CN104762075B - 油田水用缓蚀剂及制备方法以及检测方法 - Google Patents
油田水用缓蚀剂及制备方法以及检测方法 Download PDFInfo
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Abstract
一种油田水用缓蚀剂及制备方法以及检测方法，包含主剂和复配剂，其主剂是芳醛与乙二胺合成的希夫碱，复配剂是乌洛托品、OP‑10（烷基酚聚氧乙烯醚）、碘化钾、硫脲或钨酸钠，芳醛与乙二胺形成的希夫碱按照质量比例与乌洛托品、OP‑10、碘化钾、硫脲或钨酸钠复配，得到成品缓蚀剂。所需原料简单易得，主剂合成简单，无需提纯可直接使用。操作过程简便、安全，反应时间短，成本低，产率高，缓蚀效果强，适于工业规模化生产，用其检测，具有较强的实用性，在石油开采中应用具有很好的缓释性能。
Description
技术领域
本发明涉及一种石油开采油田用缓蚀剂，特别是涉及油田水用缓
蚀剂及制备方法以及检测方法。
背景技术
金属腐蚀几乎遍及各行各业，在石油开采过程中，随着含水量的增大改变了原油管道中流体原本“水在油中”的形态，加剧了原油处理、输送管道设备的腐蚀。特别是含CO2、H2S及高盐组分油井的相继出觋，也使得油井的腐蚀问题变的越来越突出，据粗略估计，腐蚀给我国石油工业造成的损失约占行业总产值的6％，而采取合适的防腐措施，可挽回30％～40％的损失。添加缓蚀剂是一种简便、有效、成本低的抑制金属材料腐蚀的方法。国内的缓蚀剂类型主要有咪唑啉型、mannich碱, 季铵盐缓蚀剂、炔醇型、吡啶型等。
在众多类型的缓蚀剂中，不同类型的缓蚀剂均存在的缺点。如炔醇类缓蚀剂的缓蚀效果好，但价格昂贵且毒性较强；脂肪胺及其衍生物、松香衍生物在酸液中的溶差；酰胺羧酸型缓蚀剂的抗高温性能较差；吡啶类以及由吡啶、喹啉等合成的季铵盐类缓蚀剂的成本较高，虽然热稳定性好，但在高温下脱附严重，需加大用量等缺点。
发明内容
为了克服现有技术的的诸多缺陷，本发明的发明目的一是提供一种以芳醛和乙二胺为原料，在一定条件下合成为主剂并通过添加其他几种化合物进行复配而成的高效油田水用缓蚀剂；另一目的是提供油田水用缓蚀剂的制备方法，再一目的是提供一种缓蚀剂的检测方法，用于解决油田回注水管道腐蚀速度较快的问题。
实现上述发明目的采用以下技术方案：
一种油田采出水用缓蚀剂，包含主剂和复配剂，其主剂是芳醛与乙二胺合成的希夫碱，复配剂是乌洛托品、OP-10（烷基酚聚氧乙烯醚）、碘化钾、硫脲或钨酸钠的一种，芳醛与乙二胺形成的希夫碱按照质量比例与乌洛托品、OP-10（烷基酚聚氧乙烯醚）、碘化钾、硫脲或钨酸钠的一种复配，得到成品缓蚀剂。
作为优选，所述的主剂为式a或式b所示的芳醛与乙二胺形成的希夫碱，
。
作为优选，主剂与乌洛托品复配的质量比例为1.0:0.04；主剂与OP-10的质量比1.0:0.05；主剂与碘化钾的质量比1.0:0.1～0.2；主剂与硫脲的质量比1.0:0.2～0.3；主剂与钨酸钠的质量比1.0:0.02。
作为优选，所述的芳醛采用肉桂醛或糠醛。
一种油田采出水用缓蚀剂的制备方法，包括下述步骤：
⑴合成主剂：
主剂合成过程中以乙醇作为溶剂，在装有温度计、回流冷凝管、磁转子的三颈烧瓶中加入芳醛和乙二胺，而后按照质量比例加入10倍于芳醛的乙醇，在70℃条件下搅拌反应两个小时，得到的反应溶液冷却静置，沉淀，抽滤，滤饼用水洗涤得到黄色固体，即为主剂；
⑵主剂与复配剂复配：
将主剂按照质量比例与复配剂复配，得到缓蚀剂。
作为优选，以肉桂醛合成的希夫碱为主剂的缓蚀剂的制备方法：在装有温度计、回流冷凝管、磁转子的三颈烧瓶中按照3：1的质量比加入肉桂醛和乙二胺，而后加入10倍于肉桂醛物质量的乙醇，在70℃条件下搅拌反应两个小时，得到的反应溶液冷却静置，得到沉淀，抽滤，滤饼用水洗涤得到黄色固体，得到的产物为缓蚀剂主剂a；
反应方程式如下：
；
按照质量比例将缓蚀剂主剂a分别与乌洛托品、OP-10、碘化钾、硫脲、钨酸钠复配得到缓蚀剂。
作为优选，以糠醛合成的希夫碱为主剂的缓蚀剂的制备方法：在250mL装有温度计、回流冷凝管、磁转子的三颈烧瓶中按照6:1的质量比加入新蒸馏后的糠醛和乙二胺，然后加入10倍于糠醛质量的乙醇，在70℃条件下搅拌反应两个小时，得到的反应溶液冷却静置，沉淀，抽滤，滤饼用水洗涤得到黄色固体，即为产物b。
反应方程式如下：
按照质量比例将缓蚀剂主剂b分别与乌洛托品、OP-10、碘化钾、硫脲、钨酸钠复配得到缓蚀剂。
一种油田采出水用缓蚀剂的检测方法，包括下述步骤：
⑴在1L水中加入氯化钠，氯化钙，六水合氯化镁，硫酸钠，碳酸氢钠，四水合氯化亚铁混合配成盐溶液；
⑵按照SY/T 5273-2000油田采出水用缓蚀剂性能评价方法，以常用的N80碳钢试片为腐蚀材料，将上述浓度的盐溶液置于高压釜内，往高压釜内加入缓蚀剂主剂，用棉线将已除油除水的两个钢片捆绑在高压釜内部支架上，封闭高压釜；
⑶氮气鼓泡5min，除去高压釜内部氧气；
⑷打入高纯二氧化碳，至压强0.5MPa，再打入氮气使得总压至1.5Mpa，调节高压釜内部温度至70℃；
⑸开动搅拌装置保持上述状态48h；
⑹取出的钢片用依次用10%盐酸溶液和8%乌洛托品洗涤，再用无水酒精浸泡2min，取出擦干称重；
⑺用两钢片腐蚀前后质量的差值的平均值作为腐蚀质量，然后以其与腐蚀时间的比值来计算腐蚀速率，并与不加缓蚀剂的空白样作为对比来评价缓蚀剂缓蚀效率。
作为优选，所述的采出水的水质构成为每升采出用水含有：氯化钠12.07～12.08g、氯化钙1.32～1.33g、氯化镁0.50～0.51g、硫酸钠0.42～0.43g、碳酸氢钠1.80～1.90g、氯化亚铁0.00286～0.00287g，或者含有其相应浓度的离子。
采用上述技术方案，与现有技术相比，本发明合成了两种芳香希夫碱，用其作为缓释主剂分别与硫脲、乌洛托品、碘化钾、烷基酚聚氧乙烯醚(OP-10)、钨酸钠复配，所需原料简单易得，主剂合成简单，无需提纯可直接使用。操作过程简便、安全，反应时间短，成本低，产率高，缓蚀效果强，适于工业规模化生产，具有较强的实用性，在石油开采中应用具有很好的缓释性能。
具体实施方式
下面结合实施例进一步描述本发明。本发明的保护范围不仅局限于下列内容的表述。
在下面的实施例中，肉桂醛、2-呋喃甲醛、乙二胺、乙醇等所有用到的化学试剂均为分析纯。
实施例1，油田采出水用缓蚀剂
缓蚀剂包含主剂和复配剂，其主剂为式a或式b所示的芳醛与乙二胺合成的希夫碱，
。
复配剂是乌洛托品、OP-10（烷基酚聚氧乙烯醚）、碘化钾、硫脲或钨酸钠，芳醛与乙二胺形成的希夫碱按照质量比例与乌洛托品、OP-10（烷基酚聚氧乙烯醚）、碘化钾、硫脲或钨酸钠等复配，得到成品缓蚀剂。主剂与乌洛托品复配的质量比例为1.0:0.04；主剂与OP-10的质量比1.0:0.05；主剂与碘化钾的质量比1.0:0.1～0.2；主剂与硫脲的质量比1.0:0.2～0.3；主剂与钨酸钠的质量比1.0:0.02。
本发明的芳醛采用肉桂醛或糠醛
主剂合成过程中需加入乙醇作为溶剂，得到的粗产物无需经过分离提纯处理，除掉溶剂后即可得到相应的作为缓蚀剂主剂使用的a或b。
A、以肉桂醛合成的希夫碱为主剂制备缓蚀剂及检测
实施例2
在250mL装有温度计、回流冷凝管、磁转子的三颈烧瓶中加入13.2g肉桂醛和2.0g乙二胺，而后加入60mL乙醇，70℃条件下搅拌反应两个小时，得到的反应溶液冷却静置，得到沉淀，抽滤，滤饼用水洗涤得到黄色固体，即为产物主剂a，其反应方程式如下：
实施例3，复配
将主剂a与乌洛托品复配的质量比例为1.0:0.04；主剂与OP-10的质量比1.0:0.05；主剂与碘化钾的质量比1.0:0.1～0.2；主剂与硫脲的质量比1.0:0.2～0.3；主剂与钨酸钠的质量比1.0:0.02等各种复配剂混合均匀，即得成品缓蚀剂。
实施例4，缓蚀剂的检测方法
在1L容量瓶中加入氯化钠 12.0720g，氯化钙 1.3209g，六水合氯化镁1.0750g，硫酸钠0.4290g，碳酸氢钠1.8177g，四水合氯化亚铁0.0045g等配成盐溶液。
按照SY/T 5273-2000油田采出水用缓蚀剂性能评价方法，以常用的N80碳钢试片为腐蚀材料，将上述容量瓶内的盐溶液置于高压釜内，并将浓度为25ppm的缓蚀剂主剂a加入高压釜，用棉线将已除油除水的两个钢片捆绑在高压釜内部支架上，封闭高压釜。氮气鼓泡5min，除去高压釜内部氧气。然后打入高纯二氧化碳，至压强0.5MPa，再打入氮气使得总压至1.5MPa。调节高压釜内部温度至70℃。开动搅拌装置保持上述状态48h。
取出的钢片用依次用10%盐酸溶液和8%乌洛托品洗涤，再用无水酒精浸泡2min，取出擦干称重。用空白试样的质量损失减去两钢片腐蚀前后质量损失的平均值作为分子，以空白试样腐蚀前后的质量损失为分母来计算缓蚀率，结果缓蚀率为η=84.5%。
B、以糠醛合成的希夫碱为主剂制备缓蚀剂剂检测
实施例5 主剂b的制备
在250mL装有温度计、回流冷凝管、磁转子的三颈烧瓶中加入9.6g蒸馏后的糠醛和1.5g乙二胺，然后加入60mL乙醇，70℃条件下搅拌反应两个小时，得到的反应溶液冷却静置，经过沉淀，抽滤，滤饼用水洗涤得到黄色固体，即为产物主剂b。
反应方程式如下：
实施例6 复配
将主剂b与乌洛托品复配的质量比例为1.0:0.04；主剂与OP-10的质量比1.0:0.05；主剂与碘化钾的质量比1.0:0.1～0.2；主剂与硫脲的质量比1.0:0.2～0.3；主剂与钨酸钠的质量比1.0:0.02等各种复配剂混合均匀，即得到成品缓蚀剂。
实施例7配置盐溶液
在1L容量瓶中加入氯化钠 12.0720g，氯化钙 1.3209g，六水合氯化镁1.0750g，硫酸钠0.4290g，碳酸氢钠1.8177g，四水合氯化亚铁0.0045g等配成盐溶液。
实施例8 检测
按照SY/T 5273-2000油田采出水用缓蚀剂性能评价方法，以常用的N80碳钢试片为腐蚀材料，将上述容量瓶内的盐溶液置于高压釜内，并将浓度为25ppm的缓蚀剂主剂b加入到高压釜，用棉线将已除油除水的两个钢片捆绑在高压釜内部支架上，封闭高压釜。氮气鼓泡5min，除去高压釜内部氧气。然后打入高纯二氧化碳，至压强0.5MPa，再打入氮气使得总压至1.5MPa。调节高压釜内部温度至70℃。开动搅拌装置保持上述状态48h。
取出的钢片依次用10%盐酸溶液和8%乌洛托品洗涤，再用无水酒精浸泡2min，取出擦干称重。用空白试样的质量损失减去两钢片腐蚀前后质量损失的平均值作为分子，以空白试样腐蚀前后的质量损失为分母来计算缓蚀率，结果缓蚀率为η=83.4%。
本发明采出水的水质构成为每升采出用水含有：氯化钠12.07～12.08g、氯化钙1.32～1.33g、氯化镁0.50～0.51g、硫酸钠0.42～0.43g、碳酸氢钠1.80～1.90g、氯化亚铁0.00286～0.00287g，或者含有其相应浓度的离子。
需要说明的是，以上关于本发明的具体描述，仅用于说明本发明而并非受限于本发明实施例所描述的技术方案，本领域的普通技术人员应当理解，仍然可以对本发明进行修改或等同替换，以达到相同的技术效果；只要满足使用需要，都在本发明的保护范围之内。
Claims (1)
1.一种油田采出水用缓蚀剂，包含主剂和复配剂，其特征在于，其主剂是芳醛或芳杂醛与乙二胺合成的希夫碱，复配剂是乌洛托品、OP-10、碘化钾、硫脲以及钨酸钠，芳醛或芳杂醛与乙二胺形成的希夫碱按照质量比例与乌洛托品、OP-10、碘化钾、硫脲以及钨酸钠的复配，得到成品缓蚀剂；
其中，所述的主剂为式a或式b所示的芳醛或芳杂醛与乙二胺形成的希夫碱，
主剂与乌洛托品复配的质量比例为1.0:0.04；主剂与OP-10的质量比1.0:0.05；主剂与碘化钾的质量比1.0:0.1～0.2；主剂与硫脲的质量比1.0:0.2～0.3；主剂与钨酸钠的质量比1.0:0.02。
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