无沉淀型有机膦螯合解堵剂的制备与性能评价[*]
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中海油能源发展股份有限公司工程技术分公司

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TE357.2???????? DOI

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国家重点研发计划课题“生物酶制剂入井体系开发及应用示范”(编号:2022YFC2105204);中海油能源发展股份有限公司工程技术公司项目“海南气井解堵技术研究与应用”(SSKJ-CG-GJ-2025-38)联合资助。


Preparation and Performance Evaluation of Non-precipitating 0rganic Phosphorus Chelating Agent Formula for Plug Removal
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    摘要:

    针对常规螯合解堵剂用于油田酸化解堵作业时,分散垢物后产生的螯合物不溶解、易堵塞储层的问题,采用多氨基多醚基亚甲基膦酸(PAPEMP)和2-膦酸丁烷-1,2,4-三羧酸(PBTCA)作为关键主剂,复配氢氟酸(HF)和二甲基二烯丙基氯化铵(DMDAAC),制备了无沉淀型有机膦螯合解堵剂PPF(包括前置酸PPF-A和主体酸PPF-B)。通过pH测试、大理石溶蚀实验、现场垢样与岩屑溶蚀实验、不同时间溶蚀率测定实验以及氟化钙二次沉淀抑制实验,对PPF体系的理化性能、溶垢能力、缓速深穿透性能和沉淀抑制性能进行了系统评价。结果表明:PPF-A和PPF-B的pH值分别为1.40和3.40,显著高于同浓度常规无机酸;PPF-A对大理石(碳酸钙)溶蚀量大(24 h溶蚀质量差达5.78 g),且经定量滤纸过滤后质量差为正值,肉眼观察溶液澄清,无钙螯合物沉淀产生;PPF-A对现场垢样的溶蚀率达57.36%,达到10%质量浓度盐酸溶蚀能力的81%;PPF-B与现场砂岩岩屑反应24 h的溶蚀率为24.23%,且溶蚀率随反应时间(2~24 h)持续增加,表现出良好的缓速深穿透性能;以PAPEMP和PBTCA为主剂的复配体系可在72 h内有效抑制氟化钙二次沉淀,溶液保持澄清,理论抑制率达95.87%。该解堵剂兼具高pH值、适度溶蚀能力、缓速深穿透及长效抑制二次沉淀等优势,适用于防止储层骨架破坏与管线腐蚀、实现深部缓速解堵及改善返排液处理困难的油田酸化解堵作业,且可避免氟化钙或螯合物沉淀对储层造成污染。

    Abstract:

    In response to the problem that when conventional chelating plugging removal agents are used in acidizing plugging removal operations in oilfields, the chelates produced after dispersing scale substances are insoluble and prone to block the reservoir, polyamino polyether methylene phosphonic acid (PAPEMP) and 2 - phosphonobutane - 1,2,4 - tricarboxylic acid (PBTCA) were used as the key main agents, and hydrofluoric acid (HF) and dimethyldiallylammonium chloride (DMDAAC) were compounded to prepare a non - precipitating organic phosphine chelating plugging removal agent PPF (including pre - acid PPF - A and main acid PPF - B). Through pH tests, marble corrosion experiments, corrosion experiments of on - site scale samples and cuttings, experiments on measuring the corrosion rate at different times, and experiments on inhibiting the secondary precipitation of calcium fluoride, the physical and chemical properties, scale dissolution ability, slow - rate deep penetration performance, and precipitation inhibition performance of the PPF system were systematically evaluated. The results show that: the pH values of PPF - A and PPF - B are 1.40 and 3.40 respectively, which are significantly higher than those of conventional inorganic acids at the same concentration; PPF - A has a large corrosion amount on marble (calcium carbonate) (the mass difference of corrosion in 24 h reaches 5.78 g), and the mass difference after filtering through quantitative filter paper is positive. The solution is clear to the naked eye, and no calcium chelate precipitation is produced; the corrosion rate of PPF - A on on - site scale samples reaches 57.36%, which is 81% of the corrosion ability of hydrochloric acid with a mass concentration of 10%; the corrosion rate of PPF - B reacting with on - site sandstone cuttings for 24 h is 24.23%, and the corrosion rate continuously increases with the reaction time (2 - 24 h), showing good slow - rate deep penetration performance; the compound system with PAPEMP and PBTCA as the main agents can effectively inhibit the secondary precipitation of calcium fluoride within 72 h, the solution remains clear, and the theoretical inhibition rate reaches 95.87%. This plugging removal agent has the advantages of high pH value, moderate corrosion ability, slow - rate deep penetration, and long - term inhibition of secondary precipitation. It is suitable for oilfield acidizing plugging removal operations to prevent the destruction of the reservoir skeleton and pipeline corrosion, achieve deep slow - rate plugging removal, and improve the difficulty of produced fluid treatment, and can avoid the pollution of the reservoir caused by the precipitation of calcium fluoride or chelates.

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  • 收稿日期:2025-02-05
  • 最后修改日期:2026-07-13
  • 录用日期:2026-07-16
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