绿泥石弱酸性解堵剂的开发与性能评价

潘定成; 韦慧莹; 张洪菁; 王贵; 丁文刚; 易小艺

doi:10.12358/j.issn.1001-5620.2022.04.019

绿泥石弱酸性解堵剂的开发与性能评价

doi: 10.12358/j.issn.1001-5620.2022.04.019

1.
中海油田服务股份有限公司油田生产事业部，天津 300450
2.
中南大学化学化工学院，长沙 410083

详细信息

作者简介:
潘定成，工程师，硕士，现在从事酸化解堵和油水井除防垢工作

通讯作者:
易小艺，博士，教授，博士生导师，现在从事配位化学、油田黏土解堵技术研究。E-mail: xyyi@csu.edu.cn

中图分类号: TE282
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出版历程
- 收稿日期: 2022-03-01
- 修回日期: 2022-05-05
- 录用日期: 2022-01-31
- 刊出日期: 2022-07-30

Development and Performance Evaluation of Weak Acid Plugging Removal Agent for Chlorite

1.
Production Optimization, China Oilfield Services Limited, Tianjin 300459
2.
College of Chemistry and Chemical Engineering, Central South University, Changsha,Hunan 410083

摘要

摘要: 黏土矿物常对油田储层造成污染和堵塞，绿泥石矿物是黏土矿物的主要组成部分之一。目前现场常采用的强酸性解堵剂腐蚀性大，作用时间短，当体系质子消耗到一定量时，体系解堵效率大大降低。为了解决以上问题，对各产地绿泥石物性分析比较，引入缓冲概念，针对性地复配了一种螯合能力强、具有缓冲能力的弱酸性解堵剂。通过室内实验研究发现：在解堵主剂质量浓度4%、pH值为5条件下，解堵剂对绿泥石24 h溶蚀率达25%，说明该解堵剂具有溶蚀率高、解堵效果好、腐蚀性弱以及配伍性好的优点。机理研究表明，解堵剂和缓冲体系有效组合，持续稳定提供一定浓度质子的特点是该弱酸性绿泥石解堵剂高效解堵的关键。WZ-X井在开发开采过程中，由于钻完井液侵入地层造成黏土膨胀与运移伤害，使用绿泥石解堵剂进行解除污染，作业后该井产液量由55.5 m³/d提升至98.0 m³/d。该技术的成功应用为油田解堵提供了新的方向。的方向。
- 解堵剂 /
- 弱酸性 /
- 缓冲体系 /
- 绿泥石 /
- 溶蚀率
Abstract: Clay minerals often pollute and block oil reservoirs. Chlorite is one of the main components of clay minerals. The strong acid as plugging remover in feature of high corrosivity and high efficiency was commonly used in the oilfields. When the protons are consumed, the efficiency of the plugging remover system is greatly reduced. To solve the problem of oilfield blockage material, this paper compares the physical properties of chlorite from various producing areas, and purposefully develops a weak acid plugging remover with a strong chelating ability to metal in clay minerals and buffering ability. The experimental research displays that under the conditions of 4% mass concentration of main plugging removal agent and pH = 5, the dissolution rate of chlorite reaches 25% under 24 h, indicating that the plugging remover has the advantages of high dissolution rate, good plugging removal effect, weak corrosion, and good compatibility. The mechanism study shows that the effective combination of plugging remover and buffer system to continuously and stably provide a certain concentration of protons is the key to the efficient plugging removal of chlorite under weak acidic conditions. During the exploitation of well WZ-X, clay swelling and migration damage were caused by drilling and completion fluid immersion into the formation. Chlorite plugging agent was used to remove pollution. After the operation, the fluid production of the well increased from 55.5 m³/d to 98 m³/d. The successful application of this technology provides a new direction for oilfield plugging removal.
- Plugging remover /
- Weak acidic condition /
- Buffer system /
- Chlorite /
- Dissolution rate

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图 1 4种绿泥石样品的X-射线粉末衍射图

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图 2 绿泥石2红外光谱图

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图 3 不同浓度的解堵剂对绿泥石溶蚀率的影响

注：实验条件为 90 ℃水浴反应4 h

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图 4 4%解堵剂A与不同类型的碱复配实验

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图 5 4%解堵剂A+氢氧化钠体系pH梯度实验

注：90 ℃下，水浴反应24 h

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图 6 WZ-X井解堵施工曲线

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表 1 植酸和柠檬酸+草酸体系对　　　绿泥石的溶蚀结果（90 ℃）

体系	反应 pH值	反应时间/h	溶蚀率/%
1%植酸	6.2	4	1.7
2%植酸	6.2		2.9
3%植酸	6.1		0.5
4%植酸	6.3		-1.4
5%植酸	6.1		1.3
2.5%草酸+5%柠檬酸	1.0		11.6
2.5%草酸+5%柠檬酸+1%HEDP	0.9		19.9

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表 2 浓度为5%的不同解堵剂对　　　绿泥石的溶蚀结果（90 ℃）

体系	反应 pH值	反应时间/h	溶蚀率/%
三（羟甲基）氨基甲烷+HCl	4.1	4	3.7
谷氨酸二乙酸四钠+HCl	4.0		5.6
草酸钠（饱和）+HCl	4.1		4.7
5-磺基水杨酸	0.8		9.7
单宁酸	1.8		9.4
葡萄糖酸钠+HCl	4.0		7.5
解堵剂A	1.4		26.8

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表 3 4%解堵剂A与磷酸氢二钠-柠檬酸缓冲体系的pH梯度实验（24 h）

体系配方	缓冲体系pH	反应体系pH	溶蚀率/%
4%解堵剂A + 磷酸氢二钠/柠檬酸缓冲体系	4.5	2.3	43.1
	4.7	2.4	41.4
	5.5	2.4	42.1
	5.9	2.5	42.0
	7.1	2.7	39.7

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表 4 解堵剂A对现场岩屑的溶蚀测试

黏土样品	主要成分/%				溶蚀率/%
黏土样品	石英	云母	钠长石	高岭土	溶蚀率/%
现场岩屑1^#	60.64	23.01		7.59	6.16
现场岩屑2^#	27.81	15.21	37.26	5.30	19.72
现场岩屑3^#	71.80	10.03	6.60		3.45
现场岩屑4^#	22.90	36.18	14.89	12.71	23.09
注：溶液pH值为3，反应时间为24 h，反应温度为90 ℃

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表 5 解堵剂A对N80钢片的腐蚀性为测试

配方	溶液pH	t/h	T/ ℃	m₁/ g	m₂/ g	腐蚀速率/g/(m²·h)	平均腐蚀速率/g/(m²·h)
4%解堵剂A+ NaOH	3.01	4	90	11.318	11.316	0.423	0.441
		4		11.288	11.286	0.460	0.441
		24		11.318	11.315	0.089	0.084
		24		11.288	11.286	0.080	0.084
	3.02	168	120	11.285	11.263	0.097	0.095
	3.02	168	120	10.807	10.786	0.094	0.095

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表 6 不同配方的滤液ICP表征结果

配方	反应前pH	t/h	溶蚀率/%	元素含量/(mg·L⁻¹)
配方	反应前pH	t/h	溶蚀率/%	Al	Mg	Si
2%植酸	6.2	4	2.8	0.3	43.7	12.9
2.5%草酸+5%柠檬酸	0.8		11.6	323.9	1206.0	345.8
2.5%草酸+5%柠檬酸+1%HEDP	0.9		19.9	349.5	1925.0	402.1
4%解堵剂A	1.5		30.2	84.8	1655.0	99.32
4%解堵剂A+NaOH	3.0		22.7	91.5	1636.0	135.2
4%解堵剂A+NaOH	3.0	24	33.0	101.7	1580.0	171.5
4%解堵剂A+0.2 mol/L磷酸氢二钠+0.1mol/L柠檬酸	2.3		43.1	284.0	2052.0	337.1
4%解堵剂A+0.2 mol/L磷酸氢二钠+0.1mol/L柠檬酸	2.7		39.7	199.6	1430	234.8

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