CN112322272B - 一种低污染多功能耐盐降阻压裂剂 - Google Patents

一种低污染多功能耐盐降阻压裂剂 Download PDF

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CN112322272B
CN112322272B CN202011077615.6A CN202011077615A CN112322272B CN 112322272 B CN112322272 B CN 112322272B CN 202011077615 A CN202011077615 A CN 202011077615A CN 112322272 B CN112322272 B CN 112322272B
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张亚明
赵卫峰
胡红
徐峰
刘继霞
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Abstract

本发明涉及一种低污染多功能耐盐降阻压裂剂，所述压裂剂中包含表面活性剂A和阴离子两亲分子B，表面活性剂A能够在较宽的温度范围内保持蠕虫状结构，由该压裂剂配制的压裂液可保证油气井在压裂施工过程中的减阻性能，同时该压裂剂还含有温敏特性的链段，能够使水溶液的黏度在一定范围内随着地层温度的升高而升高，提高了压裂液的携砂能力，拓宽了应用温度范围。本发明提供的压裂剂配制的压裂液同时具有较好的耐盐性，能够适用于多种水质，尤其是地层采出水和施工返排水，极大地节约了水资源。

Description

一种低污染多功能耐盐降阻压裂剂
技术领域
本发明涉及油田化学技术领域，具体涉及一种低污染多功能耐盐降阻压裂剂。
背景技术
压裂是油气井增产的主要手段，其一般过程为：在地面采用高压泵组，将压裂液以大于油层吸收能力的排量向井内注入，使井筒内的压力逐渐提高，当压力增高到大于油层破裂压力时，油层就会被压开，形成裂缝。继续向地层注入带有支撑剂的携砂液，可使裂缝向地层深处继续延伸。当外来压力消失后，支撑剂将会支撑起已经压开的裂缝。当压裂液返排回地面后，就会在油层中留下一条或多条裂缝，使油层与井筒之间建立起新的渗流通道。在这个过程中，压裂剂对于压裂效果起到了关键作用。随着油田勘探程度的提高，低品位非常规油气资源成为主要新增储量，此类油气藏埋藏深度跨度大。油气藏的开发一般采取水平井及体积压裂方式，体积压裂既需要压裂液降低摩阻，减少施工难度，同时还需要大量的水，返排液也需要处理达标方可返排，这给水资源及环境带来较大压力，因此压裂液提出了耐热、耐盐的要求。
发明内容
本发明的目的是提供一种低污染多功能耐盐降阻压裂剂。
本发明解决上述技术问题所采用的方案是：
一种低污染多功能耐盐降阻压裂剂，所述压裂剂中包含表面活性剂A和阴离子两亲分子B，所述的表面活性剂A结构式如下所示：
Figure BDA0002717460320000011
所述阴离子两亲分子B的结构式如下所示：
Figure BDA0002717460320000012
其中，R1选自H或者C1～C4的烷基，R2、R3独立地选自C1～C4的亚烷基，R4选自C1～C4的烷基，X为卤素元素，n＝10～60，m＝5～100，a＝1～40，b＝1～40。
优选地，所述表面活性剂A和阴离子两亲分子B的摩尔比为1：(0.5～2)。
优选地，R2与R3相同。
优选地，所述表面活性剂A的制备方法包括如下步骤：
(a)将聚氧乙烯-聚氧丙烯-聚氧乙烯嵌段聚合物和胺化催化剂加入反应釜中，进行氮气置换和氢气置换后，通入脂肪伯胺，在200～220℃下反应4～6h，去除未反应完全的脂肪伯胺，得到中间体C；
(b)将季铵化试剂与步骤(a)得到的中间体C混合溶于溶剂中，在80～100℃下反应4～10个小时，得到所述的表面活性剂A。
本发明的另一目的是提供上述的压裂剂在压裂增产作业中的应用，用于配制滑溜水压裂液或者压裂携砂液，其中压裂剂的用量为0.02％～2％。
优选地，配制所述滑溜水压裂液以及压裂携砂液所使用的水包括自来水、天然水、采出水、返排水。
优选地，配制所述滑溜水压裂液以及压裂携砂液的应用温度为15℃～120℃。
优选地，配制所述滑溜水压裂液以及压裂携砂液的耐盐能力≥20％。
优选地，配制所述滑溜水压裂液以及压裂携砂液的减阻率大于70％。
本发明采用粘弹性表面活性剂压裂剂，是一种无残渣剂，不会对油、气层带来损害，同时表面活性剂分子形成的蠕虫状胶束在一定范围内受温度、剪切力的影响较小，不会发生剪切降解。
本发明提供的压裂剂能够使配制的压裂液在15℃～120℃温度范围内保持蠕虫状结构，从而保证压裂液的减阻性能，同时大分子表面活性剂中还含有温敏特性的链段，能够使水溶液的黏度随着地层温度的升高而升高，进一步提高了压裂液的应用温度范围。
本发明提供的压裂剂具有较好的耐盐性，能够适用于多种水质，尤其是采出水和返排水，极大地节约了水资源。
具体实施方式
为更好的理解本发明，下面的实施例是对本发明的进一步说明，但本发明的内容不仅仅局限于下面的实施例。
实施例1
将聚氧乙烯-聚氧丙烯-聚氧乙烯嵌段聚合物(平均分子量2500)和胺化催化剂(Harshaw公司的Cu-203催化剂)加入低压反应釜中，依次进行4次氮气置换和4次氢气置换，采用氮气进料甲胺，其中，聚氧乙烯-聚氧丙烯-聚氧乙烯嵌段聚合物：Cu-203：甲胺的重量比为20：1：2.5。在220℃条件下还原反应6h，降温至160℃，减压除去未反应完全的甲胺，得到中间体C；将中间体C溶于无水乙醇中，配置成质量浓度30％的溶液，加入低压反应釜中，再加入氯乙醇，在90℃条件下反应6h后结束，得到表面活性剂A。
将氯乙烯单体与引发剂EHP(过氧化二碳酸二(2-乙基己)酯)混合溶于去离子水中，在50℃条件下滴加丙烯磺酸，进行聚合反应，10h后终止反应，其中氯乙烯：EHP：丙烯磺酸的重量比为1500：1：150，得到阴离子两亲分子B。
将表面活性剂A与阴离子两亲分子B以重量比2:1混合，得到材料D。加入氯化钾以及壬基酚聚氧乙烯醚NP-10与全氟辛基季铵碘化物，溶于清水中，使得材料D、氯化钾、壬基酚聚氧乙烯醚NP-10与全氟辛基季铵碘化物的质量比分别为0.2％、0.2％、0.1％、0.1％，将混合溶液搅拌4h后静置过夜，即得澄清无泡的压裂液。
实施例2
制备方法与实施例1相同，不同之处在于，采用返排水代替自来水配置压裂液。采用的返排水组成分析如下表1：
表1返排水组成分析
Figure BDA0002717460320000031
将表面活性剂A与阴离子两亲分子B以重量比2:1混合，得到材料D。加入氯化钾以及壬基酚聚氧乙烯醚NP-10与全氟辛基季铵碘化物，溶于清水中，使得材料D、氯化钾、壬基酚聚氧乙烯醚NP-10与全氟辛基季铵碘化物的质量比分别为0.2％、0.3％、0.2％、0.1％，将混合溶液搅拌4h后静置过夜，即得澄清无泡的压裂液。
实施例3
制备方法与实施例1相同，不同之处在于，采用平均分子量为345的十八醇聚氧乙烯醚取代聚氧乙烯-聚氧丙烯-聚氧乙烯嵌段聚合物来配制制备表面活性剂A，十八醇聚氧乙烯醚的用量与聚氧乙烯-聚氧丙烯-聚氧乙烯嵌段聚合物等摩尔量换算。将表面活性剂A与阴离子两亲分子B以重量比2:1混合，得到材料D。加入氯化钾以及壬基酚聚氧乙烯醚NP-10与全氟辛基季铵碘化物，溶于清水中，使得材料D、氯化钾、壬基酚聚氧乙烯醚NP-10与全氟辛基季铵碘化物的质量比分别为0.2％、0.2％、0.1％、0.1％，将混合溶液搅拌4h后静置过夜，即得澄清无泡的压裂液。
实施例4
制备方法与实施例1相同，不同之处在于，采用苯磺酸替代阴离子两亲分子B来配制压裂剂，苯磺酸的用量与阴离子两亲分子B等摩尔量换算。
分别采用摩阻测定仪、流变仪对实施例1～4所得压裂液的减阻率和粘度进行测定，各个实施例的样品采用相同的条件进行测试，结果如下表1所示：
表2性能测试结果
Figure BDA0002717460320000041
以上所述是本发明的优选实施方式而已，当然不能以此来限定本发明之权利范围，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和变动，这些改进和变动也视为本发明的保护范围。

Claims (6)

1.一种低污染多功能耐盐降阻压裂剂，其特征在于，所述压裂剂由以下方法制备：
将平均分子量2500的聚氧乙烯-聚氧丙烯-聚氧乙烯嵌段聚合物和Harshaw公司的Cu-203催化剂加入低压反应釜中，依次进行4次氮气置换和4次氢气置换，采用氮气进料甲胺，其中，聚氧乙烯-聚氧丙烯-聚氧乙烯嵌段聚合物：Cu-203：甲胺的重量比为20：1：2.5；在220℃条件下还原反应6h，降温至160℃，减压除去未反应完全的甲胺，得到中间体C；将中间体C溶于无水乙醇中，配置成质量浓度30％的溶液，加入低压反应釜中，再加入氯乙醇，在90℃条件下反应6h后结束，得到表面活性剂A；
将氯乙烯单体与引发剂EHP混合溶于去离子水中，在50℃条件下滴加丙烯磺酸，进行聚合反应，10h后终止反应，其中氯乙烯：EHP：丙烯磺酸的重量比为1500：1：150，得到阴离子两亲分子B；
将表面活性剂A与阴离子两亲分子B以重量比2:1混合，得到材料D；加入氯化钾以及壬基酚聚氧乙烯醚NP-10与全氟辛基季铵碘化物，溶于清水中，将混合溶液搅拌4h后静置过夜，即得澄清无泡的压裂剂；
材料D、氯化钾、壬基酚聚氧乙烯醚NP-10与全氟辛基季铵碘化物的质量比为0.2％、0.2％、0.1％、0.1％或0.2％、0.3％、0.2％、0.1％。
2.权利要求1所述的压裂剂在压裂增产作业中的应用，其特征在于，用于配制滑溜水压裂液或者压裂携砂液，其中压裂剂的用量为0.02％～2％。
3.如权利要求2所述的应用，其特征在于，所述滑溜水压裂液以及压裂携砂液所使用的水包括自来水、天然水、采出水、返排水。
4.如权利要求2所述的应用，其特征在于，所述滑溜水压裂液以及压裂携砂液的应用温度为15℃～120℃。
5.如权利要求2所述的应用，其特征在于，所述滑溜水压裂液以及压裂携砂液的耐盐能力≥20％。
6.如权利要求2所述的应用，其特征在于，配制所述滑溜水压裂液以及压裂携砂液的减阻率大于70％。
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