CN108949131A - 调剖体系及其使用方法 - Google Patents
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Abstract
本发明属于石油开采领域，涉及一种调剖体系及其使用方法，该调剖体系的组分包含：水溶性聚合物、交联剂和水，所述水溶性聚合物选自聚醚胺中的至少一种，聚醚胺的数均分子量小于1000。与常用的聚合物亲水凝胶堵水调剖体系不同，本发明的调剖体系没有“固水”的作用，使用时的交联反应产物不亲水并且具有粘性，从而会自发地从水中析出并吸附在岩石表面，改变岩石表面的润湿性和渗流性能。
Description
技术领域
本发明属于石油开采领域，涉及一种调剖体系及其使用方法。
背景技术
国内的主要油田都属于陆相沉积，储层非均质性严重，在注水开发过程中，由于驱替流体优先沿着渗透率较高的部位流动，波及不到渗透率较低的部位，从而造成油田采收率较低；同时，驱替流体沿着高渗透部位的突进，造成了注入流体的无效循环，国内东部几个大油田的综合含水量超过90％，这给地面系统带来沉重负荷与很高的操作成本。化学驱(聚合物驱、三元复合驱)的主要作用之一也是利用驱替流体的流变性来改善储层非均质性，并取得了成功，但在化学驱后储层的非均质性会更严重。因此，继续有效开采地下约50％剩余储量的原油的关键是开发能够控制流体突进，扩大波及效率的堵水调剖技术。堵水调剖技术在水驱、化学驱过程中广泛使用，应用原理是控制适当的条件，使注入的流体(包括成胶组分和水)形成具有一定强度的凝胶，这种凝胶是亲水的，外观上起到“固水”的作用，堵塞岩石孔隙。
最早使用的是无机凝胶。例如CN1097451A公开了以硅酸钠为主体，胺盐为活化剂的硅酸凝胶调剖体系，CN1132890C公开了以硫铝酸盐、硬石膏、生石灰、糖蜜等多种组分构成的无机凝胶调剖体系。虽然无机凝胶价格便宜，但形成的凝胶脆性强、粘弹性弱，因此应用范围有限。
有机凝胶是由高分子量聚合物和交联剂形成的凝胶体系，聚合物主要为部分水解的聚丙烯酰胺，所用的交联剂主要有两类，一类是酚醛树脂、三聚氰胺甲醛树脂、酚胺树脂，另一类是过渡金属有机交联剂，主要由Al3+、Cr3+、Ti6+、Zr4+等金属离子与适当的螯合剂形成。例如CN1221628C公开了由聚丙烯酰胺和有机交联剂苯酚、多乙烯多胺组成的有机凝胶；CN102559159A公开了一种由聚丙烯酰胺和酚醛树脂交联的凝胶体系，该调剖剂吸水膨胀，强度高，但选择性差，容易造成储层伤害。
聚丙烯酰胺和交联剂直接反应成胶速度过快，地面施工困难，因此又发明了延缓交联的凝胶体系。CN102807849A公开的冻胶型堵剂采用乌洛托品缓释甲醛，并通过柠檬酸调节体系pH值来控制释放甲醛速度，实现延缓成胶。CN103602325A提供了一种竞争包合剂，通过竞争包合剂与环糊精的包合常数，来调控苯酚的释放速度，从而延缓凝胶的成胶时间。CN102965088A公开了一种疏水缔合聚合物和柠檬酸铝凝胶体系，利用缓凝剂苹果酸钠实现了延缓交联，这有利于调剖体系的大剂量注入和深部调剖。
凝胶调剖体系的缺点是地下成胶不易控制，地面成胶又往往注入困难。为解决这个问题，本领域又发明了体膨颗粒类调剖体系(CN103205247A)，该体系是在聚合物单体聚合的同时进行部分交联反应，制成颗粒。调剖颗粒注入地层后遇水膨胀堵塞孔隙，起到堵水调剖作用，但体膨颗粒强度低剪切易破碎。另外，还提出了一种核壳型无机/有机聚合物复合微球调剖驱油剂(CN102485830A)，单体在无机纳米颗粒(如二氧化硅)的表面聚合，形成聚合物包覆的微球颗粒，该体系具有良好的耐高温高盐性和膨胀性，然而这种复合调剖微球使用时需要配成悬浮体系，对注入设备有更高要求。
以上凝胶类和体膨颗粒类调剖剂都是利用亲水聚合物的“固水”作用实现堵水调剖，如上所述地，凝胶调剖体系的缺点是地下成胶不易控制，地面成胶又注入困难，而体膨颗粒类调剖剂组分复杂，对注入设备要求高。因此，为了改善上述问题，有必要开发新的堵水调剖体系。
发明内容
为了解决现有技术存在的上述技术问题，本发明提供了一种新的堵水调剖体系，该体系使聚合物与交联剂反应形成疏水的固体材料，自发与水分离，吸附在岩石表面，改变岩石表面润湿性，从而改变地层的渗流性能，达到堵水调剖的目的。
本发明提供了一种调剖体系，该调剖体系的组分包含：水溶性聚合物、交联剂和水，所述水溶性聚合物选自聚醚胺中的至少一种，聚醚胺的数均分子量小于1000。
本发明还提供了所述调剖体系的使用方法，该方法包括：将所述水溶性聚合物的水溶液注入地层空隙中，然后转注所述交联剂的水溶液，使所述水溶性聚合物与交联剂发生交联反应，产生聚合物固体材料，吸附在岩石表面。
与常用的聚合物亲水凝胶堵水调剖体系不同，本发明的调剖体系没有“固水”的作用，与凝胶类堵水调剖体系的作用原理不同：本发明的交联反应产物本身不溶于水(不亲水)并且具有粘性，从而会自发地从水中析出并吸附在岩石表面，改变岩石表面的润湿性和渗流性能。
具体实施方式
以下对本发明的具体实施方式进行详细描述。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。
本发明提供了一种调剖体系，该调剖体系包含：水溶性聚合物、交联剂和水，所述水溶性聚合物选自聚醚胺中的至少一种，聚醚胺的数均分子量小于1000。
按照本发明，所述聚醚胺可选自水溶性的任何聚醚胺。优选情况下，所述聚醚胺的化学通式表示为：
其中，R1、R2和R3各自独立地选自直链或支链的C2～C4的脂肪族烃基(优选为饱和的脂肪烃基)，1≤m+n≤20。例如，R1、R2和R3各自独立地选自-CH(CH3)-、-CH2CH2-、-CH(CH3)CH2-或-CH2CH(CH3)-，且m个R2、n个R3相同或不同(在满足上述取值的情况下，m≥0，n≥0)。所述聚醚胺可商购获得，例如亨斯迈公司的牌号为D230、D400的产品，苏州长科实业公司的D系列、ED系列产品。
本发明中，所述交联剂能与聚醚胺发生交联反应生成聚合物交联产物，具体选自二元醛交联剂。优选地，所述交联剂选自乙二醛、戊二醛、丁二醛和乙醛酰三聚体中的至少一种。
按照本发明，所述聚醚胺分子上的两个胺基与二元醛上的两个醛基发生交联反应，生成聚合物固体材料，因此，所述交联剂的量可依据所述水溶性聚合物的量进行选择。通常地，所述水溶性聚合物与所述交联剂的摩尔比为0.5～1.5︰1。
按照一种实施方式，所述调剖体系中，所述水溶性聚合物、所述交联剂分别以各自的水溶液形式存在，即上述提到的水作为水溶性聚合物、交联剂的溶剂使用。
所述水溶性聚合物的水溶液中的水溶性聚合物浓度可参照现有的聚合物驱体系的浓度进行选择，通常浓度可以为0.5～5重量％，优选为3～5重量％。
所述交联剂的水溶液中，交联剂的浓度通常为2～10重量％。
另外，所述水溶液聚合物与交联剂的交联反应通常在碱性条件下进行。因此，在优选情况下，所述水溶性聚合物的水溶液、所述交联剂的水溶液的pH分别均大于8。
本发明还提供了所述调剖体系的使用方法，该方法包括：将所述水溶性聚合物的水溶液注入地层空隙中，然后转注所述交联剂的水溶液，使所述水溶性聚合物与交联剂发生交联反应，产生聚合物固体材料，吸附在岩石表面。
本发明中，所述交联反应的温度大于40℃，优选为50～80℃。
优选地，所述水溶性聚合物的水溶液的注入量为地层空隙体积的5～20体积％。
按照一种优选的实施方式，该使用方法具体包括：
首先，配置浓度为3～5重量％的聚醚胺的水溶液，用氢氧化钠调节溶液的pH大于8，然后将该水溶液注入到地层孔隙中；
接着，按照聚醚胺与所述交联剂的摩尔用量比为1︰1转注交联剂的水溶液(浓度为2～10重量％，pH大于8)；
最后，注入的交联剂与前期注入的聚醚胺发生交联反应，产生水不溶性的聚合物固体材料，吸附在岩石表面，从而起到堵水调剖作用。
以下将通过实施例对本发明进行详细描述。
以下实施例中，采用岩心渗流实验来评价调剖体系的性能：利用岩心驱替模拟装置，首先在温度70℃的恒温箱中岩心抽真空饱和盐水，接着以0.2mL/min的速度向岩心中注水，待注入压力恒定后记录岩心两端的稳定压差ΔP1。然后向岩心中注入一个聚醚胺水溶液段塞(流量为岩心孔隙体积的10体积％，pH为10)，接着注入二醛交联剂溶液(pH为10)，再继续注入盐水，待注入压力恒定后记录岩心两端的稳定压差ΔP2。定义残余阻力系数为：用残余阻力系数来表征调剖体系改变岩心渗流性能的幅度大小，残余阻力系数，改变幅度越大。聚醚胺选用亨斯迈公司的D400、D230系列产品，交联剂为乙二醛，聚醚胺与交联剂的摩尔比均为1︰1。
实施例1
测试条件及结果
实施例2
测试条件及结果
实施例3
测试条件及结果
实施例4
测试条件及结果
由以上可知，在人造岩心(渗透率为600mD～1000mD)上的驱油试验结果表明，实施例的驱油体系的残余阻力系数在3.5以上，远大于水的阻力系数，可以用于堵水调剖。
以上已经描述了本发明的实施例，上述说明是示例性的，并非穷尽性的，并且也不限于所披露的实施例。在不偏离所说明实施例的范围和精神的情况下，对于本技术领域的普通技术人员来说许多修改和变更都是显而易见的。
Claims (9)
1.一种调剖体系，其特征在于，该调剖体系的组分包含：水溶性聚合物、交联剂和水，所述水溶性聚合物选自聚醚胺中的至少一种，聚醚胺的数均分子量小于1000。
2.根据权利要求1所述的调剖体系，其中，所述调剖体系中，所述水溶性聚合物、所述交联剂分别以各自的水溶液形式存在，且水溶液的pH均大于8。
3.根据权利要求2所述的调剖体系，其中，所述水溶性聚合物的水溶液中，水溶性聚合物的浓度为0.5～5重量％，优选为3～5重量％。
4.根据权利要求1所述的调剖体系，其中，所述聚醚胺的化学通式为R1、R2和R3各自独立地选自直链或支链的C2～C4的脂肪族烃基，1≤m+n≤20。
5.根据权利要求1所述的调剖体系，其中，所述交联剂选自乙二醛、戊二醛、丁二醛和乙醛酰三聚体中的至少一种。
6.根据权利要求1-5中任意一项所述的调剖体系，其中，所述水溶性聚合物与所述交联剂的摩尔比为0.5～1.5︰1。
7.权利要求1-6中任意一项所述调剖体系的使用方法，其特征在于，该使用方法包括：将所述水溶性聚合物的水溶液注入地层空隙中，然后转注所述交联剂的水溶液，使所述水溶性聚合物与交联剂发生交联反应，产生聚合物固体材料，吸附在岩石表面。
8.根据权利要求7所述的使用方法，其中，所述交联反应的温度大于40℃，优选为50～80℃。
9.根据权利要求7所述的使用方法，其中，所述水溶性聚合物的水溶液的注入量为地层孔隙体积的5～20体积％。
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