CN117801801B - 一种提高低渗透油气藏压裂液返排率的界面改性剂及其制备方法和应用 - Google Patents
一种提高低渗透油气藏压裂液返排率的界面改性剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明提供了一种提高低渗透油气藏压裂液返排率的界面改性剂及其制备方法和应用,涉及油气藏压裂液技术领域。按重量份数计,包括以下组分:亲油疏水界面修饰剂20‑30份、界面偶联剂2‑10份、有机溶剂40‑50份和水20‑30份;其中,亲油疏水界面修饰剂包括3‑甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷和1H,1H,2H,2H‑全氟癸基三甲氧基硅烷中的一种或两种;界面偶联剂包括正硅酸乙酯和乙烯基三甲氧基硅烷中的一种或两种。本发明提供的提高低渗透油气藏压裂液返排率的界面改性剂,可改变岩石界面性质,增加水对岩石表面润湿角θ,当岩石表面水润湿角大于90°时,毛细管阻力值为负值,达到降低毛细管阻力的目的,进而达到提高低渗透油气藏压裂液返排率的技术效果。
Description
技术领域
本发明属于油气藏压裂液技术领域,具体涉及一种提高低渗透油气藏压裂液返排率的界面改性剂及其制备方法和应用。
背景技术
压裂液是一种具有高压高温稳定性的液体,在页岩气、煤层气、油田开发中被广泛应用。压裂液一般由水、砂、化学添加剂和其他助剂等组成。其中,水扮演了媒介的作用,砂可以增强岩层中孔隙的稳固性,化学添加剂则可以调节压裂液的性能和保证其的稳定性。压裂液的主要作用是将砂颗粒携带注入到岩层中,使其裂缝扩张并形成一个通道,使油气藏中的油气能够顺畅地流出。另外,压裂液还具有抗滤失、抗堵塞、抗污染等功能,可以防止无用杂质或沉积物进入井内,保证油气开采的顺利推进。
由此可见,压裂液的助剂成分对提高油气开采效果有重要作用。现有技术中,压裂液助排技术都是通过加入助剂降低液体表面张力,达到减小毛细管阻力的目的。但将常规压裂液应用于我国鄂尔多斯盆苏里格的上古生界山西组、石盒子组进行油气开采时,经常会出现低压致密气藏压裂后,液体滞留储层难返排、返排周期长、效率低等问题,导致目的井低产或死井的现象。
基于此问题,研发一种与降低液体表面张力无关的、提高致密油气藏压裂液返排率的界面改性剂,是本领域技术人员亟待解决的问题。
发明内容
本发明的目的在于提供一种提高低渗透油气藏压裂液返排率的界面改性剂,用于解决低压致密油气藏压裂液水锁、返排周期长、返排动力不足的难题,从而有效提高压裂液返排率、恢复储层渗流通道。
为实现上述目的,本发明提供一种提高低渗透油气藏压裂液返排率的界面改性剂,按重量份数计,包括以下组分:
亲油疏水界面修饰剂20-30份、界面偶联剂2-10份、有机溶剂40-50份和水20-30份。
在一优选的实施方式中,所述亲油疏水界面修饰剂22-28份、界面偶联剂3-7份、有机溶剂40-48份和水20-30份。
在一优选的实施方式中,所述亲油疏水界面修饰剂25份、界面偶联剂2份、有机溶剂48份和水25份。
在一优选的实施方式中,所述亲油疏水界面修饰剂20份、界面偶联剂5份、有机溶剂50份和水25份。
在一优选的实施方式中,所述亲油疏水界面修饰剂25份、界面偶联剂5份、有机溶剂45份和水25份。
在一优选的实施方式中,所述亲油疏水界面修饰剂30份、界面偶联剂5份、有机溶剂40份和水25份。
在一优选的实施方式中,所述亲油疏水界面修饰剂20份、界面偶联剂10份、有机溶剂45份和水25份。
在一优选的实施方式中,所述亲油疏水界面修饰剂包括3-甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷和1H,1H,2H,2H-全氟癸基三甲氧基硅烷中的一种或两种。
在一优选的实施方式中,所述3-甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷和1H,1H,2H,2H-全氟癸基三甲氧基硅烷的质量比为(2:8)-(4:6)。
在一优选的实施方式中,所述3-甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷和1H,1H,2H,2H-全氟癸基三甲氧基硅烷的质量比为3:7。
在本发明中,所用3-甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷,分子式为C16H38O5Si4,CAS编号为17096-07-0;所用1H,1H,2H,2H-全氟癸基三甲氧基硅烷分子式为C13H13F17O3Si,CAS编号为83048-65-1。
在一优选的实施方式中,所述界面偶联剂包括正硅酸乙酯和乙烯基三甲氧基硅烷中的一种或两种。
在一优选的实施方式中,所述正硅酸乙酯和乙烯基三甲氧基硅烷的质量比为1:(0.5-2)。
在一优选的实施方式中,所述正硅酸乙酯和乙烯基三甲氧基硅烷的质量比为1:1。
在一优选的实施方式中,所述有机溶剂包括醇基溶剂和醇醚类溶剂中的一种或多种;优选的,所述醇基溶剂包括甲醇、乙醇、丙三醇中的一种或多种;所述醇醚类溶剂包括乙二醇单丁醚、丙三醇丁醚中的一种或多种。
据Laplace方程P=2δcosθ/r可知,影响毛细阻力三因素是液体表面张力δ、水对岩石表面润湿角θ及毛细管半径r等。现有技术中通常通过降低液体表面张力的方式提高压裂液的返排率,但针对低压致密油气藏则效果较差。因此,本发明研发设计通过增加水对岩石表面润湿角,当θ>90°时,毛细管阻力为负值,起到助排的目的。为达到此目的,本发明创造性的设计了前述界面改性剂的配方及用量,使得界面改性剂通过压裂液携带至目的层时,可在地层温度下与岩石表面硅氧四面体羟基发生化学反应,显著增加油气藏地层水对岩石润湿角,大大降低了毛细管阻力。当润湿角大于90°时,毛细管阻力为负值,进而有效提高压裂液的返排效率和周期,降低压裂液对储层的伤害,恢复储层渗流通道的能力。
本发明的另一目的在于提供一种提高低渗透油气藏压裂液返排率的界面改性剂的制备方法,仅需按重量份准确称取各组分,将15-25份亲油疏水界面修饰剂、2-8份界面偶联剂、40-60份有机溶剂和20-30份水,混合均匀,搅拌即得。整体加工方法简单、高效,对作业环境和操作人员无特殊限定,尤其适合在各种工况环境下生产制备。
本发明的另一目的在于提供一种提高低渗透油气藏压裂液返排率的界面改性剂的应用,仅需将制备得到的界面改性剂加入到压裂液中,以压裂液为载体,将界面改性剂携带至目的储层,在地层温度下能对岩石表面修饰,从而提高储层返排率,恢复储层渗流通道;所述界面改性剂用量占压裂液总重量的0.1-0.5wt%。
在一优选的实施方式中,所述界面改性剂用量占压裂液总重量的0.2-0.4wt%。
在一优选的实施方式中,所述储层为致密油储层或页岩气储层;所述储层温度为30-180℃。
在一优选的实施方式中,在压裂液中加入所述界面改性剂后,岩石界面对水润湿角大于90°,返排率提高15.0-50.0wt%,返排启动压力降低1.5-6.0倍。
与现有技术相比,本发明的技术方案具有如下优点:
1、本发明配方精简,除水以外仅三组组分,易于采购和制备。在使用方法上,本发明中无需改变现有压裂液的应用方法,仅需在普通压裂液中加入少量本发明所提供的界面改性剂,即可有效提高压裂液返排率,恢复储层渗流通道,操作简便、普适性好、应用效果优异。
2、与现有技术常规构思不同,本发明通过增加水对岩石表面润湿角,当θ>90°时,毛细管阻力成为负值,起到助排的目的。且岩石表面修饰后时有效期效长,适合储层温度广30℃-180℃、提高压裂液返排率15%-50%、施工安全方便、对联合站处理油水***无影响、耐碱耐盐,适用于所有低渗油气藏储层压裂后液体返排。
附图说明
从下面结合附图对本发明实施例的详细描述中,本发明的这些和/或其它方面和优点将变得更加清楚并更容易理解,其中:
图1为本发明制备得到的界面改性剂与岩石改性的反应机理;
图2为毛细管力驱替和吸入示意图,显示毛细管驱替和吸入时,毛细管阻力表观形态与水对岩石的润湿角的关系的原理示意;
图3为本发明制备得到的界面改性剂修饰后岩石表面滴加油水滴现象。
具体实施方式
为了使本领域技术人员更好地理解本发明,下面结合附图和具体实施方式对本发明作进一步详细说明,但应当理解本发明的保护范围并不受具体实施方式的限制。
本发明实施例通过提供一种提高低渗透油气藏压裂液返排率的界面改性剂及其制备方法和应用,解决现有技术中对于低压致密气藏压裂后,液体滞留储层难返排、返排周期长、效率低等问题。通过配方及用量设计,使得界面改性剂与岩石表面的-OH发生-Si-O-共价反应。如图1所示,岩石表面的-O或-OH在自身水解作用下,与修饰剂分子中Si结合,形成稳定的Si-O结构。因此,改变了岩石界面性质,增加了水对岩石表面润湿角θ,当岩石表面水润湿角大于90°时,毛细管阻力值为负值,达到降低毛细管阻力的目的,进而达到提高低渗透油气藏压裂液返排率的技术效果。
具体的,毛细管阻力转为负值的机理为:根据Laplace方程P=2δcosθ/r可知,当流体表面张力δ与毛细管半径r一定时,毛细管阻力值与θ有关。根据表1润湿角与余弦值对应关系可以看出,当θ大于90°时,COSθ为负值,因此,毛细管阻力变为负值,大大降低了毛细管阻力。
表1润湿角与余弦值对应关系
下面通过具体实施例详细说明本申请的技术方案:
若未特别指明,本发明中所用技术手段为本领域技术人员所熟知的常规手段,本发明中所用的各种原材料、试剂、仪器和设备等均可通过市场购买得到或者可通过现有方法制备得到。本发明所用试剂如无特殊说明均为分析纯。
在本发明中,重量份可以是μg、mg、g、kg等本领域公知的重量单位,也可以是其倍数,如1/10、1/100、10倍、100倍等。
实施例1
界面改性剂的配方设计:按表2编号的不同用量设计界面改性剂组分。
其中,编号1#-4#,所用亲油疏水界面修饰剂为:3-甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷,所用界面偶联剂为正硅酸乙酯和乙烯基三甲氧基硅烷按质量比1:1,所用有机溶剂为无水乙醇;
编号5#-9#,所用亲油疏水界面修饰剂为:3-甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷和1H,1H,2H,2H-全氟癸基三甲氧基硅烷按质量比3:7,所用界面偶联剂为正硅酸乙酯和乙烯基三甲氧基硅烷按质量比1:1,所用有机溶剂为无水乙醇;
编号10#-12#,所用亲油疏水界面修饰剂为:3-甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷和1H,1H,2H,2H-全氟癸基三甲氧基硅烷按质量比3:7,所用界面偶联剂为正硅酸乙酯,所用有机溶剂为无水乙醇。
制备方法及效果:按表2编号所示重量份数准确称取原料,搅拌均匀,即得。制备得到的界面改性剂润湿角数据如表2所示。
表2界面改性剂配方设计及润湿角数据
效果例1 7#配方界面改性剂技术效果:
本发明所提供的界面改性剂形成的化学键与常规压裂液形成的物理吸附化学键有明显差异,具体如表3所示。
表3岩石界面反应化学键与物理吸附的键能对比
使用7#配方界面改性剂对岩石表面修饰后,向其表面分别滴加1滴水(染色)和1滴原油,都表现为圆球状,说明修饰效果良好,具体如图2所示。
另测试4#、8#、9#、12#润湿角在90°以上的界面改性剂,其均有与7#界面改性剂近似的键能,且修饰岩石表面后均有较好的疏水疏油效果。
效果例2 7#配方界面改性剂制备压裂液的实验效果测定
(一)提高返排率和返排启动压力降低倍数测定
(1)配制样品:按照配方A和B的原料及配比,配置样品各500ml,备用;其中,配方A:0.1%wt乳液减阻剂(聚丙烯酰胺)+0.1%wt助排剂(OP-10)+0.1%wtKCL,余量为水;
配方B:0.1%wt乳液减阻剂(聚丙烯酰胺)+0.1%wt助排剂(OP-10)+0.1%wtKCL+0.1%wt界面修饰剂(7#配方),余量为水;
(2)人造岩芯驱替实验:参考SY/T5590中第7款步骤操作。
a测试人工岩芯(选用渗透率1.0-5.0md)孔隙体积,并记为V0;
b将人造岩芯置入夹持器并安装到驱替装置上,置于60℃烘箱中,恒温60min;
c用配方A驱替,注入量为2.0PV后,用氮气返排,缓缓释放氮气,记录岩芯入口出液时的氮气压力(记为P1)和返排总液量(记为V1);
d按照a)-c)步骤,用配方B驱替,注入量为2.0PV后,用氮气返排,缓缓释放氮气,记录岩芯入口出液时的氮气压力(记为P2)和返排总液量(记为V2);平行进行三组实验。
(3)计算公式:
①提高返排率(F)按式(1)计算:
F=F2-F1………………………………………………………(1)
式中:
F——提高返排率
F1——配方A(加入助排剂)滑溜水返排率(V1/V0);
F2——配方B(加入界面修饰剂)滑溜水返排率(V2/V0);
②返排启动压力降低倍数(G)计算按(2)式计算:
G=P2/P1………………………………………………………(2)
式中:
G——返排启动压力降低倍数
P1——配方A(加入助排剂)滑溜水返排启动压力,MPa;
P2——配方B(加入界面修饰剂)滑溜水返排启动压力,MPa;
(二)水润湿角测定
a.用清水配置0.4%样品水溶液100ml,备用;
b.用两片干净的载玻片浸入a中溶液中,完全浸湿后取出;
c.放入50℃烘箱中恒温静置30min;
d按照接触角测试仪JC2000CI说明书操作步骤测试水对载玻片的接触角,并记录。
结果与讨论:在常规压裂液中加入7#配方界面改性剂,返排率可提高15.0-50.0wt%,返排启动压力降低1.5-6.0倍。
效果例3 7#配方界面改性剂制备压裂液的矿井实测数据
实验步骤:在鄂尔多斯某区块致密油储层,其储层温度为120℃左右。由混砂车车载泵或油泵按施工压裂液排量对应的比例抽到混砂罐中,边加入边施工。界面改性剂以压裂液为载体,携带至目的层,随着压裂液持续注入,裂缝不断向深部延伸、扩展,随之,界面改性剂与深部岩石表面结合发生反应,改善岩性表面。
其中,所用压裂液配方1瓜尔胶体系:0.3%界面修饰剂(7#配方)+0.3%瓜尔胶+0.1%助排剂(OP-10十二烷基酚聚氧乙烯醚)+0.1%杀菌剂(戊二醛)+0.3%粘土稳定剂(KCL)+0.1%pH调节剂(NaOH)+0.3%交联剂(硼砂),余量为水;
配方2乳液减阻剂体系:0.2%界面改性剂+0.1%乳液减阻剂(HPAM)+0.1%助排剂(OP-10十二烷基酚聚氧乙烯醚)+0.1%杀菌剂(戊二醛)+0.3%粘土稳定剂(KCL),余量为水。
实测发现,界面改性剂均不与两种配方的原料发生反应。
在现场压裂施工4口井矿场进行实验,以配方1瓜尔胶液体系压裂液处理3口实验井,以配方1未加入界面改性剂的压裂液处理空白井,对比压裂液返排率、恢复压力值、产量等,记录实测数据,结果如表4所示:
表4 3口井实验井与1口井空白井效果对比
结果与讨论:通过3口井实验井与1口井空白井效果可以看出,以空白井为基准,3口实验井平均返排率提高了27.7%;生产压力提高了6MPa;火焰高度平均高2-3m,由此可见,界面修饰剂技术应用效果非常明显。
由效果例1-3可以看出,本发明所提供的提高低渗透油气藏压裂液返排率的界面改性剂,可适用于多种配方体系的压裂液中,将其应用于致密油储层或页岩气储层压裂时,可通过增加水对岩石表面润湿角,当θ>90°时,毛细管阻力转为负值,起到助排的目的,尤其适用于所有低渗油气藏储层压裂后液体返排。
前述对本发明的具体示例性实施方案的描述是为了说明和例证的目的。这些描述并非想将本发明限定为所公开的精确形式,并且很显然,根据上述教导,可以进行很多改变和变化。对示例性实施例进行选择和描述的目的在于解释本发明的特定原理及其实际应用,从而使得本领域的技术人员能够实现并利用本发明的各种不同的示例性实施方案以及各种不同的选择和改变。本发明的范围意在由权利要求书及其等同形式所限定。
Claims (8)
1.一种提高低渗透油气藏压裂液返排率的界面改性剂,其特征在于,按重量份数计,包括以下组分:
亲油疏水界面修饰剂20-30份、界面偶联剂2-10份、有机溶剂40-50份和水20-30份;
其中,所述亲油疏水界面修饰剂包括3-甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷和1H,1H,2H,2H-全氟癸基三甲氧基硅烷中的一种或两种;
所述界面偶联剂包括正硅酸乙酯和乙烯基三甲氧基硅烷中的一种或两种。
2.如权利要求1所述提高低渗透油气藏压裂液返排率的界面改性剂,其特征在于,所述3-甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷和1H,1H,2H,2H-全氟癸基三甲氧基硅烷的质量比为(2:8)-(4:6)。
3.如权利要求1所述提高低渗透油气藏压裂液返排率的界面改性剂,其特征在于,所述正硅酸乙酯和乙烯基三甲氧基硅烷的质量比为1:(0.5-2)。
4.如权利要求1所述提高低渗透油气藏压裂液返排率的界面改性剂,其特征在于,所述有机溶剂包括醇基溶剂和醇醚类溶剂中的一种或多种。
5.如权利要求1-4任意一项所述提高低渗透油气藏压裂液返排率的界面改性剂的制备方法,包括以下步骤:
按重量份准确称取各组分,将15-25份亲油疏水界面修饰剂、2-8份界面偶联剂、40-50份有机溶剂和20-30份水,混合均匀,搅拌即得。
6.如权利要求1-4任意一项所述提高低渗透油气藏压裂液返排率的界面改性剂的应用,其特征在于,将所述界面改性剂加入到压裂液中,以压裂液为载体,将界面改性剂携带至目的储层,在地层温度下能对岩石表面修饰,从而提高储层返排率,恢复储层渗流通道;所述界面改性剂用量占压裂液总重量的0.1-0.5wt%。
7.如权利要求6所述提高低渗透油气藏压裂液返排率的界面改性剂的应用,其特征在于,所述储层为致密油储层或页岩气储层;所述储层温度为30-180℃。
8.如权利要求6所述提高低渗透油气藏压裂液返排率的界面改性剂的应用,其特征在于,在压裂液中加入所述界面改性剂后,岩石界面对水润湿角大于90°,返排率提高15.0-50.0wt%,返排启动压力降低1.5-6.0倍。
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