有机膦酸盐缓凝剂异常增稠油井水泥浆作用机理

邹亦玮; 代丹; 王义昕; 耿晨梓; 朱思佳; 姚晓

doi:10.12358/j.issn.1001-5620.2025.01.012

有机膦酸盐缓凝剂异常增稠油井水泥浆作用机理

doi: 10.12358/j.issn.1001-5620.2025.01.012

1.
中海油服油田化学研究院, 河北燕郊 065201
2.
南京工业大学材料科学与工程学院, 南京 211816

基金项目: 中海油田服务有限公司项目“海水基固井关键外加剂的开发与机理研究”（YHB23YF004）。

详细信息

作者简介:
邹亦玮，工程师，现主要从事固井技术研究和固井材料研发工作。E-mail：zouyiwei@cosl.com.cn

通讯作者:
姚晓，博士，教授，博士生导师。E-mail：yaoxiao@njtech.edu.cn。

中图分类号: TE256
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出版历程
- 收稿日期: 2024-09-28
- 修回日期: 2024-11-01
- 刊出日期: 2025-02-01

Mechanisms of Organic Phosphonate Retarders to Abnormally Thicken Oil Well Cement

1.
Cosl Oilfield Chemical Research Institute, Yanjiao, Hebei 065201
2.
College of Materials Science and Engineering, Nanjing Tech University, Nanjing, Jiangsu 211816

摘要

摘要: 有机膦酸盐是延长油井水泥浆中高温稠化时间的常用缓凝剂。通过讨论乙二胺四亚甲基膦酸钠（EDTMPS）缓凝剂对G级高抗硫（HSR）油井水泥浆稠化性能的影响，研究了EDTMPS掺量对4种不同厂家水泥稠化性能的影响。使用水化热、XRD和溶解度实验研究了EDTMPS缓凝剂在不同厂家油井水泥浆中的作用机理。结果表明，EDTMPS缓凝剂抑制了二水石膏的溶解，同时促进了C₃A溶解。失去二水石膏缓凝作用的C₃A快速水化，导致水泥浆初始稠度上升；而EDTMPS缓凝剂促进了半水石膏溶解，释放的SO₄²⁻延缓了C₃A的水化作用。通过调整G级HSR油井水泥中C₃A和二水石膏/半水石膏的含量匹配关系，可以改善水泥与EDTMPS缓凝剂的配伍性。
- 油井水泥 /
- 高温 /
- 有机膦酸盐 /
- 稠化性能 /
- 微观结构
Abstract: Organic phosphonates are generally used as retarders for cement slurries at high temperatures in Yanchang oilfield. This paper discusses the effects of the retarder sodium ethylene-diamine tetramethylene-phosphonate (EDTMPS) on the thickening performance of the class G high-sulfur-resistant (HSR) oil-well cements from four different manufacturers. The mechanisms of EDTMPS in retarding the thickening time of the four cement slurries were investigated through hydration heat measurement, XRD experiment and solubility measurement. The results of the measurement and experiment show that in the reactions of EDTMPS with the cements, EDTMPS inhibits the solution of dihydrate gypsum and accelerates the solution of C₃A, thus the retarding effect of dihydrate gypsum is inhibited and C₃A becomes fast hydrated, leading to an increase in the initial consistency of the cement slurry. On the other hand, EDTMPS can accelerate the solution of hemihydrate gypsum which releases SO₄²⁻. The SO₄²⁻ ions released slow down the hydration process of C₃A. By adjusting the concentrations of C₃A, dihydrate gypsum and hemihydrate gypsum in the class G HSR oil-well cement slurry, the compatibility of the cement slurry with EDTMPS can be improved.
- Oil-well cement /
- High temperature /
- Organic phosphonate /
- Thickening proformance /
- Microstructure

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图 1 不同掺量EDTMPS缓凝剂对4种水泥浆水化1 h物相组成的影响（80℃）

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图 2 不同掺量EDTMPS缓凝剂对4种水泥浆水化3 h物相组成的影响（80℃）

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图 3 0.5%缓凝剂EDTMPS对模型水泥浆　　(熟料+石膏)稠化性能的影响(80℃)

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表 1 4个厂家油井水泥和一种熟料的矿物组成 %

水泥	C₃S	C₂S	C₃A	C₄AF	二水石膏	半水石膏	无水石膏
Cem1	62.3	20.4	2.5	12.7	1.3	0.7	0.1
Cem2	50.9	30.0	2.4	13.1	2.3	0.6	0
Cem3	60.3	21.5	1.6	13.6	0	2.4	0.6
Cem4	53.4	23.9	4.1	13.6	3.0	2.0	0
Clin	62.5	18.9	2.4	15.5	0	0	0

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表 2 二水石膏和半水石膏的化学成分 %

石膏	SiO₂	Al₂O₃	Fe₂O₃	TiO₂	CaO	MgO	SO₃	K₂O	Na₂O	LOI
二水石膏(G)	0	0	0	0	32.23	0	46.25	0	0.02	21.50
半水石膏(B)	0	0.06	0.02	0.01	38.76	0	54.58	0	0	6.57
注：LOI指1000℃下煅烧2 h后的质量损失百分比。

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表 3 不同掺量EDTMPS缓凝剂对水泥浆稠化性能的影响（80℃，常压）

水泥	EDTMPS/ %	t_稠化/ min	t_过渡/ min	初始稠度/Bc	稠化性能
Cem1	0.1	106	60	31	稠化反转
	0.2	57	21	28
	0.3	10	9	70
	0.4	19	18	70
	0.5	4	3	70
Cem2	0.1	143	21	23	异常增稠
	0.2	181	13	42
	0.3	241	19	49
	0.4	371	13	42
	0.5	548	30	54
Cem3	0.1	139	18	17	稠化曲线平滑，过渡时间短，近乎直角稠化
	0.2	215	16	18
	0.3	301	19	15
	0.4	441	22	19
	0.5	610	30	17
Cem4	0.1	110	20	7	稠化曲线平滑，过渡时间短，近乎直角稠化
	0.2	159	19	9
	0.3	232	20	10
	0.4	362	28	11
	0.5	715	33	9

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表 4 掺入不同掺量EDTMPS缓凝剂的水泥浆物相组成定量结果（80℃） %

编号	C₃S	C₂S	C₄AF	C₃A	二水石膏	CH	非晶相
Cem1-0-1 h	59.2	15.1	11.3	0.8	0.3	0	13.5
Cem1-0-3 h	59.0	15.0	11.2	0.6	0	0	14.0
Cem1-3-1 h	60.5	15.5	11.3	1.5	0	0	11.8
Cem1-3-3 h	59.9	15.5	11.5	1.1	0	0	12.0
Cem1-5-1 h	61.5	15.8	11.5	0.6	0	0	10.5
Cem1-5-3 h	61.8	15.5	11.6	0.1	0	0	10.7
Cem2-0-1 h	44.9	30.3	12.5	1.3	3.1	0.3	8.0
Cem2-0-3 h	30.0	30.1	11.3	0	0	4.1	25.0
Cem2-3-1 h	41.1	30.1	12.1	0.7	2.1	0	13.1
Cem2-3-3 h	42.1	30.0	12.0	0.5	1.4	0.1	14.0
Cem2-5-1 h	44.8	30.4	12.4	0.6	1.8	0	10.1
Cem2-5-3 h	42.5	30.4	12.6	0.3	1.3	0	12.9
Cem3-0-1 h	53.2	19.3	11.6	1.0	0	0.5	14.4
Cem3-0-3 h	20.4	19.3	11.1	0	0	11.3	37.9
Cem3-3-1 h	54.9	19.1	11.5	1.2	0	11.5	13.3
Cem3-3-3 h	51.2	19.1	11.5	1.2	0	0	17.0
Cem3-5-1 h	54.9	19.7	11.9	1.5	0	0	12.0
Cem3-5-3 h	56.4	19.3	11.8	1.6	0	0	10.9
Cem4-0-1 h	53.0	19.7	12.4	2.7	2.7	1.3	8.1
Cem4-0-3 h	22.0	19.6	10.5	1.8	0	13.0	32.3
Cem4-3-1 h	52.1	17.1	12.5	3.0	3.3	0.8	10.3
Cem4-3-3 h	53.5	18.9	11.0	1.9	3.0	1.0	10.6
Cem4-5-1 h	53.1	20.0	11.9	3.4	3.4	1.3	7.4
Cem4-5-3 h	53.6	19.5	11.5	2.9	2.9	1.9	8.4

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表 5 石膏在纯水或ETDMPTS溶液中不同溶解时间的质量变化（80℃） g

溶剂	溶质	W₀	W₅	W₃₀
纯水	二水石膏	10.00	9.55	9.21
纯水	半水石膏	10.00	9.05	10.80
0.5%EDTMPS	二水石膏	10.00	9.70	9.62
0.5%EDTMPS	半水石膏	10.00	8.89	8.75
注：W₀为石膏初始质量；W₅和W₃₀分别为石膏溶解5 min和30 min后的剩余质量（60℃真空干燥）。

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表 6 不同石膏在水中溶解不同时间的SO₄²⁻吸光度（80℃）

石膏	5 min	10 min	20 min
二水石膏	1.85	2.07	1.95
半水石膏	1.92	1.11	1.11
二水石膏+0.5%EDTMPS	0.71	0.76	0.66
半水石膏+0.5%EDTMPS	2.13	2.00	1.91

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