CN110776608A - 一种羟基化多维纳米材料杂化分散胶及其应用 - Google Patents
一种羟基化多维纳米材料杂化分散胶及其应用 Download PDFInfo
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Abstract
本发明公开了一种羟基化多维纳米材料杂化分散胶及其应用，属于油田化学技术领域，本发明的分散胶由改性羟基化碳纳米管、丙烯酰胺、甲基丙烯酰氯改性十二烷基醇聚氧乙烯醚、N,N‑亚甲基双丙烯酰胺和聚乙二醇二丙烯酸酯在引发剂的作用下发生聚合交联反应制成，本发明通过引入甲基丙烯酰氯改性十二烷基醇聚氧乙烯醚和高度强度的纤维素碳纳米管使得本分散胶具有良好的强度以及耐温抗盐性能，同时，差异性分解的双重交联体系赋予本分散胶良好的缓膨性，使得其在地面配样时几乎不膨胀，在近井地带缓慢膨胀，因而可以达到地层深部，实现有效封堵、使得深部液流转向，提高采收率。
Description
技术领域
本发明涉及油田化学技术领域，具体涉及一种羟基化多维纳米材料杂化分散胶及其应用。
背景技术
随着石油的进一步开发，油藏开采向更深的储层发展，出现了油藏条件更加苛刻的高温、高盐油藏。与此同时，水驱采油后的剩余油分布不均，导致油水两相交错式分布。高渗区域经注入水的长期冲刷形成优势通道，注采矛盾进一步加剧。如何实现高温高盐油藏稳油控水以及进一步提高原油采收率是我们面临的挑战。
对于高温高盐油藏，受油藏高温(>80℃)的影响，以流度控制为主的聚合物驱、聚合物/表面活性剂二元驱、聚合物/表面活性剂/碱三元复合驱以及聚合物增强泡沫调驱长期稳定性差，有效期短；受油藏强非均质性的影响，以降低界面为主的表面活性剂驱油由于优势通道的存在，蹿流现象严重，最终导致波及体积小，采收率低。有效提高高温高盐油藏采收率的途径是向注水井中注入化学体系，包括无机颗粒、凝胶和分散胶来有效封堵高渗条带，使注入水液流转向去低渗层，扩大波及体积。
然而，目前无机颗粒不具备吸水膨胀性或膨胀性很差，不能有效的封堵高渗层实现深部液流转向；整体凝胶虽能够直接将高渗层堵死，但是存在伤害低渗层的潜在危害；分散胶能够对高渗层实现有效封堵，且“堵而不死”，但常规的分散胶耐温、抗盐性差，在高温高盐油藏中其膨胀性的长期稳定性较差。
发明内容
针对常规分散胶耐温抗盐性差的缺点，本发明的目的是提供一种满足高温高盐油藏使用条件的羟基化多维纳米材料杂化分散胶。
本发明采用以下技术方案为：
一种羟基化多维纳米材料杂化分散胶，该分散胶由高强度纤维素—改性羟基化碳纳米管、丙烯酰胺、甲基丙烯酰氯改性十二烷基醇聚氧乙烯醚、N,N-亚甲基双丙烯酰胺和聚乙二醇二丙烯酸酯在引发剂的作用下发生聚合交联反应制备而成，其各组分的质量百分含量为：
丙烯酰胺15％～25％，
改性羟基化碳纳米管0.01％～0.1％，
甲基丙烯酰氯改性十二烷基醇聚氧乙烯醚0.5％～5％，
聚乙二醇二丙烯酸酯：0.05％～0.5％
N,N-亚甲基双丙烯酰胺0.05％～0.5％
引发剂0.02％～0.1％
其余为水。
所述的引发剂为偶氮二异丁脒盐酸盐、过硫酸盐或者氧化还原引发体系。
该分散胶所用的改性羟基化碳纳米管的结构式如下：
所用的甲基丙烯酰氯改性十二烷基醇聚氧乙烯醚的结构式如下：
n为氧乙烯的聚合度，7≤n≤40。
上述羟基化多维纳米材料杂化分散胶主要通过单体经引发剂引发聚合交联而得，最后经过烘干、粉碎、筛分和再粉碎制备而成，具体的制备步骤如下所示：
(1)搅拌速度为200～400r/min条件下，将改性羟基化碳纳米管、丙烯酰胺、甲基丙烯酰氯改性十二烷基醇聚氧乙烯醚、N,N-亚甲基双丙烯酰胺和聚乙二醇二丙烯酸酯加入到水中，完全加入后继续搅拌1小时，得到黑色的液体。
(2)向步骤(1)中得到的黑色液体通入N2除氧30分钟，然后加入引发剂，再继续通N230分钟。
(3)升温至30℃～60℃，保温3小时，得到黑色的凝胶块。
(4)将上述凝胶块通过烘干、粉碎、筛分和再粉碎后，得到羟基化多维纳米材料杂化分散胶。
本发明的另一目的是提供上述羟基化多维纳米材料杂化分散胶在高温高盐油藏的应用，本分散胶具有良好的缓膨性，使得其在地面配样时几乎不膨胀，将其注入地层后，在近井地带缓慢膨胀，可到达地层深部继续膨胀实现有效封堵、使得深部液流转向，提高采收率。
与现有技术相比，本发明具有以下有益效果：
该分散胶的原料配方中加入了改性羟基化碳纳米管，与引发体系/交联体系构建三维空间网络结构，将高强度纤维素碳纳米管引入到三维空间网络结构中，改善了传统的预交联凝胶颗粒强度低、耐温抗盐性差的缺点；甲基丙烯酰氯改性十二烷基醇聚氧乙烯醚的引入提高了分散胶的抗盐性，尤其是抗钙镁离子的性能；本分散胶具有差异性分解的双重交联体系，因而具有良好的缓膨性，将其应用于高温高盐油层时，其地面配样时几乎不膨胀，在近井地带缓慢膨胀，因此能够到地层深部继续膨胀实现有效封堵。
附图说明
图1为实施例1分散胶的缓膨性能图。
具体实施方式
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，现对本发明的技术方案进行以下详细说明，但不能理解为对本发明的可实施范围的限定。
(一)实施例
羟基化多维纳米材料杂化分散胶，由以下原料组分组成：0.01g改性羟基化碳纳米管，23g丙烯酰胺，2g甲基丙烯酰氯改性十二烷基醇聚氧乙烯醚(聚氧乙烯醚的聚合度为20)，0.1gN,N-亚甲基双丙烯酰胺，0.1g聚乙二醇二丙烯酸酯，0.008g过硫酸铵，75g去离子水。
制备工艺：搅拌条件下将0.01g改性羟基化碳纳米管，23g丙烯酰胺，2g甲基丙烯酰氯改性十二烷基醇聚氧乙烯醚，0.1gN,N-亚甲基双丙烯酰胺和0.1g聚乙二醇二丙烯酸酯加入到75g去离子水中，然后继续搅拌1小时得到黑色的液体；通入N230分钟后将0.008g的过硫酸铵在搅拌条件下加入到前述液体中；再次通入N230分钟；将温度升高至60℃后保温3小时，得到黑色的凝胶块；最后经过烘干、粉碎、筛分和再粉碎后，得到羟基化多维纳米材料杂化分散胶。
实施例2
羟基化多维纳米材料杂化分散胶，由以下原料组分组成：0.03g改性羟基化碳纳米管，20g丙烯酰胺，5g甲基丙烯酰氯改性十二烷基醇聚氧乙烯醚，0.2gN,N-亚甲基双丙烯酰胺，0.07g聚乙二醇二丙烯酸酯，0.004g过硫酸铵/0.004g亚硫酸氢钠，75g去离子水。
制备工艺：搅拌条件下将0.03g改性羟基化碳纳米管，20g丙烯酰胺，5g甲基丙烯酰氯改性十二烷基醇聚氧乙烯醚(聚氧乙烯醚的聚合度为30)，0.2gN,N-亚甲基双丙烯酰胺和0.07g聚乙二醇二丙烯酸酯加入到75g去离子水中，然后继续搅拌1小时得到黑色的液体；通入N230分钟后将0.004g过硫酸铵/0.004g亚硫酸氢钠在搅拌条件下加入到前述液体中；再次通入N230分钟；将温度升高至30℃后保温3小时，得到黑色的凝胶块；最后经过烘干、粉碎、筛分和再粉碎后，得到羟基化多维纳米材料杂化分散胶。
(二)性能测试
(1)缓膨性
采用激光粒度仪测量实施例1制备的羟基化多维纳米材料杂化分散胶的中值粒径，根据不同温度下凝胶颗粒的中值粒径计算相应的膨胀倍数，以此来判断凝胶颗粒的缓膨性。从图1可知，随着温度的升高，分散胶膨胀倍数增加。现场配注是一个由地面到油藏深部的过程，在地面配注时为了保证分散胶的注入性，要求分散胶膨胀倍数低，而进入地层深部后需要缓慢的膨胀到最大倍数。由图1可知，该分散胶在低温时膨胀倍数小，有利于地面配注，随着温度的升高，膨胀倍数增大，有助于油藏深部调驱。
(2)强度与韧性
由于碳纳米管的引入，分散胶的强度得到了较高的提升。采用转向压力法评价实施例1中准备的分散胶的强度，实验用水矿化度10万，温度90℃。通过以下实验步骤计算分散胶的韧性：1)记录分散胶颗粒通过筛网时的最大压力P1max；2)收集通过后的分散胶在相同的速度下再次通过筛网，记录通过时的最大压力P2max，3)计算其韧性系数(P2max/P1max)。
表1、羟基化多维纳米材料杂化分散胶的转向压力与韧性
(3)调驱性能
利用国内某油藏提供的油水样、岩心及油藏资料，油藏条件(实验温度90℃，矿化度：10万)进行高、低渗透率岩心并联驱油实验。实验步骤如下：1)测试岩心基本参数后饱和原油，记录原油饱和度；2)水驱至含水率为98％；3)注入0.3PV以实施例1制备的分散胶颗粒配置的浓度为1500mg/L的溶液；4)后续水驱至含水率为98％。整个驱替过程中的速度为0.5mL/min。岩心参数及实验结果如表1所示。
由于渗透率级差较大，水驱过程中的低渗岩心未启动，高渗岩心采收率为48.8％。注入分散胶后，低渗层采收率提高20.4％同时高渗层的采收率提高18.9％。说明分散胶能够有效的进行非均质性调控，扩大注入水波及体积，启动低渗层。
表4-6不同渗透率级差条件下注分散胶调驱实验结果
对本领域的技术人员来说，可根据以上描述的技术方案以及构思，做出其它各种相应的改变以及形变，而所有的这些改变以及形变都应该属于本发明权利要求的保护范围之内。
Claims (3)
1.一种羟基化多维纳米材料杂化分散胶，其特征在于，由以下质量含量的组分发生聚合交联反应制备而成：
所述改性羟基化碳纳米管结构式如下：
所述甲基丙烯酰氯改性十二烷基醇聚氧乙烯醚的结构式如下：
式中，n为氧乙烯的聚合度，7≤n≤40。
2.根据权利要求1所述的羟基化多维纳米材料杂化分散胶，其特征在于，所述引发剂为偶氮二异丁脒盐酸盐、过硫酸盐或者氧化还原引发体系。
3.如权利要求1所述羟基化多维纳米材料杂化分散胶在高温高盐油藏的应用。
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