适用于碳酸盐岩储层的固体酸解堵体系

李继勇; 孙玉海; 卢占国; 张云芝; 孟博; 宋时权; 吴洋

doi:10.12358/j.issn.1001-5620.2022.04.018

适用于碳酸盐岩储层的固体酸解堵体系

doi: 10.12358/j.issn.1001-5620.2022.04.018

1.
胜利油田石油工程技术研究院, 山东东营 257000
2.
西南石油大学化学化工学院, 成都 610500

详细信息

作者简介:
李继勇，1967年生，硕士，高级工程师，主要从事油田化学剂质量监督管理工作。E-mail：lijiyong727.slyt@sinopec.com

通讯作者:
吴洋，电话 18780235896；E-mail:190468850@qq.com

中图分类号: TE357
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出版历程
- 收稿日期: 2022-02-16
- 修回日期: 2022-03-20
- 录用日期: 2022-04-20
- 刊出日期: 2022-07-30

A Solid Acid Block Removing System for Carbonate Reservoirs

1.
The Petroleum Engineering Technology Research Institute, Sinopec Shengli Oilfield Branch Company, Dongying，Shandong 257000
2.
College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500

摘要

摘要: 传统的液体酸解堵体系，多使用盐酸、硝酸等常规液体酸。在存放、运输和使用过程中，液体酸存在设备成本高和安全风险大的问题。选用氨基磺酸、柠檬酸、二乙基三胺五乙酸为基础，对这3种不同类型固体酸的溶蚀性能、稳定铁离子能力进行性能评价。利用复配实验，调控3种固体酸的比例，确定最优的复配固体酸配方为m（氨基磺酸）∶m（柠檬酸）∶m（二乙基三胺五乙酸）为8∶1∶1。以此复配固体酸为主剂，加入缓蚀剂、渗透剂、黏土防膨剂构建得到固体酸解堵体系。该固体解堵体系具有较好的溶蚀碳酸钙能力，对大理石的溶蚀率达到27.65%，良好的稳定铁离子的能力，络合铁离子容量达到643.71 mg/L。通过岩心流动实验表明，该固体酸解堵体系的注入体积达到10 PV时，可以提高岩心渗透率20%以上。现场利用固体酸体系施工后，施工井产量较高。
- 固体酸 /
- 碳酸盐岩 /
- 解堵 /
- 络合
Abstract: Conventional acid block removing systems generally are formulated with common liquid acids such as hydrochloric acid or nitric acid. These liquid acids have high costs and safety risks in storing, transportation and operation. To solve these problems, three solid acids, which are sulfamic acid, citric acid and diethyl triamine penta-acetic acid, are selected to study their dissolution capacity and capability of stabilizing iron ions. By adjusting the ratio of the three acids, the optimum ratio was determined to be∶m(sulfamic acid)∶m(citric acid)∶m(diethyl triamine penta-acetic acid) = 8∶1∶1. A solid acid block removing system was formulated using the compound solid acid as the main additive, coupled with corrosion inhibitor, penetrant and clay swelling inhibitor. This solid acid block removing system has the ability to dissolve calcium carbonate; a percent rate of dissolution of 27.65% of marble was obtained with the solid acid block removing system. The solid acid block removing system has iron ion complex capacity of 643.71 mg/L, a good iron ion stabilizing performance. Core flow experimental results showed that when the solid acid block removing system was injected into the core by 10 PV, the permeability of the core was increased by at least 20%. Field operation has shown that the application of this solid acid block removing system resulted in higher production rate of hydrocarbons.
- Solid acid /
- Carbonate rock /
- Block removing /
- Complex

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图 4 固体酸在鄂尔多斯盆地井的酸化施工曲线

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图 1 温度对复配固体酸溶蚀碳酸钙性能的影响

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图 2 经盐酸溶蚀前后的大理石微观结构

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图 3 经固体酸溶蚀前后大理石的微观结构

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表 1 3种固体酸对大理石的溶蚀能力

样品	加量/%	溶蚀前质量/g	溶蚀后质量/g	溶蚀率/%
氨基磺酸	5	42.45	38.28	9.82
	10	40.88	32.98	19.32
	15	41.34	29.89	27.70
	20	42.98	28.48	33.74
柠檬酸	5	40.67	38.83	4.52
	10	41.00	37.28	9.07
	15	40.96	35.95	12.23
	20	40.73	34.69	14.83
二乙基三胺五乙酸	1	42.53	42.23	0.71
	3	41.29	40.51	1.89
	5	40.88	39.86	2.50

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表 2 3种解堵剂稳定铁离子能力

样品	加量/%	沉淀	Fe³⁺/mg·L⁻¹
氨基磺酸	5	有	32.57
	10	有	36.21
	15	有	38.33
	20	有	41.69
柠檬酸	5	无	613.45
	10	无	622.73
	15	无	618.26
	20	无	625.15
二乙基三胺五乙酸	1	无	624.86
	3	无	631.52
	5	无	629.72

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表 3 氨基磺酸和柠檬酸复配后的性能

氨基磺酸∶柠檬酸	碳酸钙溶蚀率/ %	稳定铁离子能力
氨基磺酸∶柠檬酸	碳酸钙溶蚀率/ %	沉淀	Fe³⁺/ mg·L⁻¹
9∶1	27.15	有	478.66
8∶2	25.61	有	585.93
7∶3	23.06	无	627.41

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表 4 氨基磺酸和二乙基三胺五乙酸复配后的性能

氨基磺酸∶二乙基三胺五乙酸	碳酸钙溶蚀率/ %	稳定铁离子能力
氨基磺酸∶二乙基三胺五乙酸	碳酸钙溶蚀率/ %	沉淀	Fe³⁺/ mg·L⁻¹
9∶1	26.00	无	625.37
8∶2	24.30	无	631.08
7∶3	20.61	无	629.58

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表 5 3种固体酸解堵剂复配后的性能

氨基磺酸∶柠檬酸∶ 二乙基三胺五乙酸	碳酸钙溶蚀率/%	沉淀	Fe³⁺/ mg·L⁻¹
8∶0.6∶1.4	23.86	无	635.58
8∶0.8∶1.2	24.68	无	629.64
8∶1.0∶1.0	25.82	无	631.18
8∶1.2∶0.8	26.57	有	561.73
8∶1.4∶0.6	26.73	有	533.22

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表 6 不同浓度复配固体酸有效H⁺浓度

固体酸浓度/%	H⁺浓度/（mol ·L⁻¹）	盐酸浓度/%
4	0.43	1.57
8	0.84	3.07
12	1.32	4.82
16	1.74	6.35
20	2.08	7.59

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表 7 加入缓蚀剂的复配固体酸对钢片的缓蚀性能

样品	加量/%	腐蚀前质量/g	腐蚀后质量/g	腐蚀速率/ g/(h ·m²)
多效缓蚀剂	0.5	10.9450	10.8896	10.18
缓蚀剂CT-3	0.5	10.8319	10.7760	10.28
缓蚀剂AHS-90	0.5	10.9045	10.8848	3.62

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表 8 加入渗透剂后复配固体酸降低表面张力和界面张力能力

样品	表面张力/（mN/m）	界面张力/（mN/m）
CDJ-1	30.41	2.85
CDEM-12	28.25	1.86
SX1-07	27.83	2.77
注：渗透剂加量为0.25%

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表 9 加入黏土防膨剂后复配固体酸的防膨性能

样品	膨胀体积/mL	防膨率/%
清水	10.00
煤油	0.50
FNP-3	1.60	88.42
WND-06	1.55	88.95
SNH-501	1.15	93.16
注：黏土防御剂加量为1%

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表 10 不同注入量的固体解堵体系对渗透率的提升情况

处理情况	注入量/ PV	渗透率/ mD	渗透率提升/%
前	10	0.39	23.08
后	10	0.48	23.08
前	20	0.62	25.81
后	20	0.78	25.81
前	30	0.37	32.43
后	30	0.49	32.43

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参考文献(11)

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