CN113802124A - 一种抑制硫化氢腐蚀的缓蚀剂及其应用 - Google Patents
一种抑制硫化氢腐蚀的缓蚀剂及其应用 Download PDFInfo
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Abstract
本发明属石油加工助剂领域，尤其涉及一种针对硫化氢腐蚀为主的含有多环吲哚嗪衍生物季胺盐化合物腐蚀抑制剂及其应用，以重量百分含量计，包括多环吲哚嗪衍生物季胺盐1～60%；缓蚀剂1～70%；表面活性剂1～10%；溶剂1～90%。缓蚀剂为咪唑啉衍生物、磷酸酯、脂肪酸或季铵盐中的一种或两种以上的混合物。咪唑啉衍生物为菜籽油、花生油、塔尔油、葵花籽油或棕榈油与多胺化合物反应而成，其链长为16～22。本发明缓蚀剂用量小，效率高，成膜坚固，稳定性好，具有更低浓度下达到低腐蚀速率。
Description
技术领域
本发明属石油开采油田化学助剂领域，尤其涉及一种针对硫化氢腐蚀为主的含有多环吲哚嗪衍生物季胺盐化合物抑制硫化氢腐蚀的缓蚀剂及其应用。
背景技术
金属腐蚀造成巨大的经济损失，每年因金属腐蚀造成的损失占国民生产总值相当大一部分。在油气开采中，二氧化碳(CO2)和硫化氢(H2S)是常含有的伴生腐蚀性气体，对金属管线及设备可产生严重腐蚀，而且严重影响油气田集输系统可靠性及使用寿命。例如我国西部普光气田所产天然气H2S含量高达15％以上,CO2含量为8％以上，当体系中CO2/H2S分压相对比小于20时，腐蚀是以H2S控制型为主(B.F.Pots等,Improvement on De Waard-Milliams corrosion prediction and application to corrosion management,NACEcorrosion 2002,paper 02235)。硫化氢为主的腐蚀性较强，可造成局部点蚀和氢致开裂，由于硫化氢为剧毒气体，腐蚀泄露微量可致命，造成严重安全事故。
针对以H2S为主的油气田腐蚀,主要的防腐手段有采用高镍基合金钢防腐、涂层防腐与缓蚀剂防腐,其中采用高镍基合金钢虽然使得材质的防腐性能及整体的安全性能大大提高,但此类材质主要价格昂贵，增加油气田开发成本,而涂层的主要问题是使用条件受限且容易脱落。添加缓蚀剂是金属腐蚀防护中一种简单的、有效的、价廉的方法，适用于水溶液、酸性溶液、碱性溶液、有机溶剂和大气等各种环境中以防止金属的腐蚀，在石油天然气开采和集输过程中得到广泛的应用。缓蚀剂是指在金属的腐蚀介质中，加入微量或少量即可使金属材料在该介质中的腐蚀速度显著降低的物质。咪唑啉及其衍生物类缓蚀剂以其独特的分子结构，吸附性能较好，对于H2S、CO2腐蚀有一定的抑制效果，但单独使用对于高含硫化氢的腐蚀作用有限，缓蚀剂通常复配达到最佳效果，例如喹啉季胺盐复配以咪唑啉可减缓硫化氢为主的腐蚀速度。
发明内容
本发明旨在克服现有技术的不足之处而提供一种缓蚀剂用量小，效率高，成膜坚固，稳定性好，具有更低浓度下达到低腐蚀速率的抑制硫化氢腐蚀的缓蚀剂。
本发明还提供一种抑制硫化氢腐蚀的缓蚀剂的应用。
为解决上述技术问题，本发明是这样实现的：
一种抑制硫化氢腐蚀的缓蚀剂，以重量百分含量计，包括：
作为一种优选方案，本发明所述多环吲哚嗪衍生物季胺盐的分子结构式如下：
进一步地，本发明所述缓蚀剂为咪唑啉衍生物、磷酸酯、脂肪酸或季铵盐中的一种或两种以上的混合物。
进一步地，本发明所述咪唑啉衍生物为菜籽油、花生油、塔尔油、葵花籽油或棕榈油与多胺化合物反应而成，其链长为16～22。
进一步地，本发明所述磷酸酯为烷基磷酸酯，其烷基链长在12～22之间。
进一步地，本发明所述溶剂为甲醇、乙醇、异丙醇、乙二醇、丁醇、含苯环芳香溶剂与石油醚中的一种或两种以上的混合物。
进一步地，本发明所述表面活性剂为阴离子、阳离子、两性离子、非离子型表面活性剂中的一种或两种以上的混合物。
进一步地，本发明所述腐蚀抑制剂总活性浓度在配方中含量为1～90％，加注到腐蚀环境中时，在腐蚀液体中含量为1～1000ppm。
上述抑制硫化氢腐蚀的缓蚀剂在油气田开发和集输中的应用。
本发明含有多环吲哚嗪衍生物季胺盐化合物可以在含H2S为主的腐蚀条件下具有更低浓度下达到低腐蚀速率，缓蚀剂用量减小可降低缓蚀剂对环境的影响。本发明咪唑啉衍生物从菜籽油，花生油，塔尔油，葵花籽油，棕榈油等与多胺反应获得，并可以继续反应形成聚氧乙烯加成衍生物，能够与金属表面的结合形成牢固的金属保护膜，稳定性好。实验结果显示，含有多环吲哚嗪衍生物季胺盐的缓蚀剂具有更低的腐蚀速率，更好的缓蚀效果，并且没有局部腐蚀。
附图说明
下面结合具体实施方式对本发明作进一步说明。本发明的保护范围不仅局限于下列内容的表述。
图1为未含多环吲哚嗪衍生物季胺盐腐蚀抑制剂应用效果图；
图2为本发明腐蚀抑制剂应用效果图。
具体实施方式
本发明腐蚀抑制剂含有多环吲哚嗪衍生物季胺盐化合物和咪唑啉衍生物的混合物的以硫化氢为主缓蚀剂。
多环吲哚嗪衍生物季胺盐的二聚体结构如下式I所示：
其反离子为Cl-，上述多环吲哚嗪衍生物季胺盐含量在1～60％(重量)。
咪唑啉衍生物为链长16～22,可为菜籽油，花生油，塔尔油，葵花籽油，棕榈油，油酸等与多胺反应获得的，咪唑啉并可以继续与环氧乙烷反应形成聚氧乙烯加成衍生物。其他缓蚀剂中间体还可包括烷基磷酸酯、季胺盐、脂肪酸等，其烷基链长在12～22之间。缓蚀剂在产品中含量为1～70％(重量)。
对于水分散性差的缓蚀剂，可以加入表面活性剂作为分散剂和润湿剂，它可以包括阴离子，阳离子，两性离子，非离子型表面活性剂及其混合物。阴离子包括烷基磺酸盐，烷基苯磺酸盐，烷基硫酸脂盐，脂肪醇聚氧乙烯醚硫酸盐，烷基磷酸酯等。阳离子表面活性剂包括烷基季胺盐，双烷基季胺盐，烷基酰胺季胺盐，烷基二甲基苄基氯化胺。两性表面活性剂包括烷基羧基甜菜碱，烷基酰胺丙基羧基甜菜碱，烷基酰胺丙基羟磺基甜菜碱，烷基羟磺基甜菜碱等，非离子表面活性剂包括脂肪醇聚氧乙烯醚，烷基酚聚氧乙烯醚，二乙醇酰胺，以上表面活性剂烷基长度为8～18的含饱和或不饱和键，直链或支链。表面活性剂在产品中含量为1～10％(重量)。
溶剂包括甲醇、乙醇、异丙醇、乙二醇、丁醇、含苯环芳香溶剂或石油醚等。溶剂在产品中含量1～90％(重量)。
所述缓蚀剂在配方中活性含量重量百分比为1～70％。
复配腐蚀抑制剂现场使用可以通过泵注连续注入到含硫化氢腐蚀的井筒或者集输管线中，加注到应用环境中时为1～1000ppm。
实施例
为了进一步阐述本发明在含H2S为主的腐蚀环境中效果，本发明给出下述实施例，但实施列并不是用来以任何方式限制本发明的范围。
H2S缓蚀剂配方为表1所示，多环吲哚嗪衍生物季胺盐(BQD)参照中国专利申请CN108410444中实施列2方法合成，喹啉季胺盐为沙洋科若星化工有限公司产品，油酸咪唑啉为佳化化学股份有限公司产品，配方含量比为有效物含量。
表1-复配配方组成
| 腐蚀抑制剂A | 腐蚀抑制剂B | |
| 油酸咪唑啉 | 15％ | 15％ |
| 喹啉季胺盐 | 12％ | |
| 多环吲哚嗪衍生物季胺盐(BQD) | 12％ | |
| 壬基酚聚氧乙烯醚-10 | 3％ | 3％ |
| 甲醇 | 70％ | 70％ |
上述腐蚀抑制剂A的制备方法如下：
将油酸咪唑啉、喹啉季胺盐、壬基酚聚氧乙烯醚-10及甲醇，于温度30℃搅拌20分钟，即可。
上述腐蚀抑制剂B的制备方法如下：
将油酸咪唑啉、多环吲哚嗪衍生物季胺盐(BQD)、壬基酚聚氧乙烯醚-10及甲醇于温度30℃搅拌20分钟，即可。
腐蚀测试实验如下，实验腐蚀挂片材质为L360，尺寸为50x10x3mm，使用600号与1000号砂纸把挂片表面处理平整，用显微镜放大100倍观察管片表面，确保没有划痕与材料本身没有点蚀。用丙酮与无水乙醇分别浸泡5分钟，去除残留在金属表面的油脂，用冷风吹干，测量挂片的重量，精确到0.0001g。腐蚀测试模拟水如下表2。
表2-模拟水组成(mg/L)
| HCO<sub>3</sub><sup>-</sup> | Mg<sup>2+</sup> | Cl<sup>-</sup> | Na<sup>+</sup>,K<sup>+</sup> | SO<sub>4</sub><sup>2-</sup> | B<sup>3+</sup> | Ca<sup>2+</sup> | 总矿化度 |
| 238 | 484 | 63,900 | 35,000 | 445 | 60 | 5,080 | 105,207 |
盐水配好后添加一定浓度的缓蚀剂，预先用高纯氮气除氧18小时，再通过真空吸入2升的釜中1.6升溶液后再除氧1小时，然后开启搅拌器，加热到60℃,通入H2S分压到0.21MPa，饱和溶解半小时，再通入CO2分压到0.48Mpa，饱和溶解半小时，设置挂片在400rpm下旋转。测试72小时后，冷却装置。取出挂片依次用丙酮、乙醇放入超声波仪器清洗，并用橡皮擦擦拭挂片表面除去腐蚀产物膜，再清洗干燥称量测试后挂片重量，计算腐蚀速率，每次实验放入3个同样挂片，腐蚀速率取其平均值。腐蚀速率(rcorr)可由下面的公式计算：
缓蚀率＝(r空白-r加缓蚀剂)*100/r空白；
其中：rcorr－平均腐蚀速率，mm/y；m－测试前挂片的重量，g；mt－测试后的挂片重量，g；S1－挂片的表面积，cm2；ρ－挂片材料密度，g/cm3；t－挂片测试时间，h。
表3-动态腐蚀失重测试结果
典型的腐蚀后挂片照片如图1及图2所示。图1为未含多环吲哚嗪衍生物季胺盐腐蚀抑制剂应用效果图。图2为本发明腐蚀抑制剂应用效果图。腐蚀抑制剂浓度100ppm。
腐蚀测试后挂片外观照片以上结果显示，含有多环吲哚嗪衍生物季胺盐的缓蚀剂B具有更低的腐蚀速率，更好的缓蚀效果，并且没有局部腐蚀。
以上所公开的本发明的具体描述或实施例，在不超过现有公开的实验手段的范围内可以制出或实施。本发明优选的实施方式所描述的所有的技术方案或方法，仅用于说明本发明而并非受限于本发明具体描述或实施例，本领域的普通技术人员应当理解，那些不违反本发明的概念、范围和精神的修改或等同替换，以达到相同的技术效果的技术手段，均在本发明的保护范围之内。
Claims (9)
1.一种抑制硫化氢腐蚀的缓蚀剂，其特征在于，以重量百分含量计，包括：
2.根据权利要求1所述抑制硫化氢腐蚀的缓蚀剂，其特征在于：所述多环吲哚嗪衍生物季胺盐的分子结构式如下：
3.根据权利要求2所述抑制硫化氢腐蚀的缓蚀剂，其特征在于：所述缓蚀剂为咪唑啉衍生物、磷酸酯、脂肪酸或季铵盐中的一种或两种以上的混合物。
4.根据权利要求3所述抑制硫化氢腐蚀的缓蚀剂，其特征在于：所述咪唑啉衍生物为菜籽油、花生油、塔尔油、葵花籽油或棕榈油与多胺化合物反应而成，其链长为16～22。
5.根据权利要求3所述抑制硫化氢腐蚀的缓蚀剂，其特征在于：所述磷酸酯为烷基磷酸酯，其烷基链长在12～22之间。
6.根据权利要求5所述抑制硫化氢腐蚀的缓蚀剂，其特征在于：所述溶剂为甲醇、乙醇、异丙醇、乙二醇、丁醇、含苯环芳香溶剂与石油醚中的一种或两种以上的混合物。
7.根据权利要求6所述抑制硫化氢腐蚀的缓蚀剂，其特征在于：所述表面活性剂为阴离子、阳离子、两性离子、非离子型表面活性剂中的一种或两种以上的混合物。
8.根据权利要求7所述抑制硫化氢腐蚀的缓蚀剂，其特征在于：所述腐蚀抑制剂总活性浓度在配方中含量为1～90％，加注到腐蚀环境中时，在腐蚀液体中含量为1～1000ppm。
9.一种如权利要求1～8任一所述抑制硫化氢腐蚀的缓蚀剂在油气田开发和集输中的应用。
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