CN103571449B - 一种长效油井用粘土稳定剂及其制备和应用 - Google Patents
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Abstract
本发明涉及一种长效油井用粘土稳定剂及其制备和应用；将环氧氯丙烷和短链多电荷阳离子聚季铵盐按摩尔比为1～2：1加入反应器，同时加入5‑15%质量的溶剂和1‑5%质量的催化剂，搅拌升温至30‑100℃，反应2‑6小时，制得无色透明液体即为长效油井用粘土稳定剂；本粘土稳定剂相对分子量小，分子尺寸范围小，可以防止粘土稳定剂堵塞致密储层微孔喉，减轻对低渗透油层渗透率的伤害，本粘土稳定剂中主剂含有多个阳离子点，进一步提升了粘土稳定剂分子与储层的结合点数目，提高了防膨性能，制备工艺简单，材料易得，可以赋予压裂液体系长效的粘土稳定性能。
Description
技术领域
本发明涉及石油开采领域，特别涉及一种适合致密油储层油井压裂增产工艺所使用的长效粘土稳定剂及其制备和应用。
背景技术
我国致密油气资源丰富，主要分布在鄂尔多斯、四川、松辽、渤海湾、准噶尔等盆地，勘探评价表明仅致密油总资源量达110～135亿吨。随着勘探开发技术的不断进步，特别是水平井体积压裂技术的突破，致密油开发已在长庆油田、大庆油田及吐哈等油田进行先导性试验。
致密油储层中粘土矿物成分复杂，这些粘土矿物多由硅氧四面体和铝氧八面体组成，层间表面均为氧化层，联结力弱。当与水接触时，粘土矿物中可交换的Si4+、Al3+阳离子在水中分别被Al3+和Fe2+、Mg2+阳离子取代，由此产生了过剩的负电荷,使晶层之间相互排斥，导致粘土膨胀、分散，并在水流的冲力下发生运移。目前致密油储层改造主要为大规模、大排量、低砂比、低粘携砂，在这种大规模的水力压裂施工过程中，大量水溶液与粘土接触，使粘土发生膨胀、分散及运移，进而降低储层渗透率或堵塞储层通道。因此有必要使用粘土稳定剂来提高作业液体的防膨率，降低粘土分散运移，提高储层渗透率。
常用的粘土稳定剂为带多个电荷的阳离子、季铵盐表面活性剂、聚胺和聚季铵等。以上粘土稳定剂均可抑制粘土膨胀和运移，但存在一些问题：多电荷阳离子在压裂施工中需要合适的前置液和后置液，容易引起堵塞；季铵盐表面活性剂会使硅酸盐变为油润湿，从而降低岩石中烃的相对渗透率；聚胺类粘土稳定剂的有效期短，费用高；聚季铵类相对分子量大会加重对低渗透油层渗透率的伤害。
发明内容
本发明的目的是提供一种具有长效性、吸附能力强、相对分子质量小、对地层适应性强的长效油井用粘土稳定剂及其制备和应用，防止粘土矿物水化膨胀、分散运移，降低对低渗透油层渗透率的伤害。
本发明所述的长效油井用粘土稳定剂的制备方法：
采用环氧氯丙烷和短链多电荷阳离子聚季铵盐反应，同时加入5-15%重量的溶剂和1-5%重量的引发剂，搅拌升温至30-100℃，反应2-6小时，制得无色透明液体即为长效油井用粘土稳定剂，氧氯丙烷和短链多电荷阳离子聚季铵盐摩尔比为1～2：1。
所述的短链多电荷阳离子聚季铵盐为白色粉末或颗粒，其分子量为2-10万，阳离子度为10%-20%。
所述的溶剂为甲醇、乙醇、丙醇、异丙醇中的一种。
所述的引发剂为亚硫酸氢钾、过硫酸钠、硫酸铁铵，亚硫酸钠中的一种。
本发明的有益效果是：
1.本发明的长效油井用粘土稳定剂相对分子量小，分子尺寸范围分布小，可以防止粘土稳定剂堵塞致密储层微孔喉，减轻对低渗透油层渗透率的伤害。
2.本发明的粘土稳定剂中主剂含有多个阳离子点，进一步提升了粘土稳定剂分子与储层的结合点数目，提高了防膨性能。
3.本发明的粘土稳定剂可通过多个附着点强烈吸附在粘土表面，不易分解，粘土稳定剂的有效期长。
4.本发明的粘土稳定剂与压裂液配伍性能良好，在压裂基液中加入体积浓度为0.5%的粘土稳定剂无沉淀生成。
5.本发明使用的原料易得，制备过程简单。
具体实施方式
下面通过具体实施例对本发明做详细地说明。
实施例1：
将装有磁力搅拌、温度计的三口烧瓶置于磁力搅拌器控温电热套上，向三口烧瓶中加入摩尔比为2：1的环氧氯丙烷和短链多电荷阳离子聚季铵盐，同时加入10%重量的乙醇和2%重量的亚硫酸钠，搅拌升温至70℃，持续搅拌5小时，得到无色透明液体即为长效油井用粘土稳定剂。
实施例2：
将装有磁力搅拌、温度计的三口烧瓶置于磁力搅拌器控温电热套上，向三口烧瓶中加入摩尔比为1.8：1的环氧氯丙烷和短链多电荷阳离子聚季铵盐，同时加入10%重量的甲醇和2%重量的亚硫酸氢钾，搅拌升温至80℃，持续搅拌4小时，得到无色透明液体即为长效油井用粘土稳定剂。
实施例3：
将装有磁力搅拌、温度计的三口烧瓶置于磁力搅拌器控温电热套上，向三口烧瓶中加入摩尔比为1.0：1的环氧氯丙烷和短链多电荷阳离子聚季铵盐，同时加入10%重量的异丙醇和2%重量的亚硫酸钠，搅拌升温至70℃，持续搅拌6小时，得到无色透明液体即为长效油井用粘土稳定剂。
实施例4：
将装有磁力搅拌、温度计的三口烧瓶置于磁力搅拌器控温电热套上，向三口烧瓶中加入摩尔比为1.2：1的环氧氯丙烷和短链多电荷阳离子聚季铵盐，同时加入10%重量的乙醇和2%重量的过硫酸钠，搅拌升温至80℃，持续搅拌6小时，得到无色透明液体即为长效油井用粘土稳定剂。
Claims (3)
1.一种长效油井用粘土稳定剂的制备方法，其特征在于：
将环氧氯丙烷和短链多电荷阳离子聚季铵盐按摩尔比为1～2：1加入反应器，同时加入5-15％重量的溶剂和1-5％重量的引发剂，搅拌升温至30-100℃，反应2-6小时，制得无色透明液体即为长效油井用粘土稳定剂；
所述的短链多电荷阳离子聚季铵盐为白色粉末或颗粒，其分子量为2-10万，阳离子度为10％-20％；
所述的溶剂为甲醇、乙醇、丙醇、异丙醇中的一种。
2.一种长效油井用粘土稳定剂，其特征在于：它是由权利要求1所述的长效油井用粘土稳定剂的制备方法制备的。
3.一种权利要求2所述的长效油井用粘土稳定剂的应用，其特征在于：用作油井用粘土稳定剂，使用时在压裂基液中加入体积浓度为0.5％的粘土稳定剂即可。
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| CN108329902A (zh) * | 2018-01-23 | 2018-07-27 | 中国石油天然气股份有限公司 | 一种油田出水配制压裂液用的耐盐粘土稳定剂及其制备方法 |
| CN111471440B (zh) * | 2020-05-28 | 2022-03-29 | 陕西科技大学 | 一种多阳离子防膨剂及其制备方法和应用 |
| CN112251213B (zh) * | 2020-10-15 | 2022-09-23 | 中国地质科学院水文地质环境地质研究所 | 地热系统中的复合化学刺激剂 |
| CN114989801A (zh) * | 2022-06-15 | 2022-09-02 | 胜利油田华滨化工有限责任公司 | 一种小阳离子粘土稳定剂及其制备方法 |
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| CN102702424A (zh) * | 2012-05-25 | 2012-10-03 | 西南石油大学 | 两性离子聚合物、其制备方法及在盐酸基压裂液中的应用 |
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| CN102702424A (zh) * | 2012-05-25 | 2012-10-03 | 西南石油大学 | 两性离子聚合物、其制备方法及在盐酸基压裂液中的应用 |
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| 耐冲刷、长效聚季铵型阳离子粘土稳定剂的研制;谢长宇;《石油化工应用》;20080630;第27卷(第3期);第1.2节 * |
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