CN109810040B - 一种曼尼希碱季铵盐耐高温酸化缓蚀剂的制备方法及应用 - Google Patents
一种曼尼希碱季铵盐耐高温酸化缓蚀剂的制备方法及应用 Download PDFInfo
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- C07D209/04—Indoles; Hydrogenated indoles
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Abstract
本发明公开了一种曼尼希碱季铵盐耐高温酸化缓蚀剂的制备方法及应用，制备如下：(1)将胺类物质吲哚、二苯甲基哌啶、二苯基乙胺、二苄胺或者二异丙醇胺溶于有机溶剂中，缓慢加入醛类物质3‑(2‑噻吩基)苯甲醛或肉桂醛，放入恒温水浴锅中，60‑80℃下搅拌反应1‑3h，然后将酮类物质苄叉丙酮、二苯乙烯丙酮或1,1‑二苯基丙酮加入其中，调节PH值至3—4，反应7‑10h，冷却至室温，减压蒸馏除去溶剂，得到曼尼希碱；(2)将曼尼希碱溶于有机溶剂中，加入季铵化试剂氯甲基萘、氯化苄或者三苯氯甲烷，在70‑90℃反应14‑16h，冷却至室温，减压蒸馏。本发明简单可行，原料无毒，安全环保，制备的酸化缓蚀剂对油气井碳钢的酸腐蚀有明显的抑制作用。
Description
技术领域
本发明涉及缓蚀剂材料领域中一种曼尼希碱季铵盐耐高温酸化缓蚀剂的制备方法及其应用。
背景技术
在油气田增产改造过程中，压裂酸化已经成为主流的油气田增产改造方式。在酸压过程中，酸液的注入可以很大程度上解除油气井筒以及地层堵塞，提高基质渗透率，从而提高油气采收率。但是酸化施工也会给油田带来诸多问题，在酸化施工过程中，盐酸等酸液的注入会造成油气井管柱、施工管线和金属设备的腐蚀，严重时可能导致井下管材突发性破裂事故，管线穿孔，存在严重安全隐患，同时被酸液溶蚀的金属铁离子又可能对地层造成伤害。为了防止酸液对油管、套管以及施工设备的腐蚀，在酸液中添加缓蚀剂是必不可少且最为常用、有效的防腐措施。目前大部分市售缓蚀剂存在高温下易结焦、分层、溶解分散性能不稳定、原料有毒、易燃易爆、污染较大等缺点。
“一种炔醇类曼尼希碱缓蚀剂及其合成方法与应用”(201610436640.6),通过对缓蚀剂关键合成方法的原料、配比、工艺步骤等进行改进，制备得到的缓蚀剂无毒、环境友好，缓蚀效果好、且可耐高温，尤其适用于作为盐酸缓蚀剂在酸洗碳钢中使用。但所用原料丙炔醇为剧毒物质，易燃易爆，腐蚀性强。
“一种高水溶性、耐高温曼尼希碱缓蚀剂中间体及其制备方法”(201410086970.8)，不适用任何溶剂，只在碱金属醇盐催化剂存在下，醛、酮、胺缩合物与亲水基表面活性剂反应得到高水溶性、耐高温曼尼希碱缓蚀剂中间体。由于不使用任何溶剂，解决了使用溶剂带来的产品含量低或难于回收利用的缺点，解决了其他缓蚀剂水溶性差、在高温下易分解的缺点，减少了有毒物质对生产带来的不便，且能抑制高温盐酸酸化腐蚀。但所用原料碱金属醇盐如甲醇钠等对氧气敏感，易燃易爆，具有强腐蚀性。
“一种三氮唑改性曼尼希碱化合物及其制备方法”(201610073911.6)，通过Mannich反应、酮的环氧化反应、醚的开环反应制得三氮唑改性曼尼希碱缓蚀剂，由于曼尼希碱是以N和O原子为活性中心的缓蚀剂分子，其中的孤对电子可以以配位键的形式与金属离子络合形成聚合物，且能与金属原子结合，以吸附膜的形式覆盖在设备表面起到缓蚀作用。但是原料氢氧化锂等为高毒物质，对制备工艺要求高，不利于安全生产和环境保护。
因此，研制一种配方简单、合成条件温和、无毒安全、绿色环保，且能满足目前油气井酸化施工苛刻要求的新型耐高温酸化缓蚀剂具有重要的意义。
发明内容
本发明的目的在于提供一种曼尼希碱季铵盐耐高温酸化缓蚀剂的制备方法及其应用，该制备方法简单可行，制得的缓蚀剂在高温下具有良好的缓蚀性能，而且原料无毒，安全环保，使用该季铵盐缓蚀剂作为油气井酸化缓蚀剂时，在盐酸溶液中具有良好的溶解性，对油气井碳钢的酸腐蚀有明显的抑制作用。
为实现上述技术目的，本发明提供以下技术方案。
一种曼尼希碱季铵盐耐高温酸化缓蚀剂的制备方法，依次包括以下步骤：
(1)将胺类物质吲哚、二苯甲基哌啶、二苯基乙胺、二苄胺或者二异丙醇胺溶于有机溶剂中，缓慢加入醛类物质3-(2-噻吩基)苯甲醛或肉桂醛，放入恒温水浴锅中，60-80℃下搅拌反应1-3h，然后将酮类物质苄叉丙酮、二苯乙烯丙酮或1,1-二苯基丙酮以一定比例加入其中，使用盐酸溶液调节反应体系PH值至3—4，反应7-10h，冷却至室温后，减压蒸馏除去溶剂，得到曼尼希碱；
(2)将曼尼希碱溶于有机溶剂中，按一定比例加入季铵化试剂氯甲基萘、氯化苄或者三苯氯甲烷，在70-90℃反应14-16h，冷却至室温后，减压蒸馏制得曼尼希碱季铵盐耐高温酸化缓蚀剂。
进一步地，步骤(1)中胺类物质、醛类物质、酮类物质的摩尔比为1:1:1-1:1:2。
进一步地，所述有机溶剂为乙醇或乙腈。
进一步地，步骤(2)中曼尼希碱与季铵化试剂的摩尔比为1:1-1:2。
所述曼尼希碱季铵盐耐高温酸化缓蚀剂的应用，是指将其作为油气井酸化缓蚀剂，由于其在酸液中具有良好的分散性和溶解性，对油气井碳钢的酸腐蚀有明显的抑制作用。
该酸化缓蚀剂的反应历程如下：
本发明制备方法简单，反应机理为：醛、酮等具有活泼α-H的化合物与醛、胺在乙醇等溶液中回流，使酮的α-H被胺甲基取代，反应也成为胺甲基化反应。首先羰基质子化，胺对羰基发生亲核加成，去质子，氮上的电子转移，水离去，可以得到一个亚胺离子中间体，亚胺离子作为亲电试剂，进攻含活泼氢化合物的烯醇型结构，失去质子，便得到产物曼尼希碱。本发明制备的曼尼希碱季铵盐中含有羰基、胺基等极性基团，其中的氮、氧原子都含有未共用的电子，可进入铁原子的空轨道形成配位键，使缓蚀剂分子吸附在金属表面。为使缓蚀剂在金属表面吸附更加牢固，加入π键吸附即缓蚀剂分子中含有π键或大π键，其中的电子进入金属原子的空轨道，形成π键吸附紧紧吸附在铁上，抑制其腐蚀；此外，该缓蚀剂分子中的多个羟基可以大大地提高缓蚀剂的分散性和在酸液中的溶解性。
具体实施方式
下面通过实施例进一步说明本发明。
实施例1
一种曼尼希碱季铵盐耐高温酸化缓蚀剂的制备方法，包括以下步骤：
(1)将1.97g二苄胺加入到250mL三颈烧瓶中，然后缓慢加入1.88g 3-(2-噻吩基)苯甲醛，同时加入70mL无水乙醇作为溶剂并搅拌均匀，并将反应体系放入恒温水浴锅中，70℃下搅拌反应1h；
(2)向烧瓶中加入1.46g苄叉丙酮，使用盐酸溶液调节反应体系PH值至4，反应8h，冷却至室温后，减压蒸馏除去溶剂，得到曼尼希碱；
(3)将上述曼尼希碱产物5.13g加入到250mL三颈烧瓶中，加入110mL无水乙醇作为溶剂并搅拌均匀，缓慢加入1.27g氯化苄搅拌均匀，在80℃下搅拌反应12h，冷却至室温后，减压蒸馏制得曼尼希碱季铵盐缓蚀剂。
本实施例所用原料苄叉丙酮、二苄胺上的氮原子具有较高的活性，在上述反应条件下，所得季铵盐酸化缓蚀剂具有良好的缓蚀性能。
上述制备方法的具体反应方程式如下：
实施例2
一种曼尼希碱季铵盐耐高温酸化缓蚀剂的制备方法，包括以下步骤：
(1)将2.51g二苯甲基哌啶加入到250mL三颈烧瓶中，然后缓慢加入1.32g肉桂醛，同时加入100mL无水乙醇作为溶剂并搅拌均匀，并将反应体系放入恒温水浴锅中，70℃下搅拌反应1h；
(2)向烧瓶中加入3.12g二苯乙烯丙酮，使用盐酸溶液调节反应体系PH值至4，反应8h，冷却至室温后，减压蒸馏除去溶剂，得到曼尼希碱；
(3)将上述曼尼希碱产物6.77g加入到250mL三颈烧瓶中，加入120mL乙腈作为溶剂并搅拌均匀，缓慢加入1.76g氯甲基萘搅拌均匀，在85℃下搅拌反应12h，冷却至室温后，减压蒸馏制得曼尼希碱季铵盐缓蚀剂。
实施例3
一种曼尼希碱季铵盐耐高温酸化缓蚀剂的制备方法，包括以下步骤：
(1)将1.17g吲哚加入到250mL三颈烧瓶中，然后缓慢加入1.32g肉桂醛，同时加入90mL无水乙醇作为溶剂并搅拌均匀，并将反应体系放入恒温水浴锅中，80℃下搅拌反应1h；
(2)向烧瓶中加入1.46g苄叉丙酮，使用盐酸溶液调节反应体系PH值至3，反应9h，冷却至室温后，减压蒸馏除去溶剂，得到曼尼希碱；
(3)将上述曼尼希碱产物3.77g加入到250mL三颈烧瓶中，加入110mL无水乙醇作为溶剂并搅拌均匀，缓慢加入2.78g三苯氯甲烷搅拌均匀，在80℃下搅拌反应13h，冷却至室温后，减压蒸馏制得曼尼希碱季铵盐缓蚀剂。
实施例4
一种曼尼希碱季铵盐耐高温酸化缓蚀剂的制备方法，包括以下步骤：
(1)将1.33g二异丙醇胺加入到250mL三颈烧瓶中，然后缓慢加入1.88g3-(2-噻吩基)苯甲醛，同时加入120mL乙腈作为溶剂并搅拌均匀，并将反应体系放入恒温水浴锅中，80℃下搅拌反应1.5h；
(2)向烧瓶中加入3.12g二苯乙烯丙酮，使用盐酸溶液调节反应体系PH值至4，反应10h，冷却至室温后，减压蒸馏除去溶剂，得到曼尼希碱；
(3)将上述曼尼希碱产物6.33g加入到250mL三颈烧瓶中，加入130mL无水乙醇作为溶剂并搅拌均匀，缓慢加入1.76g氯甲基萘搅拌均匀，在80℃下搅拌反应14h，冷却至室温后，减压蒸馏制得曼尼希碱季铵盐缓蚀剂。
性能测试1缓蚀剂的水溶性测定
测定实施例1-4制得的缓蚀剂的水溶性以及在90℃下，添加铁离子稳定剂、粘土稳定剂、助排剂等体系的配伍性，具体过程为：分别称取缓蚀剂各0.1g，分别溶于200mL20％的盐酸溶液中，搅拌，观察其溶解情况；配制添加铁离子稳定剂柠檬酸、粘土稳定剂氯化钾、助排剂OP-10或氟碳表面活性剂等的20％的盐酸酸液体系，分别称取缓蚀剂各0.1g，加入其中，观察其配伍性，结果见表1。
表1不同缓蚀剂的水溶性及配伍性测试
| 缓蚀剂 | 水溶性 | 配伍性 |
| 实施例1 | 易溶的红褐色透明液体 | 均一透明，无分层 |
| 实施例2 | 易溶的红褐色透明液体 | 均一透明，无分层 |
| 实施例3 | 易溶的红褐色透明液体 | 均一透明，无分层 |
| 实施例4 | 易溶的红褐色透明液体 | 均一透明，无分层 |
由表1可知，本发明制得的缓蚀剂水溶性优异，且在高温盐酸体系中与各种添加剂配伍性良好，体系均一透明，无分层现象。
性能测试2缓蚀剂的缓蚀性能测定
以20％盐酸作为为腐蚀介质，采用P110碳钢，于90℃通过4h腐蚀挂片失重实验测定实施例1-4的缓蚀性能，缓蚀剂用量均为1000ppm，结果见表2。
表2各缓蚀剂的缓蚀性能测定
由表2可知，通过本发明方法制得的缓蚀剂具有良好的缓蚀效果。
综上所述，本发明制备工艺简单可行，制得的缓蚀剂为离子型，在酸溶液中具有良好的水溶性，在90℃高温条件下，对油气井碳钢的腐蚀有明显的抑制作用，且挂片清洗后表面平整，无明显点蚀，说明本发明制得的缓蚀剂具有耐酸耐高温特性。
Claims (5)
1.一种曼尼希碱季铵盐耐高温酸化缓蚀剂的制备方法，依次包括以下步骤：
（1）将胺类物质吲哚、二苯甲基哌啶、二苯基乙胺或者二苄胺溶于有机溶剂中，缓慢加入醛类物质3-(2-噻吩基)苯甲醛，放入恒温水浴锅中，60-80℃下搅拌反应1-3h，然后将酮类物质苄叉丙酮或者二苯乙烯丙酮加入其中，使用盐酸溶液调节反应体系PH值至3—4，反应7-10h，冷却至室温后，减压蒸馏除去溶剂，得到曼尼希碱；
（2）将曼尼希碱溶于有机溶剂中，加入季铵化试剂氯甲基萘、氯化苄或者三苯氯甲烷，在70-90℃反应14-16h，冷却至室温后，减压蒸馏制得曼尼希碱季铵盐耐高温酸化缓蚀剂。
2.如权利要求1所述的一种曼尼希碱季铵盐耐高温酸化缓蚀剂的制备方法，其特征在于，所述步骤（1）中胺类物质、醛类物质、酮类物质的摩尔比为1:1:1-1:1:2。
3.如权利要求1所述的一种曼尼希碱季铵盐耐高温酸化缓蚀剂的制备方法，其特征在于，所述有机溶剂为乙醇或乙腈。
4.如权利要求1所述的一种曼尼希碱季铵盐耐高温酸化缓蚀剂的制备方法，其特征在于，所述步骤（2）中曼尼希碱与季铵化试剂的摩尔比为1:1-1:2。
5.如权利要求1、2、3或4所述的一种曼尼希碱季铵盐耐高温酸化缓蚀剂的应用，是指将其作为油气井酸化缓蚀剂，对油气井碳钢的酸腐蚀有明显的抑制作用。
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