CN106749899A - 一种抗高温高盐调剖堵水用聚合物成胶剂的制备方法 - Google Patents
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Abstract
本发明公开了一种抗高温高盐调剖堵水用聚合物成胶剂的制备方法，在聚合物的合成过程中引入了多种耐温抗盐抗水解功能单体，加入了适量改性助剂，通过对分子主链进行设计适当调整功能单体与酰胺基团的摩尔百分比，从而使合成出的聚合物在极端油藏条件下(温度≥110℃，矿化度≥10万ppm)交联形成的冻胶强度较高、热稳定性较好，同时能保证足够的交联时间，在苛刻油藏条件下能有效的起到封堵效果；在造粒过程中引入了少量稳定剂，进一步提高了聚合物的溶解性与热稳定性。该聚合物粘均分子量较低(1000万以下)，溶解性较好，与有机交联剂交联形成的冻胶型调剖堵水剂抗高温高盐能力强、成胶时间自由可控、成胶强度高且热稳定性较好。
Description
技术领域
本发明属于油井堵水领域，具体涉及一种抗高温高盐调剖堵水用聚合物成胶剂的制备方法。
背景技术
目前，国内陆上大部分油田都处于开发中后期，油井出水已成为影响原油采收的一个严重问题。油井大量出水会大大增加开发费用，并加剧管线腐烛、结垢等，因此进行油井堵水非常必要。
机械堵水法在油田开发早期使用较多，但到了开发中后期，由于出现水淹、水窜、水锥等现象，仅靠机械方法不能满足堵水要求，此时就需利用化学堵水法。像我国西北油田、吐哈油田等高温油藏地层温度一般在90～120℃，且处于高含水阶段，现有的调剖剂多数易受温度、矿化度、地层剪切等因素的影响而降解失效。如塔里木油田井底循环温度110℃左右，且多为水平井，现有的调剖剂很难达到现场施工要求。因此，研制迟效型耐高温深部调剖剂可以从根本上解决高温高含水油藏水驱“短路”的问题。
聚丙烯酰胺类凝胶堵水剂是研究和应用较为广泛的一种化学堵水剂，一般由丙烯酰胺的聚合物和交联剂直接制备而获得，但此类凝胶堵水剂已表现出如下问题:—是所用聚合物的粘均分子量较高，会导致储层孔道的大分子滞留伤害；二是在低渗透地层中凝胶的注入能力较差，给现场施工带来困难；三是凝胶用于高温高盐深井中，为保证在成胶前能注入到目的地层，不易很好的控制凝胶的延迟成胶时间且成胶的热稳定性较差；四是目前我国应用最广的是聚合物类的铬凝胶，其胶体抗剪切性良好可以进行有效调堵，但铬凝胶热稳定性差，100℃以上脱水降解速率快，且重金属离子对地下水体污染严重。
因此，研制一种抗高温高盐、有效作用期长、适用于有机交联剂的调剖堵水用聚合物成胶剂具有重要的意义。
发明内容
本发明的目的在于提供一种有效作用期长、适用于有机交联剂的抗高温高盐调剖堵水用聚合物成胶剂的制备方法。
本发明解决其技术问题所采用的技术方案是：一种抗高温高盐调剖堵水用聚合物成胶剂的制备方法，包括以下步骤：
1)将丙烯酰胺单体、甲基丙烯酰胺单体、N-叔丁基丙烯酰胺单体和2-丙烯酰胺基-2-甲基丙磺酸配成一定浓度的水溶液，用碱调节水溶液的pH值为7～8；
2)将调制好的反应液降温至5～8℃，加入到聚合反应器中通氮气30分钟，在氮气保护下依次加入乳液助剂、改性助剂与引发剂，控制聚合反应的初温在8～10℃，绝热聚合4～6小时；
3)聚合升到最高温后保温2小时，将所得胶体取出，切割造粒，加入稳定剂混合均匀，烘干，研磨，筛分得白色聚合物颗粒。
具体地，所述各组分的重量百分比如下：
丙烯酰胺单体10％～20％
甲基丙烯酰胺单体1％～2％
N-叔丁基丙烯酰胺1％～2％
2-丙烯酰胺基-2-甲基丙磺酸单体15％～20％
引发剂0.005％～0.01％
改性助剂0.02％～0.05％
乳液助剂0.2％～0.5％
余量为水和碱量之和。
具体地，所述步骤1)中的碱为离子膜液碱。
具体地，所述步骤2)中的引发剂是由过硫酸盐氧化剂与亚硫酸氢盐还原剂组成的氧化还原引发体系；所述过硫酸盐采用质量浓度1％的过硫酸钾水溶液或过硫酸铵水溶液；所述亚硫酸氢盐采用质量浓度1％的亚硫酸氢钠水溶液。
具体地，所述步骤2)中的改性助剂为质量浓度为5％的二乙烯三胺水溶液。
具体地，所述步骤2)中的乳液助剂为可溶于水的水包油型液体石蜡油乳化液，所述液体石蜡油有效含量为20wt％。
具体地，所述步骤3)中的稳定剂为亚磷酸酯类抗氧剂的一种或两种，稳定剂加入量为胶粒总重量的0.5～1％。
本发明具有以下有益效果：本发明的制备方法与现有技术相比，在对分子主链进行设计时引入了多种耐温抗盐功能性单体，从而提高了聚合物成胶剂的耐温抗盐性与热稳定性；引入的改性助剂二乙烯三胺在有甲醛存在时可与酰胺基团发生胺甲基化反应从而与聚合物分子主链相连，形成支链，支链的空间位阻作用有效迟滞了酚醛交联体系的交联作用，从而使聚合物在高温高盐条件下交联成冻胶的时间有效延迟，保证了足够的成胶时间；加入的乳液助剂可均匀分散于整个聚合体系中并随着聚合反应的进行逐步释放出石蜡油，从而有效解决了胶块与反应器内壁的粘连问题，使出料顺畅，同时使后续造粒烘干过程顺畅，胶粒之间不互相粘连，分散均匀；造粒过程中加入的稳定剂可有效屏蔽氧的作用，避免胶粒在烘干过程中产生水不溶物，同时可进一步提高聚合物的热稳定性。该聚合物粘均分子量较低，溶解性较好，适合于低渗透油层的泵注且与有机交联剂作用形成的冻胶型调剖堵水剂抗高温高盐能力强、成胶强度高且热稳定性较好。
具体实施方式
实施例1
将丙烯酰胺晶体加入到配料容器中，加入去离子水充分溶解，再分别加入2-丙烯酰胺基-2-甲基丙磺酸、甲基丙烯酰胺、N-叔丁基丙烯酰胺充分溶解，再加入浓度32wt％的离子膜液碱调节pH为7.5。将配制好的物料降温至8℃并移入聚合反应器中，通氮气驱氧至30分钟时首先加入乳液助剂，通氮气至35分钟时加入5％的改性助剂，通氮气至40分钟时依次加入1％过硫酸钾和1％亚硫酸氢钠组成的引发剂体系于8℃引发反应，继续通氮气5分钟后停止并密封，绝热聚合反应4小时，升到最高温后保温2小时得到胶块。取出胶块，切割、造粒，取300g胶粒加入1.5g稳定剂混合均匀，将胶粒烘干、粉碎、过筛得调剖堵水用聚合物产品。
其中，各组分的重量百分比如下：丙烯酰胺单体15％，2-丙烯酰胺基-2-甲基丙磺酸单体20％，甲基丙烯酰胺单体1％，N-叔丁基丙烯酰胺1.2％，乳液助剂0.25％，改性助剂0.03％，引发剂0.008％，余量为水和液碱量之和。
实施例2
将丙烯酰胺晶体加入到配料容器中，加入去离子水充分溶解，再分别加入2-丙烯酰胺基-2-甲基丙磺酸、甲基丙烯酰胺、N-叔丁基丙烯酰胺充分溶解，再加入浓度32wt％的离子膜液碱调节pH为7。将配制好的物料降温至5℃并移入聚合反应器中，通氮气驱氧至30分钟时首先加入乳液助剂，通氮气至35分钟时加入5％的改性助剂，通氮气至40分钟时依次加入1％过硫酸钾和1％亚硫酸氢钠组成的引发剂体系于9℃引发反应，继续通氮气5分钟后停止并密封，绝热聚合反应5小时，升到最高温后保温2小时得到胶块。取出胶块，切割、造粒，取300g胶粒加入3g稳定剂混合均匀，将胶粒烘干、粉碎、过筛得调剖堵水用聚合物产品。
其中，各组分的重量百分比如下：丙烯酰胺单体10％，2-丙烯酰胺基-2-甲基丙磺酸单体17％，甲基丙烯酰胺单体1.5％，N-叔丁基丙烯酰胺1.5％，乳液助剂0.2％，改性助剂0.05％，引发剂0.01％，余量为水和液碱量之和。
实施例3
将丙烯酰胺晶体加入到配料容器中，加入去离子水充分溶解，再分别加入2-丙烯酰胺基-2-甲基丙磺酸、甲基丙烯酰胺、N-叔丁基丙烯酰胺充分溶解，再加入浓度32wt％的离子膜液碱调节pH为8。将配制好的物料降温至7℃并移入聚合反应器中，通氮气驱氧至30分钟时首先加入乳液助剂，通氮气至35分钟时加入5％的改性助剂，通氮气至40分钟时依次加入1％过硫酸钾和1％亚硫酸氢钠组成的引发剂体系于10℃引发反应，继续通氮气5分钟后停止并密封，绝热聚合反应6小时，升到最高温后保温2小时得到胶块。取出胶块，切割、造粒，取300g胶粒加入2.4g稳定剂混合均匀，将胶粒烘干、粉碎、过筛得调剖堵水用聚合物产品。
其中，各组分的重量百分比如下：丙烯酰胺单体18％，2-丙烯酰胺基-2-甲基丙磺酸单体15％，甲基丙烯酰胺单体1.8％，N-叔丁基丙烯酰胺2％，乳液助剂0.5％，改性助剂0.02％，引发剂0.005％，余量为水和液碱量之和。
实施例4
将丙烯酰胺晶体加入到配料容器中，加入去离子水充分溶解，再分别加入2-丙烯酰胺基-2-甲基丙磺酸、甲基丙烯酰胺、N-叔丁基丙烯酰胺充分溶解，再加入浓度32wt％的离子膜液碱调节pH为7.8。将配制好的物料降温至6℃并移入聚合反应器中，通氮气驱氧至30分钟时首先加入乳液助剂，通氮气至35分钟时加入5％的改性助剂，通氮气至40分钟时依次加入1％过硫酸钾和1％亚硫酸氢钠组成的引发剂体系于8℃引发反应，继续通氮气5分钟后停止并密封，绝热聚合反应4小时，升到最高温后保温2小时得到胶块。取出胶块，切割、造粒，取300g胶粒加入1.8g稳定剂混合均匀，将胶粒烘干、粉碎、过筛得调剖堵水用聚合物产品。
其中，各组分的重量百分比如下：丙烯酰胺单体20％，2-丙烯酰胺基-2-甲基丙磺酸单体16％，甲基丙烯酰胺单体2％，N-叔丁基丙烯酰胺1％，乳液助剂0.4％，改性助剂0.04％，引发剂0.007％，余量为水和液碱量之和。
实施例5：根据Q/LBM0500对聚合物性能进行评价，使用乌氏粘度计采用一点法对聚合物粘均分子量进行测试，用模拟地层水(矿化度100000mg/L)配制浓度为0.3％的聚合物溶液，加入交联剂苯酚(体系质量的0.08％)、六亚甲基四胺(体系质量的0.1％)和稳定剂硫脲(体系质量的0.3％)，搅拌均匀后取20g成胶液置于安剖瓶中，用酒精灯封口，110℃恒温加热并测定冻胶体系的成胶时间、冻胶强度和冻胶稳定性。所得实验结果如下表：
| 编号 | 分子量 | 成胶时间 | 冻胶强度 | 冻胶稳定性 |
| 实例1 | 985万 | 15h | 35470mpa·s | 35天未破胶 |
| 实例2 | 900万 | 18h | 30120mpa·s | 40天未破胶 |
| 实例3 | 850万 | 24h | 28060mpa·s | 48天未破胶 |
| 实例4 | 840万 | 23h | 27560mpa·s | 45天未破胶 |
从实验数据可以看出，本发明的抗高温高盐调剖堵水用聚合物与有机交联剂作用形成的冻胶体系成交时间均在15h以上且成胶时间可自由调整，冻胶强度均在20000mpa·s以上，冻胶稳定性均大于30天，适合高温高盐油藏调剖堵水需求。因此，该聚合物是一种抗高温高盐、有效作用期长、与有机交联剂作用效果显著的调剖堵水用聚合物成胶剂。
以上是本发明的具体实施例，对本发明的技术方案做进一步描述，但是本发明的保护范围并不限于这些实施例。凡是不背离本发明构思的改变或等同替代均包括在本发明的保护范围之内。
Claims (8)
1.一种抗高温高盐调剖堵水用聚合物成胶剂的制备方法，其特征在于，包括以下步骤：
1)将丙烯酰胺单体、甲基丙烯酰胺单体、N-叔丁基丙烯酰胺单体和2-丙烯酰胺基-2-甲基丙磺酸配成一定浓度的水溶液，用碱调节水溶液的pH值为7～8；
2)将调制好的反应液降温至5～8℃，加入到聚合反应器中通氮气30分钟，在氮气保护下依次加入乳液助剂、改性助剂与引发剂，控制聚合反应的初温在8～10℃，绝热聚合4～6小时；
3)聚合升到最高温后保温2小时，将所得胶体取出，切割造粒，加入稳定剂混合均匀，烘干，研磨，筛分得白色聚合物颗粒。
2.根据权利要求1所述的制备方法，其特征在于，所述各组分的重量百分比如下：
丙烯酰胺单体 10％～20％
甲基丙烯酰胺单体 1％～2％
N-叔丁基丙烯酰胺 1％～2％
2-丙烯酰胺基-2-甲基丙磺酸单体 15％～20％
引发剂 0.005％～0.01％
改性助剂 0.02％～0.05％
乳液助剂 0.2％～0.5％
余量为水和碱量之和。
3.根据权利要求1所述的制备方法，其特征在于，所述步骤1)中的碱为离子膜液碱。
4.根据权利要求1所述的制备方法，其特征在于，所述步骤2)中的引发剂是由过硫酸盐氧化剂与亚硫酸氢盐还原剂组成的氧化还原引发体系。
5.根据权利要求4所述的制备方法，其特征在于，所述过硫酸盐采用质量浓度1％的过硫酸钾水溶液或过硫酸铵水溶液；所述亚硫酸氢盐采用质量浓度1％的亚硫酸氢钠水溶液。
6.根据权利要求1所述的制备方法，其特征在于，所述步骤2)中的改性助剂为质量浓度为5％的二乙烯三胺水溶液。
7.根据权利要求1所述的制备方法，其特征在于，所述步骤2)中的乳液助剂为可溶于水的水包油型液体石蜡油乳化液，所述液体石蜡油有效含量为20wt％。
8.根据权利要求1所述的制备方法，其特征在于，所述步骤3)中的稳定剂为亚磷酸酯类抗氧剂的一种或两种，稳定剂加入量为胶粒总重量的0.5～1％。
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Denomination of invention: A preparation method of polymer gelling agent for profile control and water plugging with high temperature and high salt resistance Effective date of registration: 20230209 Granted publication date: 20190219 Pledgee: Guangdong Development Bank Co.,Ltd. Dongying Branch Pledgor: DONGYING BAOMO ENVIRONMENTAL ENGINEERING Co.,Ltd. Registration number: Y2023980032332 |
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