CN106588776A - 一种高含h2s/co2缓蚀剂的制备方法 - Google Patents

一种高含h2s/co2缓蚀剂的制备方法 Download PDF

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CN106588776A
CN106588776A CN201510664853.XA CN201510664853A CN106588776A CN 106588776 A CN106588776 A CN 106588776A CN 201510664853 A CN201510664853 A CN 201510664853A CN 106588776 A CN106588776 A CN 106588776A
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赵志忠
赵乾翔
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Beijing Tyco Ande Technology Development Co Ltd
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Abstract

本发明属于高含H2S/CO2油气田集输管线腐蚀防护技术,涉及H2S/CO2缓蚀剂的制备方法。随着目前,我国报道的防止H2S/CO2腐蚀的缓蚀剂大多数缓蚀剂由两种或多种有机物质复配组成。然而抗高浓度H2S和高浓度CO2腐蚀的缓蚀剂不多,常用的油酸、环烷酸咪唑啉、酰胺类缓蚀剂通常抗H2S腐蚀性能难以满足应用要求。而高含H2S/CO2油气井的开发和集输过程中,H2S腐蚀占主导地位,因此需要用更长链的脂肪酸与多胺反应形成分子量更大的咪唑啉、酰胺分子,并且复配芳香酸与脂肪环胺合成酰胺,使缓蚀剂形成的吸附膜更为完整、致密。从而满足高含H2S/CO2环境中腐蚀防护的技术要求。本发明为了解决上述问题,提供一种制备方法简单,且对高含H2S/CO2环境缓蚀效果好的缓蚀剂的制备方法。

Description

一种高含H2S/CO2缓蚀剂的制备方法
技术领域
随着国内外高含H2S/CO2油气井的开发,对抗H2S/CO2缓蚀剂提出了更高的技术要求。实际应用表明,缓蚀剂仍是一种十分有效的不可或缺的主要防腐手段。
目前,我国报道的防止H2S/CO2腐蚀的缓蚀剂大多数是酰胺、咪唑啉衍生物、有机胺、季胺盐、喹啉、页氮、醛类、丙炔醇、炔氧甲基季胺盐、松香胺衍生物等。大多数缓蚀剂由两种或多种有机物硬复配组成。然而抗高浓度H2S和高浓度CO2腐蚀的缓蚀剂不多,有待进一步研究开发,以适应石油天然气能源工业生产发展的需要。
背景技术
背景相关技术
随着国内外高含H2S/CO2油气井的开发,对抗H2S/CO2缓蚀剂提出了更高的技术要求。实际应用表明,缓蚀剂仍是一种十分有效的不可或缺的主要防腐手段。
目前,我国报道的防止H2S/CO2腐蚀的缓蚀剂大多数是酰胺、咪唑啉衍生物、有机胺、季胺盐、喹啉、页氮、醛类、丙炔醇、炔氧甲基季胺盐、松香胺衍生物等。大多数缓蚀剂由两种或多种有机物质复配组成。然而抗高浓度H2S和高浓度CO2腐蚀的缓蚀剂不多,有待进一步研究开发,以适应石油天然气能源工业生产发展的需要。
与本发明相关的现有技术
目前国内外所使用的缓蚀剂基本上都是吸附型缓蚀剂,如链状有机胺及其衍生物,咪唑啉及其盐或咪唑啉衍生物季胺盐类,松香胺衍生物。在高含H2S/CO2油气井的开发方面:双咪唑啉、含多个苯环的咪唑啉季胺盐、松香衍生物、较大分子量含氮的化合物,都是很有前景的研究方向。
现有技术的缺点
常用的油酸、环烷酸咪唑啉、酰胺类缓蚀剂通常抗H2S腐蚀性能难以满足应用要求。而高含H2S/CO2油气井的开发和集输过程中,H2S腐蚀占主导地位,因此需要在传统常用咪唑啉、酰胺的基础上进行优化和复配。
发明内容
本发明所要解决的技术问题(发明目的)
使用更长链的脂肪酸与多胺反应形成分子量更大的咪唑啉、酰胺分子,并且复配芳香酸与脂肪环胺合成酰胺,使缓蚀剂形成的吸附膜更为完整、致密。从而满足高含H2S/CO2环境中腐蚀防护的技术要求。
本发明为了解决上述问题,提供一种制备方法简单,且对高含H2S/CO2环境缓蚀效果好的缓蚀剂的制备方法。
本发明提供的完整技术方案(发明方案)
本发明涉及一种长链咪唑啉化合物、芳香酸脂肪环胺酰胺的合成和高含H2S/CO2缓蚀剂的制备方法,包括:长链咪唑啉化合物、芳香酸脂肪环胺酰胺、溶剂。该缓蚀剂用于高含H2S/CO2的集输管线。本发明采用长链脂肪酸-芥酸与胺分子间脱水、分子内脱水反应,生成长链咪唑啉化合物;苯甲酸与脂肪环胺反应生成酰胺;两者与溶剂复配,形成的缓蚀剂吸附膜对高浓度H2S/CO2腐蚀具有良好的保护作用。
本发明是通过以下技术方案来实现:
一种长链咪唑啉化合物具有如下结构通式:
式中的n中碳原子数量为1、2、3或4。
苯甲酸脂肪环胺化合物具有如下结构式:
一种高含H2S/CO2缓蚀剂,包括以下组分:
长链咪唑啉化合物40-55重量%;
苯甲酸脂肪环胺酰胺10-15重量%;
溶剂30-50重量%;
其中,长链咪唑啉化合物具有如下结构通式:
式中的n中碳原子数量为1、2、3或4。
苯甲酸脂肪环胺化合物具有如下结构式:
所述脂肪环胺为:吗啉、环己胺、哌嗪。
所述溶剂为200#溶剂汽油、柴油、甲苯、二甲苯。
一种高含H2S/CO2缓蚀剂的制备方法,其特征在于,包括以下步骤:
步骤1:制备长链咪唑啉化合物:
按顺序在反应器中加入摩尔比为1.0∶1.1~1.5的芥酸和多胺,在搅拌条件下升温至120-140℃开始回流,保持回流1.5~2.0h;再升温至150~170℃,回流4.0~5.0h进行酰胺化反应;继续升温至240~260℃回流3.0-4.0h进行环化反应,得到棕色粘稠液体,即为目标产物;
步骤2:
在反应器中加入摩尔比为1.0∶1.1~1.2的苯甲酸和脂肪环胺,在搅拌条件下升温至140-160℃开始回流,保持回流4.0~5.0h进行酰胺化反应,得到棕色粘稠液体,即为目标产物;
步骤3:按照质量百分比分别称取含长链咪唑啉化合物、苯甲酸脂肪环胺酰胺和溶剂,互相混合,搅拌均匀,即得到H2S/C02缓蚀剂。
所述长链脂肪羧酸为:芥酸。
所述多胺为:二乙烯三胺、三乙烯四胺、四乙烯五胺、五乙烯六胺。
所述脂肪环胺为:吗啉、环己胺、哌嗪。
所述溶剂为200#溶剂汽油、柴油、甲苯、二甲苯。
与现有技术相比,本发明具有以下有益的技术效果:
本发明采用长链脂肪酸-芥酸与多胺分子间脱水、分子内脱水反应,生成长链咪唑啉化合物;苯甲酸与脂肪环胺反应生成酰胺;两者与溶剂复配,形成的缓蚀剂吸附膜对H2S/CO2腐蚀具有良好的保护作用。
本发明所提供的缓蚀剂用于高含H2S/CO2的集输管线和设备的腐蚀防护。
具体实施方式
下面结合具体的实施例对本发明做进一步的详细说明,所述是对本发明的解释而不是限定。
实施例1
按顺序在反应器中加入摩尔比为1.0∶1.1~1.5的芥酸和五乙烯六胺,在搅拌条件下升温至120-140℃开始回流,保持回流1.5~2.0h;再升温至150~170℃,回流4.0~5.0h进行酰胺化反应;继续升温至240~260℃回流3.0-4.0h进行成环反应,得到棕色粘稠液体,即为目标产物;
在反应器中加入摩尔比为1.0∶1.1~1.2的苯甲酸和吗啉,在搅拌条件下升温至140-160℃开始回流,保持回流4.0~5.0h进行酰胺化反应,得到棕色粘稠液体,即为目标产物;
将含量为:含长链咪唑啉:46重量%,苯甲酸吗啉酰胺:12重量%,甲苯:42重量%,互相混合,搅拌均匀。
实施例2
按顺序在反应器中加入摩尔比为1.0∶1.1~1.5的芥酸和三乙烯四胺,在搅拌条件下升温至120-140℃开始回流,保持回流1.5~2.0h;再升温至150~170℃,回流4.0~5.0h进行酰胺化反应;继续升温至240~260℃回流3.0-4.0h进行成环反应,得到棕色粘稠液体,即为目标产物;
在反应器中加入摩尔比为1.0∶1.1~1.2的苯甲酸和环己胺,在搅拌条件下升温至140-160℃开始回流,保持回流4.0~5.0h进行酰胺化反应,得到棕色粘稠液体,即为目标产物;
将含量为:含长链咪唑啉:42重量%,苯甲酸环己胺酰胺:15重量%,二甲苯:43重量%,互相混合,搅拌均匀。
实施例3
按顺序在反应器中加入摩尔比为1.0∶1.1~1.5的芥酸和二乙烯三胺,在搅拌条件下升温至120-140℃开始回流,保持回流1.5~2.0h;再升温至150~170℃,回流4.0~5.0h进行酰胺化反应;继续升温至240~260℃回流3.0-4.0h进行成环反应,得到棕色粘稠液体,即为目标产物;
在反应器中加入摩尔比为1.0∶1.1~1.2的苯甲酸和哌嗪,在搅拌条件下升温至140-160℃开始回流,保持回流4.0~5.0h进行酰胺化反应,得到棕色粘稠液体,即为目标产物;
将含量为:含长链咪唑啉:45重量%,苯甲酸哌嗪酰胺:13重量%,200#溶剂汽油:40重量%,互相混合,搅拌均匀。
实施例4
为了检验本发明高含H2S/CO2缓蚀剂的应用性能,进行了实验评价。评价条件为:温度60℃;转速800rpm;总压4MPa(硫化氢分压1.5MPa,二氧化碳1MPa);缓蚀剂添加浓度为200ppm;试片材质:P110;挂片周期:168小时。
表1 模拟水组成
表2 腐蚀速率数据
编号 浓度(ppm) 腐蚀速率(mm/a)
对比例4 0 0.6015
实施例1 200 0.0731
实施例2 200 0.0624
实施例3 200 0.0562

Claims (9)

1.一种长链咪唑啉类化合物,其特征在于,具有如下结构通式:
式中的n中碳原子数量为1、2、3或4。
2.一种苯甲酸脂肪环胺酰胺化合物,其特征在于,具有如下结构式:
脂肪环胺为:吗啉、环己胺、哌嗪。
3.一种高含H2S/CO2缓蚀剂,其特征在于,包括以下组分:
长链咪唑啉化合物40-55重量%;
苯甲酸脂肪环胺酰胺10-15重量%;
溶剂30-50重量%;
其中,长链咪唑啉化合物具有如下结构通式:
式中的n中碳原子数量为1、2、3或4。
苯甲酸脂肪环胺酰胺具有如下结构式:
4.根据权利要求3所述的H2S/CO2缓蚀剂,其特征在于,所述溶剂为200#溶剂汽油、柴油、甲苯、二甲苯。
5.一种制备权利要求3所述的H2S/CO2缓蚀剂的制备方法,其特征在于,包括以下步骤:
步骤1:按一定顺序在反应器中加入摩尔比为1.0∶1.1~1.5的芥酸和多胺,搅拌,在搅拌条件下升温至120-140℃开始回流,保持回流1.5~2.0h;再升温至150~170℃,回流4.0~5.0h进行酰胺化反应;继续升温至240~260℃回流3.0-4.0h进行成环反应,得到棕色粘稠液体,即为目标产物;
步骤2:在反应器中加入摩尔比为1.0∶1.1~1.5的苯甲酸和脂肪环胺,搅拌,在搅拌条件下升温至120-140℃开始回流,保持回流4.0~5.0h进行酰胺化反应,得到棕色粘稠液体,即为目标产物;
步骤3:按照质量百分比分别称取含长链咪唑啉化合物、苯甲酸脂肪环胺酰胺和溶剂,互相混合,搅拌均匀,即得到H2S/CO2缓蚀剂。
6.根据权利要求5所述的制备方法,其特征在于,所述长链羧酸为:芥酸。
7.根据权利要求5所述的制备方法,其特征在于,所述多胺为:二乙烯三胺、三乙烯四胺、四乙烯五胺、五乙烯六胺。
8.根据权利要求5所述的制备方法,其特征在于,所述脂肪环胺为:吗啉、环己胺、哌嗪。
9.根据权利要求5所述的制备方法,其特征在于,所述低分子醇溶剂为200#溶剂汽油、柴油、甲苯、二甲苯。
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