CN114716985A - 一种小阳离子低聚防膨季铵盐粘土稳定剂及其制备方法 - Google Patents
一种小阳离子低聚防膨季铵盐粘土稳定剂及其制备方法 Download PDFInfo
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- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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Abstract
本发明公开了一种小阳离子低聚防膨季铵盐粘土稳定剂及其制备方法,小阳离子低聚防膨季铵盐粘土稳定剂由质量比为100:23‑58的多羟基季铵盐水溶液和环氧丙烷组成;其中,所述多羟基季铵盐水溶液包括以下重量份的组分:428‑858份的水、2‑122份的苛性碱、60‑150份的低碳羟基胺和80‑300份的短链氯醇,本发明的目的提供一种小阳离子低聚防膨季铵盐粘土稳定剂及其制备方法,得到的小阳离子低聚防膨季铵盐粘土稳定剂具有阻止粘土吸水膨胀、对粘土颗粒进行架桥和束缚、阻止其运移的效果。
Description
技术领域
本发明属于油气田开采防止粘土膨胀和运移技术领域,具体涉及一种小阳离子低聚防膨季铵盐粘土稳定剂及其制备方法。
背景技术
几乎所有的油气田地层都不同程度地含有粘土矿物,其种类主要有蒙脱石、高岭石、伊利石、绿泥石、伊蒙混层、绿蒙混层六大类。这些粘土在钻井、压裂、酸化、注水等作业过程中遇到水就会产生膨胀、分散和运移,从而对地层孔隙造成堵塞和伤害,引起地层的油气产量降低。为了预防和减少这类事件的发生,就需要在上述作业施工中使用防止粘土膨胀、分散和运移的粘土稳定剂。因此,性能优良、地层适应性好的粘土稳定剂对油气层保护及增产具有重要意义。
目前所用的粘土稳定剂主要有无机盐类、无机多核聚合物、阳离子表面活性剂、阳离子季铵盐、阳离子季铵盐聚合物几大类。
少量的阳离子季铵盐聚合物在水中解离产生高正电价的阳离子,可以同时与多个粘土颗粒形成多点吸附,从而在粘土颗粒之间形成网桥结构,有效防止粘土颗粒的膨胀与运移,且耐冲刷、长效性好,因而近年来受到广泛应用。
但针对低渗透油气层,阳离子季铵盐聚合物在应用过程中存在两方面的问题:(1)如果季铵周围部分的分子存在亲油性的结构、如长链或者环状有机结构,聚合物在地层表面吸附后会造成岩石表面亲油、造成地层伤害,降低渗透率、增加原油的流动阻力;(2)如果这类聚合物的分子量过大,反而会堵塞低渗透储层孔喉,降低储层渗透率。因此,以短链和直链型小阳离子季铵盐为基础而合成的低分子量聚合物,以适应低渗透油层的应用,是近几年国内外开发的重点。
中国专利公布号CN112745233A“一种适用于低渗透油藏的小分子粘土稳定剂及其制备方法”,所述方法是先将N ,N-二(2-氯乙基)-1-丙胺与环氧氯丙烷发生接枝反应,接枝数为1-5,制得分子量为222-806的小分子季铵盐型阳离子聚合物,然后再将其与无机盐混合而成。其中围绕季铵周围部分结构为两个氯乙基,这种有机氯的结构有改变岩石表面至亲油的风险。
中国专利公布号CN109439292A“黏土稳定剂”,所述方法是先合成一种小阳离子聚合物,聚合物与十二烷基二甲基苄基氯化铵、羟基铝进行复配得到的粘土稳定剂。其中的小阳离子聚合物是将聚醚多元醇、氢氧化钾溶液、环氧氯丙烷、多乙烯多胺、冰乙酸进行反应而得到。 其中围绕季铵周围部分结构为含12个碳链的多乙烯多胺,结构链较长,有改变岩石表面至亲油的风险。
发明内容
本发明主要目的是,针对现有技术的不足,提供一种小阳离子低聚防膨季铵盐粘土稳定剂及其制备方法,所得小阳离子低聚防膨季铵盐粘土稳定剂具有阻止粘土吸水膨胀、对粘土颗粒进行架桥和束缚、阻止其运移的效果。
为实现上述目的,本发明采用以下技术方案:
本发明的目的之一,提供一种小阳离子低聚防膨季铵盐粘土稳定剂,由质量比为100:23-58的多羟基季铵盐水溶液和环氧丙烷组成;
其中,所述多羟基季铵盐水溶液包括以下重量份的组分:428-858份的水、2-122份的苛性碱、60-150份的低碳羟基胺和80-300份的短链氯醇。
优选的是,所述的一种小阳离子低聚防膨季铵盐粘土稳定剂中,所述水为纯净水或软化水。
优选的是,所述的一种小阳离子低聚防膨季铵盐粘土稳定剂中,所述苛性碱为氢氧化钾或氢氧化钠。
优选的是,所述的一种小阳离子低聚防膨季铵盐粘土稳定剂中,所述低碳羟基胺选自一乙醇胺、二乙醇胺或三乙醇胺。
优选的是,所述的一种小阳离子低聚防膨季铵盐粘土稳定剂中,所述短链氯醇为氯乙醇或氯丙醇。
优选的是,所述的一种小阳离子低聚防膨季铵盐粘土稳定剂中,所述多羟基季铵盐水溶液1000份和环氧丙烷348份;所述多羟基季铵盐水溶液由水、氢氧化钠、三乙醇胺和氯乙醇按质量比768.5∶2∶149∶80.5制成。
本发明还提供一种上述的小阳离子低聚防膨季铵盐粘土稳定剂的制备方法,包括以下步骤:
(1)按照配方份,在反应器中用水将苛性碱溶解,加入低碳羟基胺搅拌15分钟以上至混合均匀,然后在搅拌的条件下滴加短链氯醇,滴加过程中控制温度在40℃-60℃之间,滴加完成后再在60℃-80℃进行反应,生成物为多羟基季铵盐水溶液;
(2)反应完成后,将反应器抽真空至-0.2MPa至-0.3MPa,再充氮气至0.2MPa至0.3MPa,将反应器中的空气利用氮气进行置换,然后将反应器中多羟基季铵盐水溶液升温至60℃后,滴加环氧丙烷,滴加过程中保持反应温度在60℃-90℃,环氧丙烷加完后再在60℃-90℃进行反应,即得到小阳离子低聚防膨季铵盐粘土稳定剂。
优选的是,所述的制备方法中,在步骤(1)中,反应时间为1-3小时。
优选的是,所述的制备方法中,在步骤(2)中,反应时间为0.5-2.0小时。
本发明制备的小阳离子低聚防膨季铵盐粘土稳定剂是一种含有多个亲水性羟基的有机多价阳离子小分子聚合物,一方面通过多价阳离子在粘土晶层的吸附阻止粘土吸水膨胀,另一方面通过一定长度的分子链对周围的粘土颗粒进行架桥和束缚、阻止其运移,具有适用范围广,用法简单,用量少,抗酸液、盐液、碱液和耐油水的冲刷,长久有效。由于产品为多羟基小分子量聚合物,不会对地层微孔孔喉形成堵塞、亲水性好,适合于低渗透、特低渗透油气层所用的活性水、射孔液、压裂液、钻井液及酸化液等入井工作液体。
本发明的其它优点、目标和特征将部分通过下面的说明体现,部分还将通过对本发明的研究和实践而为本领域的技术人员所理解。
附图说明
图1为小阳离子低聚防膨季铵盐粘土稳定剂的制备方法工艺流程图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
本发明实施例提供一种小阳离子低聚防膨季铵盐粘土稳定剂及其制备方法,如图1所示,该方法通过以下步骤实现:
步骤一:多羟基季铵盐的制备。
其重量份配比为:水428~858份、苛性碱2~122份、低碳羟基胺60~150份、短链氯醇80~300份;
具体地,所述水为纯净水或软化水。
所述苛性碱为氢氧化钾或氢氧化钠。
所述低碳羟基胺选自一乙醇胺、二乙醇胺或三乙醇胺。
所述短链氯醇为氯乙醇或氯丙醇。
按照所述配比,在反应器中用水将苛性碱溶解,加入低碳羟基胺搅拌15分钟以上至混合均匀,然后在搅拌的条件下滴加短链氯醇,滴加过程中控制温度在40℃-60℃之间,滴加完成后再在60℃-80℃下反应1-3小时,生成物为多羟基季铵盐水溶液。
特别地,当短链氯醇与叔胺类低碳羟基胺反应时,碱只做为催化剂,反应式如下:
式中:n=2,3
而当短链氯醇与与伯胺、仲伯胺类低碳羟基胺反应时,碱既是催化剂,又是中和剂。其反应式如下:
式中:m=1-2;n=2,3;
步骤二:聚合反应。
其重量份配比为:多羟基季铵盐水溶液1000份、环氧丙烷230~580份;
在完成第一步化学反应后,按照所述配比,将反应器中的空气利用氮气进行置换,置换次数不低于三次。然后将反应器中多羟基季铵盐水溶液升温至60℃后,滴加环氧丙烷,滴加过程中保持反应温度在60℃-90℃。环氧丙烷加完后再在60℃-90℃保温1小时,即得到小阳离子低聚防膨季铵盐粘土稳定剂。
以二乙醇胺生成的季铵盐为例,所述的聚合反应化学反应式如下:
式中:1≤n≤4
下面,提供本发明的具体实施案,但并不限于本实施例:
实施例1:
于带搅拌器和加热装置的密闭反应器中加入768.5份水和2份氢氧化钠,搅拌,使氢氧化钠完全溶解,加入149份三乙醇胺,搅拌15分钟以上至混合均匀,然后在搅拌的条件下滴加80.5份氯乙醇,滴加过程中控制温度在40℃-60℃之间,滴加完成后再在60℃-80℃下反应2小时,生成物为多羟基季铵盐水溶液。
对反应器抽真空至-0.2MPa至-0.3MPa之间,再充氮气至0.2MPa至0.3MPa之间,反复进行三次。再抽真空至-0.2MPa至-0.3MPa之间,升温至60℃后,分次加入环氧丙烷348份。每次加入环氧丙烷时反应器内压力不高于0.3MPa,待反应器内压力低于0.1MPa时再次加料。环氧丙烷加完后再在60℃-90℃保温1小时,即得到小阳离子低聚防膨季铵盐粘土稳定剂。
利用该方法制备的产品性能见附表中的实施例1。利用实施例1制备的小阳离子低聚防膨季铵盐粘土稳定剂,防膨率达到了83.7%,针对0.32毫达西的特低渗岩芯的渗透率提高了36.8%。
实施例2:
于带搅拌器和加热装置的密闭反应器中加入692份水和42份氢氧化钠,搅拌,使氢氧化钠完全溶解,加入105份二乙醇胺,搅拌15分钟以上至混合均匀,然后在搅拌的条件下滴加161份氯乙醇,滴加过程中控制温度在40℃-60℃之间,滴加完成后再在60℃-80℃下反应3小时,生成物为多羟基季铵盐水溶液。
对反应器抽真空至-0.2MPa至-0.3MPa之间,再充氮气至0.2MPa至0.3MPa之间,反复进行三次。再抽真空至-0.2MPa至-0.3MPa之间,升温至60℃后,分次加入环氧丙烷464份。每次加入环氧丙烷时反应器内压力不高于0.3MPa,待反应器内压力低于0.1MPa时再次加料。环氧丙烷加完后再在60℃-90℃保温1小时,即得到小阳离子低聚防膨季铵盐粘土稳定剂。
利用该方法制备的产品性能见附表中的实施例2。利用实施例2制备的小阳离子低聚防膨季铵盐粘土稳定剂,防膨率达到了85.1%,,针对0.21毫达西的特低渗岩芯的渗透率提高了33.2%。
实施例3:
于带搅拌器和加热装置的密闭反应器中加入753.5份水和3份氢氧化钾,搅拌,使氢氧化钾完全溶解,加入149份三乙醇胺,搅拌15分钟以上至混合均匀,然后在搅拌的条件下滴加94.5份氯乙醇,滴加过程中控制温度在40℃-60℃之间,滴加完成后再在60℃-80℃下反应3小时,生成物为多羟基季铵盐水溶液。
对反应器抽真空至-0.2MPa至-0.3MPa之间,再充氮气至0.2MPa至0.3MPa之间,反复进行三次。再抽真空至-0.2MPa至-0.3MPa之间,升温至60℃后,分次加入环氧乙烷440份。每次加入环氧丙烷时反应器内压力不高于0.3MPa,待反应器内压力低于0.1MPa时再次加料。环氧乙烷加完后再在60℃-90℃保温1小时,即得到小阳离子低聚防膨季铵盐粘土稳定剂。
利用该方法制备的产品性能见附表中的实施例3。利用实施例3制备的小阳离子低
聚防膨季铵盐粘土稳定剂,防膨率达到了81.3%,针对0.26毫达西的特低渗岩芯的渗透率提
高了30.9%。
实施案例编号 | 实施例1 | 实施例2 | 实施例3 |
防膨率,% | 83.7 | 85.1 | 81.3 |
岩芯渗透提高率,% | 36.8 | 33.2 | 30.9 |
以上所述,仅为本发明的较佳实施例而已,并非用于限定本发明的保护范围。
Claims (9)
1.一种小阳离子低聚防膨季铵盐粘土稳定剂,其特征在于,由质量比为100:23-58的多羟基季铵盐水溶液和环氧丙烷组成;
其中,所述多羟基季铵盐水溶液包括以下重量份的组分:428-858份的水、2-122份的苛性碱、60-150份的低碳羟基胺和80-300份的短链氯醇。
2.根据权利要求1所述的小阳离子低聚防膨季铵盐粘土稳定剂,其特征在于:所述水为纯净水或软化水。
3.根据权利要求1所述的小阳离子低聚防膨季铵盐粘土稳定剂,其特征在于:所述苛性碱为氢氧化钾或氢氧化钠。
4.根据权利要求1所述的小阳离子低聚防膨季铵盐粘土稳定剂,其特征在于:所述低碳羟基胺选自一乙醇胺、二乙醇胺或三乙醇胺。
5.根据权利要求1所述的小阳离子低聚防膨季铵盐粘土稳定剂,其特征在于:所述短链氯醇为氯乙醇或氯丙醇。
6.根据权利要求1所述的小阳离子低聚防膨季铵盐粘土稳定剂,其特征在于:所述多羟基季铵盐水溶液1000份和环氧丙烷348份;所述多羟基季铵盐水溶液由水、氢氧化钠、三乙醇胺和氯乙醇按质量比768.5:2:149:80.5制成。
7.一种如权利要求1-6任一项所述的小阳离子低聚防膨季铵盐粘土稳定剂的制备方法,其特征在于,包括以下步骤:
(1)按照配方份,在反应器中用水将苛性碱溶解,加入低碳羟基胺搅拌15分钟以上至混合均匀,然后在搅拌的条件下滴加短链氯醇,滴加过程中控制温度在40℃-60℃之间,滴加完成后再在60℃-80℃进行反应,生成物为多羟基季铵盐水溶液;
(2)反应完成后,将反应器抽真空至-0.2MPa至-0.3MPa,再充氮气至0.2MPa至0.3MPa,将反应器中的空气利用氮气进行置换,然后将反应器中多羟基季铵盐水溶液升温至60℃后,滴加环氧丙烷,滴加过程中保持反应温度在60℃-90℃,环氧丙烷加完后再在60℃-90℃进行反应,即得到小阳离子低聚防膨季铵盐粘土稳定剂。
8.如权利要求7所述的制备方法,其特征在于:在步骤(1)中,反应时间为1-3小时。
9.如权利要求7所述的制备方法,其特征在于:在步骤(2)中,反应时间为0.5-2.0小时。
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