Study on and Application of Calcium Fluoride Precipitation Inhibitor for Acid Jobs
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摘要: 针对海上油田氟化钙二次沉淀导致酸化效果变差及酸化用氟化钙沉淀抑制剂评价缺乏稳定可靠实验方法的问题，测试了强酸对氟化钙二次沉淀的溶蚀效果，分析了酸化过程中生成氟化钙的粒径特征，形成了1套氟化钙沉淀抑制剂优选评价的实验方法，研发出1种氟化钙沉淀抑制剂BYZ-01。实验表明，4%BYZ-01加量条件下，土酸溶液中基本无氟化钙沉淀产生，研发的BYZ-01现场应用效果显著。酸化过程中产生的氟化钙二次沉淀物特征认识及酸化用氟化钙沉淀抑制剂优选评价方法的建立，对指导酸化中氟化钙二次沉淀抑制研究和制定酸化用沉淀抑制剂检测标准方法意义重大。Abstract: In offshore well stimulation, the secondary precipitation of calcium fluoride (CaF2) generally results in poor acid job quality, and methods for evaluating the quality of inhibitors for secondary precipitation of CaF2 cannot produce stable and reliable results. To deal with this problem, several strong acids were tested for their performance in dissolving the secondary precipitate of CaF2, and the particle size characteristics of the CaF2 generated during acid operation was analyzed. Based on the test results and the analysis, an experimental method of selecting and evaluating CaF2 precipitation inhibitors was established, and a CaF2 precipitation inhibitor BYZ-01 was developed and selected. Field experimental results show that at a concentration of 4%, there is no CaF2 precipitation in mud acid solution, demonstrating that BYZ-01 has remarkable field application effect. The understanding of the characteristics of the CaF2 secondary precipitates generated in acid job and the establishment of the method for evaluating CaF2 precipitation inhibitors for acid job have a significant importance to guiding the study on the inhibition of secondary CaF2 precipitation in acid job and the establishment of new methods for evaluating precipitation inhibitors.
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表 1 不同沉淀抑制剂抑制氟化钙生成效果
沉淀抑制剂 初始 1 h后 2 h后 空白（土酸） 透明清澈 浑浊 底部明显沉淀 聚马来酸 略黄清澈 浑浊 底部明显沉淀 十二烷基葡萄糖苷 表层多泡沫，清澈透明 浑浊 底部明显沉淀 多氨基多醚基亚甲基膦酸 透明清澈 浑浊 底部明显沉淀 聚磷酸铵 透明清澈 浑浊 底部明显沉淀 双-1.6-亚乙基三胺五甲叉膦酸 淡黄清澈 清澈 底部少量沉淀 2-丙烯酰胺-2-甲基丙磺酸 透明清澈 清澈 底部明显沉淀 2-羟基膦酰基乙酸 略黄清澈 清澈 底部明显沉淀 二乙烯三胺五甲叉膦酸 透明清澈 清澈 底部少量沉淀 羟基乙叉二膦酸 透明清澈 清澈 底部明显沉淀 氨基三亚甲基膦酸 透明清澈 清澈 底部明显沉淀 氮基三乙酸 透明清澈 清澈 底部明显沉淀 2-膦酸丁烷-1，2，4-三羧酸 透明清澈 浑浊 底部明显沉淀 氨基三亚甲基膦酸 透明清澈 浑浊 底部明显沉淀 羟基乙叉二膦酸 透明清澈 清澈 底部明显沉淀 BYZ-01（自制） 透明清澈 清澈 清澈 
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表 2 不同浓度BYZ-01抑制氟化钙生成效果
100 g土酸
中BYZ-01
加量/%2 h后
沉淀物
质量/g2 h后氟化钙沉淀
抑制率/%72 h后
沉淀物
质量/g72 h后氟化钙沉淀
抑制率/%0 5.85 0 5.85 0 1 4.26 27.18 4.20 28.21 2 2.97 49.23 2.89 50.60 2 1.21 79.32 1.15 80.34 4 0.04 99.32 0 100.00 5 0 100.00 0 100.00
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