O/W型	乳白色	4	不分层
5	7.5%+7.5%	O/W型	乳白色	4	轻微分层
6	7.5%+10%	O/W型	浅黄色	3	不分层
7	10%+5%	O/W型	乳白色	4	不分层
8	10%+7.5%	O/W型	乳白色	3	严重分层
9	10%+10%	O/W型	浅黄色	3	严重分层

实验序号	1	2	3	4	5	6	7	8	9
硬度/HA	18	25	31	47	55	60	52	61	70
固化时间/min	80	70	50	70	55	45	50	50	40

升温速率β/（K/min）	5	10	15	20
固化反应热/（J/g）	345.38	415.02	565.1	618.38
起始温度T₀/K	91.3	96.7	102.1	107.3
峰顶温度T_p/K	134.7	146.3	156.1	164.7
终止温度T_f /K	154.2	173.1	189.1	204.2

β/ （K/min）	T_p /K	ln β	ln （β/T_p²）	1/T_p
5	407.85	1.609 4	-10.412 4	0.002 45
10	419.45	2.302 6	-9.775 3	0.002 38
15	429.25	2.708 1	-9.416 0	0.002 33
20	437.85	2.995 7	-9.168 0	0.002 28

拟合函数	β=0特征温度	特征温度值/K	T/℃
T₀=1.068β+359.15	预固化温度	359.15	86
T_p =1.996β+402.65	固化温度	402.65	129.5
T_f =3.32β+411.80	后固化温度	411.80	138.65

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填砂管编号	堵前渗透率/μm²	堵后渗透率/μm²	封堵率/%
1	3.38	0.11	96.84
2	1.82	0.05	97.12
3	0.78	0.02	97.42