CN102954931A - 评价油井管用钢耐硫化氢腐蚀性能的电化学测试溶液 - Google Patents
评价油井管用钢耐硫化氢腐蚀性能的电化学测试溶液 Download PDFInfo
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 35
- 238000005260 corrosion Methods 0.000 title claims abstract description 30
- 230000007797 corrosion Effects 0.000 title claims abstract description 30
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 25
- 239000010959 steel Substances 0.000 title claims abstract description 25
- 239000003129 oil well Substances 0.000 title claims abstract description 23
- 238000000840 electrochemical analysis Methods 0.000 title claims abstract description 17
- 239000012085 test solution Substances 0.000 title claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000007789 sealing Methods 0.000 claims description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 238000011156 evaluation Methods 0.000 claims description 4
- 238000002242 deionisation method Methods 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 238000012360 testing method Methods 0.000 abstract description 35
- 238000000034 method Methods 0.000 abstract description 7
- 230000010287 polarization Effects 0.000 abstract description 5
- 238000004458 analytical method Methods 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract 3
- 150000003568 thioethers Chemical class 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 239000005308 flint glass Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000019086 sulfide ion homeostasis Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
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Abstract
本发明提供一种评价油井管用钢耐硫化氢腐蚀性能的电化学测试溶液，根据以下反应方程式将不同浓度的硫化物加入氯化物溶液中，溶剂为去离子水，置于封闭的电解池中，通氮气除氧气，加入乙酸反应，并调节溶液pH值，封闭电解池，静置，形成电化学溶液：
Description
技术领域
本发明属于电化学测试溶液技术领域，尤其涉及一种用于冶金行业评价油井管用钢耐硫化氢腐蚀性能的电化学测试溶液。
背景技术
油井管用钢作为重要的石油勘探用钢，在石油工业用钢的总量中，油井管用钢占40%以上。目前世界油气田中大约1/3含有硫化氢气体，在我国的几大油气田如四川、长庆、中原、华北、塔里木油气田都含有不同程度的硫化氢气体。硫化氢腐蚀往往会在远低于材料本身屈服强度时就突然发生断裂，重大灾难极易发生，造成不可挽回的损失。油井管用钢耐硫化氢腐蚀性能直接影响其使用寿命，因此客观评价油井管用钢的耐硫化氢腐蚀性能就显得尤为重要。耐硫化氢腐蚀性能是油井管用钢的一个重要的使用性能，现已有一系列的常规试验测试方法，主要包括标准拉伸试验、弯梁试验、C型环试验、双悬臂梁试验和电化学测试。标准拉伸试验、弯梁试验、C型环试验和双悬臂梁试验都能较直接的评价油井管用钢的耐硫化氢腐蚀性能，但都存在试验条件苛刻、试验周期长、试样加工精度要求高、试验结果反应的信息量少等缺点。并且硫化氢气体是一种有毒气体，对试验的保障措施和人员的操作要求非常高。电化学测试包括腐蚀电位法、极化法、电化学阻抗法等，是正确和客观评价金属材料耐蚀性能的一种数字化测试技术，它可以测定油井管用钢在电解质溶液中的腐蚀电位、极化电阻或阻抗值，通过这些数据可算得金属的溶解速率，定量、快速地评价油井管用钢的耐硫化氢腐蚀性能。
在耐硫化氢腐蚀性能的电化学测试过程中，电解质溶液腐蚀环境的选择是极为重要的。目前，电化学方法检测所用电解质溶液中含有的硫化氢是FeS和盐酸发生化学反应由启普发生器制备，产生的硫化氢气体通入去离子水至饱和，即得到饱和硫化氢溶液，再用去离子水稀释至各种质量分数，之后采用碘量滴定方法测试硫化氢溶液的浓度。该方法得到的硫化氢溶液掺杂HCl，影响试验测试结果。
综上所述，检测油井管用钢耐硫化氢腐蚀性能的电化学测试技术的关键因素之一是正确选择一种电解质溶液腐蚀环境，该环境可快速地获得稳定的电化学条件，且对不同条件的硫化氢腐蚀环境表现的电化学参数有明显的差异，目前还没有符合上述条件的电解质溶液，即电化学测试溶液。
发明内容
本发明的目的在于提供一种新的电化学测试溶液。该溶液能够快速、安全地测试油井管用钢耐硫化氢腐蚀性能，以解决现有标准拉伸试验、弯梁试验、C型环试验、双悬臂梁试验和慢应变速率拉伸试验试验条件苛刻、试验周期长、试样加工精度要求高、试验结果反应的信息量少等缺点。
本发明是这样实现的，该评价油井管用钢耐硫化氢腐蚀性能的电化学测试溶液，根据反应方程式（1）将不同浓度的硫化物加入氯化物溶液中，溶剂为去离子水，置于封闭的电解池中，通氮气除氧气，加入乙酸反应，并调节溶液pH值，封闭电解池，静置，便形成硫化氢水溶液，也即电化学溶液：
2CH3COOH+S2-→2CH3COO-+H2S （1）。
本发明所述电化学溶液在室温下的pH值为4～6；所述的氯化物包括氯化钠、氯化钾，浓度为0.10~0.85mol/L；所述的硫化物包括硫化钠、硫化钾，浓度为0.003~0.04mol/L；所述的去离子水的电导率≤5μs/cm。
本发明方法简单，操作方便，安全性强；采用本发明能以量化的数值反映出油井管用钢在不同条件硫化氢腐蚀环境中的耐硫化氢腐蚀性能的差异，且检测结果准确；以极化电阻的大小来检测油井管用钢的耐硫化氢腐蚀性能，试验结果分析简单，试验时间短。
具体实施方式
下面通过实施例对本发明做进一步的说明。
本发明实施例按以下步骤配制电化学测试溶液：根据反应方程式（1）将不同浓度的硫化物加入氯化物溶液中，溶剂为去离子水，置于封闭的电解池中，通氮气除氧气20min，加入乙酸反应，并调节溶液pH值，封闭电解池，静置15min。
本发明实施例的具体数据见表1，实施例的试验结果见表2。
表1 本发明实施例数据
表2 本发明实施例试验结果
以上实施例的试验步骤为：用粗砂纸去除试样表面氧化膜，再用1000#金相砂纸打磨，酒精脱水，冷风吹干，静置5min后，安装于工作电极处。用橡皮套、橡皮塞将电解池密封。将本发明电化学溶液置于电解池中。进行开路电位的测试，当电位在120s时间内的变化值小于5mV时，开路电位稳定。然后，开始进行线性极化的测试，试样条件：扫描速度0.166mV/s。其中工作电极（即研究电极）为待测试片、参比电极为甘汞电极（SCE）、辅助电极为铂丝网。从表2可见，应用本发明电化学测试溶液测得的极化电阻值差异性显著。
表3 为3种不同硫化氢试验方法的时间差别。从中不难看出，本发明试验时间明显缩短。
表3 试验时间差别
从上述实施例可见，采用本发明电解液能够有差异性地、快速地测试油井管用钢耐硫化氢腐蚀性能。
Claims (3)
1.一种评价油井管用钢耐硫化氢腐蚀性能的电化学测试溶液，其特征在于，根据反应方程式（1）将不同浓度的硫化物加入氯化物溶液中，溶剂为去离子水，置于封闭的电解池中，通氮气除氧气，再加入乙酸反应，并调节溶液pH值，封闭电解池，静置，便形成硫化氢水溶液，也即电化学测试溶液：
i.2CH3COOH+S2-→2CH3COO-+H2S （1）。
2.根据权利要求1所述的评价油井管用钢耐硫化氢腐蚀性能的电化学测试溶液，其特征在于所述电化学溶液室温下的pH值为4～6。
3.根据权利要求1所述的评价油井管用钢耐硫化氢腐蚀性能的电化学测试溶液，其特征在于所述的氯化物包括氯化钠、氯化钾，浓度为0.10~0.85mol/L；所述的硫化物包括硫化钠、硫化钾，浓度为0.003~0.04mol/L；所述去离子水的电导率≤5μs/cm。
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| CN103901084A (zh) * | 2014-03-21 | 2014-07-02 | 哈尔滨工程大学 | 一种高强钢氢损伤的表面吸附氢快速检测方法 |
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| CN102305761A (zh) * | 2011-08-01 | 2012-01-04 | 西南石油大学 | 酸性介质输送管道焊缝及母材腐蚀模拟试验装置及方法 |
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| CN102305761A (zh) * | 2011-08-01 | 2012-01-04 | 西南石油大学 | 酸性介质输送管道焊缝及母材腐蚀模拟试验装置及方法 |
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| BORIS M. MIKSIC ET AL.: "Effectiveness of the Corrosion Inhibitors for the Petroleum Industry Under Various Flow Conditions", 《NATIONAL ASSOCIATION OF CORROSION ENGINEERS》, 31 December 2009 (2009-12-31), pages 4 * |
| M. A. LUCIO-GARCIA ET AL.: "A study of hydroxyethyl imidazoline as H2S corrosion inhibitor using electrochemical noise and electrochemical impedance spectroscopy", 《J APPL ELECTROCHEM》, vol. 40, 27 September 2009 (2009-09-27), XP019769836 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103901084A (zh) * | 2014-03-21 | 2014-07-02 | 哈尔滨工程大学 | 一种高强钢氢损伤的表面吸附氢快速检测方法 |
| CN103901084B (zh) * | 2014-03-21 | 2016-01-27 | 哈尔滨工程大学 | 一种高强钢氢损伤的表面吸附氢快速检测方法 |
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