CN113403042A - 一种有机-无机纳米复合水凝胶及水基钻井液 - Google Patents
一种有机-无机纳米复合水凝胶及水基钻井液 Download PDFInfo
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Abstract
本发明公开了一种有机‑无机纳米复合水凝胶封堵剂及水基钻井液。该水基钻井液所用封堵剂为有机‑无机纳米复合水凝胶,所述有机‑无机纳米复合水凝胶合成原料包括二氧化硅,甲基丙烯酸,N,N‑二甲基丙烯酰胺,N,N‑亚甲基双丙烯酰胺;所述钻井液包含有本发明的有机‑无机纳米复合水凝胶。本发明的有机‑无机纳米复合水凝胶作为纳米封堵剂,其粒径分布在30‑600nm之间,可以有效阻止钻井液滤液侵入地层,防止井壁坍塌等事故的发生,特别适用于页岩地层的纳米封堵,其制备方法原理可靠,具有广阔的市场前景。
Description
技术领域
本发明涉及油气田钻井技术领域,具体涉及一种有机-无机纳米复合水凝胶封堵剂及其包含有该纳米封堵剂的水基钻井液。
背景技术
目前在国内和国外钻井中,经常存在井壁不稳定问题,国内外数百口井的统计说明,所钻泥页岩地层占所钻总地层的70%,而90%以上的井塌发生在泥页岩地层。页岩具有特殊的裂缝一孔隙结构,属超低孔、低渗类型,多为纳米级孔喉。针对页岩气的成藏特征,水平井钻井已成为页岩气开发的主要钻井方式。不管使用水基钻井液体系或者油基钻井液体系钻页岩地层都会出现井壁垮塌的现象,其根本原因是“水力劈裂作用”,钻井液或滤液进入裂缝,使裂缝张开,同时大大降低缝面间摩擦力,使坍塌压力大幅度上升。若不能有效封堵住裂缝阻断泥浆液相进入裂缝,则不能防塌。
钻井液中常用的磺化沥青或乳化沥青的粒径大多在微米级别,能对微米级别的裂缝进行有效封堵,但对于尺寸一般在纳米-微米之间的裂缝,其粒子只能在裂缝表面沉积,极易被钻井液冲刷,钻具的碰撞等作用破坏,起不到良好的封堵效果。因此对易造成井壁失稳的纳米孔缝进行有效的封堵是保持井壁稳定的重点,也是钻井工程中急需解决的难点
发明内容
针对目前常规封堵剂无法有效封堵泥页岩中的纳米裂缝而导致的井壁失稳问题,本发明提供了一种有机-无机纳米复合水凝胶封堵剂,其粒径为纳米级,能够有效对泥页岩地层中的纳米级裂缝进行封堵,从而达到稳定井壁的目的。且研制了一种能适用于页岩地层的新型纳米封堵水基钻井液替代油基钻井液能够解决井壁稳定、储层污染等问题。
为实现上述目的,本发明的技术方案为:一种有机-无机纳米复合水凝胶封堵剂及其水基钻井液。所述有机-无机纳米复合水凝胶封堵剂的原料包括为二氧化硅,甲基丙烯酸,N,N- 二甲基丙烯酰胺,所述有机-无机纳米复合水凝胶封堵剂的制备步骤如下:
(1)纳米二氧化硅的改性:将纳米二氧化硅置于75-80℃真空干燥箱中干燥10-12h,准确称取干燥后的纳米二氧化硅2-3g,加入到40-50mL乙醇/水的分散液中,超声分散40-50min,然后边搅拌边滴加2-3gKH550,在75-80℃反应8-10h后,用乙醇洗涤,反复3-5次,最后置于55-60℃真空干燥箱中干燥8-10h得到改性纳米二氧化硅。
(2)有机-无机纳米复合水凝胶的制备:
①向反应器中加入改性后的纳米二氧化硅,加超纯水超声分散10-15min;
②加入共聚单体甲基丙烯酸和N,N-二甲基丙烯酰胺,交联剂N,N-亚甲基双丙烯酰胺,保持快速搅拌至溶解,通入氮气20-30min;
③将反应体系升温至55-60℃,保持搅拌,将过硫酸铵加入到混合体系内,恒温反应3-4h;
④反应完毕后,将反应体系降至20-25℃,制备得的样品用蒸馏水洗涤至中性,接着在烘箱中60-70℃干燥;
⑤将烘干的样品进行研磨,然后密封保存。
所述改性后的纳米二氧化硅的加量为甲基丙烯酸与N,N-二甲基丙烯酰胺总重量的 5-15%;
所述甲基丙烯酸的加量为3-3.5g;
所述甲基丙烯酸与N,N-二甲基丙烯酰胺的重量比为1:1-1.5;
所述N,N-亚甲基双丙烯酰胺的加量为0.02-0.06g;
所述过硫酸铵的加量为0.05-0.12g。
本发明的另一种目的是提供一种水基钻井液,所述钻井液添加有本发明所述的一种有机- 无机纳米复合水凝胶封堵剂。
以重量份计,所述钻井液的组成如下:100重量份的水+2-4重量份膨润土+0.1-0.3重量份 NaOH+0.03-0.05重量份KPAM+0.5-0.8重量份PAC-LV+4-5重量份RSTF+4-6重量份SMP-1+4-5重量份FRH+3-4重量份PPL+4-6重量份FK-10+0.3-0.5重量份SP-80+1-5重量份有机-无机纳米复合水凝胶封堵剂+1-1.5重量份除硫剂+5-15重量份重晶石。
本发明有益效果如下:
本发明所制备的有机-无机纳米复合水凝胶的粒径分布在30-600nm之间,能够有效的对泥页岩地层中的纳米级别裂缝进行封堵,从而达到稳定井壁的效果;本发明所使用的水基钻井液在泥页岩地层条件下的流变性、稳定性以及封堵性等方面性能良好。
附图说明
图1为实施例一中有机-无机纳米复合水凝胶的粒径分布图;
图2为实施例二中有机-无机纳米复合水凝胶的粒径分布图。
具体实施方式
下面将结合本发明实施例,对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
本实施例中,若无特殊说明,所述的份数均为重量份数。
一、有机-无机纳米复合水凝胶的合成:
实施例1:
纳米二氧化硅的改性:将纳米二氧化硅置于75℃真空干燥箱中干燥12h,准确称取干燥后的纳米二氧化硅2g,加入到40mL乙醇/水的分散液中,超声分散45min,然后边搅拌边滴加2.5gKH550,在75℃反应9h后,用乙醇洗涤,反复4次,最后置于58℃真空干燥箱中干燥10h得到改性纳米二氧化硅。
有机-无机纳米复合水凝胶的制备:向反应器中加入0.3g改性后的纳米二氧化硅,加50ml 超纯水超声分散12min;加入3g共聚单体甲基丙烯酸和3gN,N-二甲基丙烯酰胺,0.04g交联剂N,N-亚甲基双丙烯酰胺,保持快速搅拌至溶解,通入氮气25min;将反应体系升温至55℃,保持搅拌,将0.06g过硫酸铵加入到混合体系内,恒温反应3h;反应完毕后,将反应体系降至22℃,制备得的样品用蒸馏水洗涤至中性,接着在烘箱中65℃干燥。
实施例2:
纳米二氧化硅的改性:将纳米二氧化硅置于80℃真空干燥箱中干燥12h,准确称取干燥后的纳米二氧化硅2.5g,加入到45mL乙醇/水的分散液中,超声分散50min,然后边搅拌边滴加3gKH550,在80℃反应8h后,用乙醇洗涤,反复5次,最后置于60℃真空干燥箱中干燥9h得到改性纳米二氧化硅。
有机-无机纳米复合水凝胶的制备:向反应器中加入0.65g改性后的纳米二氧化硅,加50ml 超纯水超声分散15min;加入3g共聚单体甲基丙烯酸和3.5gN,N-二甲基丙烯酰胺,0.05g 交联剂N,N-亚甲基双丙烯酰胺,保持快速搅拌至溶解,通入氮气30min;将反应体系升温至 60℃,保持搅拌,将0.08g过硫酸铵加入到混合体系内,恒温反应4h;反应完毕后,将反应体系降至25℃,制备得的样品用蒸馏水洗涤至中性,接着在烘箱中70℃干燥。
为了进一步说明本发明有机-无机纳米复合水凝胶封堵剂以及水基钻井液的效果,对实施例1、实施例2制备的有机-无机纳米复合水凝胶封堵剂以及水基钻井液进行性能测试。
二、性能测试
1、有机-无机纳米复合水凝胶封堵剂粒径测试
利用美国布鲁克海文仪器公司生产的BI-200SM型激光散射仪对纳米微乳液封堵剂进行粒径测试,两个实施例中制备的有机-无机纳米复合水凝胶封堵剂粒径测试结果分别如图1、图2所示。本发明有机-无机纳米复合水凝胶封堵剂的粒径分布在30-600nm之间,平均粒径为77nm,说明本发明合成的封堵剂是纳米尺寸的,且该封堵剂分布范围宽,能有效封堵不同纳米尺寸的纳米裂缝。
2.钻井液流变性能和失水造壁性能测试
本发明主要以以下具体配方对有机-无机纳米复合水凝胶封堵剂的应用方式进行说明。以100质量份的水为基准,具体配方为:以重量份计,所述钻井液的组成如下:100重量份的水 +2-4重量份膨润土+0.1-0.3重量份NaOH+0.03-0.05重量份KPAM+0.5-0.8重量份PAC-LV+4-5 重量份RSTF+4-6重量份SMP-1+4-5重量份FRH+3-4重量份PPL+4-6重量份FK-10+0.3-0.5 重量份SP-80+1-5重量份有机-无机纳米复合水凝胶封堵剂+1-1.5重量份除硫剂+5-15重量份重晶石。
具体配制过程如下∶
(1)、预水化膨润土浆
在100质量份温度为70℃的自来水中加入3质量份的膨润土,在室温下搅拌均匀后加入 0.25质量份的NaOH,充分搅拌30min后,密封静置水化24h。
(2)、钻井液的配制
分别取400mL预水化土膨润土浆4份,再依次加入0.3重量份NaOH,0.05重量份KPAM, 0.7重量份PAC-LV,5重量份RSTF,6重量份SMP-1,5重量份FRH,4重量份PPL,5重量份FK-10,0.5重量份SP-80,1.4重量份除硫剂,14重量份重晶石。每加入一种物质,需搅拌10~15min。
搅拌均匀后,分别向4份膨润土浆中加入0、4g、8g、12g、16g上述方式制备的有机-无机纳米复合水凝胶封堵剂,制得含有机-无机纳米复合水凝胶封堵剂添加量不同的五种钻井液,分别命名为钻井液1、钻井液2、钻井液3、钻井液4和钻井液5,其中钻井液1不含有机-无机纳米复合水凝胶封堵剂,作为空白实验组。
依据中华人民共和国国家标准GB/T 16783.1-2014《石油天然气工业钻井液现场测试第1 部分∶水基钻井液》,分别对步骤配制好的钻井液进行老化前后钻井液流变性和失水造壁性进行测试,结果记录在表1中。
表1钻井液流变性能及滤失性能记录表
注∶AV—表观黏度,单位为mPa·s;PV—塑性黏度,单位为mPa·s;YP—动切力,单位为Pa;API—常温中压滤失量,单位为mL;HTHP—高温高压滤失量,单位为mL。
由表1所示的结果可以看出,与不加有机-无机纳米复合水凝胶封堵剂的钻井液相比,当有机-无机纳米复合水凝胶在钻井液中加量为4-16质量份时,钻井液性能未受到明显的影响,表明该钻井液封堵剂具有良好的配伍性能。随着有机-无机纳米复合水凝胶封堵剂加量的增加,在同一实验条件下钻井液的表观黏度、塑性黏度逐渐增大,对切力的影响较小。在150℃下老化16h后的钻井液,随着有机-无机纳米复合水凝胶封堵剂加量的增加,高温高压滤失量逐渐减小,且在加量为12质量份时高温高压滤失量最小,说明有机-无机纳米复合水凝胶封堵剂具有良好的流变性能和失水造壁性能,能有效降低钻井液高温高压滤失量,在高温环境下也能提供较好的封堵性能,有效阻止滤液进入地层,提高井壁稳定性。
3、钻井液封堵性能测试
使用人造岩芯模拟地层纳微米裂缝地层,通过测量钻井液体系在人造岩芯中的平均流量,通过达西公式,计算加入有机-无机纳米复合水凝胶封堵剂前后,人造岩芯的渗透率 K=Qμl/(AΔP),从而计算得到有机-无机纳米复合水凝胶封堵剂对人造岩芯的封堵率,评价其封堵性能。表2所示为有机-无机纳米复合水凝胶对人造岩芯封堵效果记录表。
表2人造岩芯封堵性的评价实验数据表
注∶岩芯长度为5cm,直径为2.5cm。
由表2所表示的结果可知,与不加有机-无机纳米复合水凝胶封堵剂的基浆相比,加入不同比例有机-无机纳米复合水凝胶封堵剂后,对岩芯的封堵率增加了,且当加入有机-无机纳米复合水凝胶封堵剂为12g时,对岩芯的封堵率均达到95%,这表明有机-无机纳米复合水凝胶封堵剂可以对微裂缝实现有效的封堵,进而阻止钻井液进入岩芯。
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,虽然本发明已以较佳实施例揭露如上,然而并非用以限定本发明,任何熟悉本专业的技术人员,在不脱离本发明技术方案范围内,当可利用上述揭示的技术内容作出些许更动或修饰为等同变化的等效实施例,但凡是未脱离本发明技术方案的内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。
Claims (5)
1.一种有机-无机纳米复合水凝胶封堵剂及水基钻井液,其特征在于,所述一种有机-无机纳米复合水凝胶的原料为二氧化硅(15+5nm),甲基丙烯酸,N,N-二甲基丙烯酰胺,采用步骤如下制备而成:
(1)纳米二氧化硅的改性:将纳米二氧化硅置于75-80℃真空干燥箱中干燥10-12h,准确称取干燥后的纳米二氧化硅2-3g,加入到40-50mL乙醇/水的分散液中,超声分散40-50min,然后边搅拌边滴加3-氨丙基三乙氧基硅烷(KH550)2-3g,在75-80℃反应8-10h后,用乙醇洗涤,反复3-5次,最后置于55-60℃真空干燥箱中干燥8-10h得到改性纳米二氧化硅;
(2)有机-无机纳米复合水凝胶的制备:
①向反应器中加入改性后的纳米二氧化硅,加超纯水超声分散10-15min;
②加入共聚单体甲基丙烯酸和N,N-二甲基丙烯酰胺,交联剂N,N-亚甲基双丙烯酰胺,保持快速搅拌至溶解,通入氮气20-30min;
③将反应体系升温至55-60℃,保持搅拌,将过硫酸铵加入到混合体系内,恒温反应3-4h;
④反应完毕后,将反应体系降至20-25℃,制备得的样品用蒸馏水洗涤至中性,接着在烘箱中60-70℃干燥;
⑤将烘干的样品进行研磨,然后密封保存。
2.根据权利要求1所述的一种有机-无机纳米复合水凝胶封堵剂及水基钻井液,其特征在于,所述改性后的纳米二氧化硅的加量为甲基丙烯酸和N,N-二甲基丙烯酰胺总重量的5-15%;所述甲基丙烯酸的加量为3-3.5g,甲基丙烯酸与N,N-二甲基丙烯酰胺的重量比为1:1-1.5,N,N-亚甲基双丙烯酰胺的加量为0.02-0.06g,过硫酸铵的加量为0.05-0.12g。
3.一种水基钻井液,其特征在于,所述钻井液中添加有权利要求1-3任一所述的有机-无机纳米复合水凝胶封堵剂。
4.根据权利要求3所述的水基钻井液,其特征在于,所述钻井液包括以下组分:水,膨润土,NaOH,聚丙烯酰胺钾盐(KPAM),聚阴离子纤维素(PAC-LV),腐植酸丙磺酸酰胺多元共聚物(RSTF),磺化酚醛树脂(SMP-1),酰胺基胺(FRH),防卡润滑剂(FK-10),防卡降滤失剂(PPL),乳化剂(SP-80),有机-无机纳米复合水凝胶封堵剂,除硫剂,CaO,重晶石。
5.根据权利要求4所述的水基钻井液,其特征在于,以100重量份的水为基准,所述膨润土的加量为2-4重量份,所述NaOH的加量为0.1-0.3重量份,所述KPAM的加量为0.03-0.05重量份,所述PAC-LV的加量为0.5-0.8重量份,所述RSTF的加量为4-5重量份,所述SMP-1的加量为4-6重量份,所述FRH的加量为4-5重量份,所述PPL的加量为3-4重量份,所述SP-80的加量为0.3-0.5重量份,所述有机-无机纳米复合水凝胶封堵剂的加量为1-5重量份,所述除硫剂的加量为1-1.5重量份,所述重晶石的加量为5-15重量份。
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