CN108485633A - 一种新型网状聚季胺油气井页岩防膨剂的制备方法 - Google Patents
一种新型网状聚季胺油气井页岩防膨剂的制备方法 Download PDFInfo
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Abstract
本发明以1，4，7，10‑四氮杂环十三烷为起始原料，首先将其与两分子的环氧乙烷反应生成网状分子，然后再与四分子的碘甲烷反应，生成含季氨离子的网状聚合物分子，本发明提供了一种制备抑制油气井页岩粘土膨胀的高效防膨剂的新途径。
Description
技术领域
本发明属原油开采助剂领域，特别是涉及一种由1，4，7，10-四氮杂环十三烷、碘甲烷和环氧乙烷为原料的油气井页岩防膨剂的制备方法。
背景技术
多数油气储层中含有一定量的粘土矿物，如高岭石、蒙脱石、伊利石和绿泥石等，这些粘土矿物多由硅氧四面体和铝氧八面体组成层状结构，其中蒙脱石由两层硅氧四面体夹一层铝氧八面体组成，层间表面均为氧层，层与层之间作用力较弱，当与水分子接触时，水分子可进入晶层之间，使晶层表面的阳离子在水中解离扩散，形成扩散双电层，表面带电，晶层之间相互排斥，产生膨胀，引起地层渗透率大大降低。对于高岭石、伊利石和绿泥石而言，水虽然引不起其膨胀，但随着蒙脱土的膨胀，油气层被破坏，在地层流体冲刷下，这些粘土可分散成片状微粒而运移，进入地层孔隙，堵塞喉道，也会降低地层渗透率。尤其低渗透油气藏，因粘土膨胀造成的渗透率下降严重影响着油气生产，因此阻止粘土膨胀是油气生产中必须采取的措施，而粘土防膨剂的使用是防治粘土膨胀的主要手段。目前粘土防膨剂的种类众多，包括无机化合物、有机化合物和聚合物，其中最具代表性的是聚季胺。目前所使用的聚季胺粘土防膨剂多为线型高分子，即使通过交联可以得到一定程度的网状结构，但对于油气井的页岩防膨效果十分不理想。因此，开发一种网状聚季胺防膨剂以解决页岩防膨是油气井正常生产所急需的。
防止粘土吸水膨胀的关键是阻止水分子插入粘土层之间，而粘土表面带负电荷，具有网状结构的聚季胺分子因带有多个正电荷能够在页岩表面强力吸附，在页岩表面生成一面网，从而阻止水分子插入粘土层之间。
本发明以1，4，7，10-四氮杂环十三烷、碘甲烷和环氧乙烷为原料制备了一种网状分子结构的聚季胺，能够通过较强的静电相互作用吸附于油气井页岩表面，在页岩表面铺就了一张网，阻止水分子对页岩中的层状粘土的插入，进而阻止了粘土的吸水膨胀。
发明内容
本发明以1，4，7，10-四氮杂环十三烷为起始原料，首先将其与两分子的环氧乙烷反应生成网状分子，然后再与四分子的碘甲烷反应，生成含季氨离子的网状聚合物分子，本发明提供了一种制备抑制油气井页岩膨胀的高效防膨剂的新途径。
具体实施方式
实施例1
将0.1mol 1，4，7，10-四氮杂环十三烷、5.00g氢氧化钠和100ml蒸馏水加入250ml三口反应瓶中，搅拌溶解，水浴升温至85℃，通入氮气10分钟，氮气保护下缓慢通入0.2mol环氧乙烷，控制温度不超过90℃，需要3小时，通完环氧乙烷后继续于85℃反应2小时，然后再缓慢滴加0.4mol碘甲烷，需要3小时，滴完后继续保温反应1小时，冷却至室温，生成黄色均匀液体。
实施例2
将油气井页岩样品粉碎，过120目筛，于110℃条件下真空烘干4h，冷却至室温，放置于干燥器内备用；准确称取5.00g粉粹的页岩样装入压模内，制作岩样，用HTP-3A型高温高压泥页岩膨胀仪测定页岩的膨胀率和实施例1样品对页岩的防膨率，结果见表1至表4。
表1 不同型号页岩的膨胀率
表2 不同浓度实施例1样品溶液对1#页岩的防膨率
表3 不同浓度实施例1样品溶液对2#页岩的防膨率
表4 不同浓度实施例1样品溶液对3#页岩的防膨率
Claims (1)
1.一种由1，4，7，10-四氮杂环十三烷、碘甲烷和环氧乙烷为原料的油气井页岩防膨剂的制备方法，包括下列步骤：
(1)将0.1mol1，4，7，10-四氮杂环十三烷、5.00g氢氧化钠和100ml蒸馏水加入250ml三口反应瓶中，搅拌溶解，水浴升温至85℃，通入氮气10分钟，氮气保护下缓慢通入0.2mol环氧乙烷，控制温度不超过90℃，需要3小时，通完环氧乙烷后继续于85℃反应2小时，然后再缓慢滴加0.4mol碘甲烷，需要3小时，滴完后继续保温反应1小时，冷却至室温，生成黄色均匀液体。
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101263211A (zh) * | 2005-07-13 | 2008-09-10 | 哈利伯顿能源服务公司 | 作为井漏控制剂材料的水溶胀性聚合物 |
| CN101316615A (zh) * | 2005-11-29 | 2008-12-03 | 马林克罗特公司 | 双官能金属螯合共轭物 |
| US20140243557A1 (en) * | 2013-02-28 | 2014-08-28 | Basf Se | Polyamines and process for preparation thereof |
| WO2015128021A1 (de) * | 2014-02-26 | 2015-09-03 | Basf Se | Verfahren zur herstellung von polyaminen |
| JP2016514178A (ja) * | 2013-02-28 | 2016-05-19 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | ポリアミン及びその製造方法 |
| CN107312507A (zh) * | 2016-04-27 | 2017-11-03 | 中国石油化工股份有限公司 | 一种黏土稳定剂及其应用 |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101263211A (zh) * | 2005-07-13 | 2008-09-10 | 哈利伯顿能源服务公司 | 作为井漏控制剂材料的水溶胀性聚合物 |
| CN101316615A (zh) * | 2005-11-29 | 2008-12-03 | 马林克罗特公司 | 双官能金属螯合共轭物 |
| US20140243557A1 (en) * | 2013-02-28 | 2014-08-28 | Basf Se | Polyamines and process for preparation thereof |
| JP2016514178A (ja) * | 2013-02-28 | 2016-05-19 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | ポリアミン及びその製造方法 |
| WO2015128021A1 (de) * | 2014-02-26 | 2015-09-03 | Basf Se | Verfahren zur herstellung von polyaminen |
| CN107312507A (zh) * | 2016-04-27 | 2017-11-03 | 中国石油化工股份有限公司 | 一种黏土稳定剂及其应用 |
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