CN113265234A - 一种耐高温碳纳米管杂化压裂液及其制备方法 - Google Patents
一种耐高温碳纳米管杂化压裂液及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种耐高温碳纳米管杂化压裂液及其制备方法。该耐高温碳纳米管杂化压裂液包括:稠化剂、交联剂、助排剂、粘土稳定剂、破乳剂、NaHCO3和改性碳纳米管,余量水;其中,所述稠化剂为瓜胶原粉、羟丙基瓜尔胶、羧甲基羟丙基瓜尔胶中的一种或两种以上的混合物;所述改性碳纳米管为水性丙烯酸树脂包覆的碳纳米管。本发明采用非常经济的水性丙烯酸树脂包覆在碳纳米管表面,水溶性的水性丙烯酸树脂极大的增加了碳纳米管的水分散性,得到了一种价格低廉的耐温、抗剪切的碳纳米管杂化高温压裂液体系。
Description
技术领域
本发明涉及瓜胶压裂液技术领域,具体涉及一种耐高温碳纳米管杂化压裂液及其制备方法。
背景技术
瓜胶压裂液已被广泛应用在油田的增产改造中,现有的压裂液体系基本能满足国内主要的储层需要,但是随着勘探开发的发展,越来越深的井被开发,随之井底的温度也越来越高,同时施工时,液体承受的剪切时间更长,所以对压裂液的性能提出了更高的要求。
为了提高压裂液的耐温性能,人们研发了耐高温的稠化剂,使得稠化剂在高温下主链能保持稳定;采用重金属交联剂,使交联形成的网络结构更加致密,抗剪切性能增强;使用温度稳定剂去除体系中的氧,消除高温下氧的氧化作用。但是采用改进稠化剂、重金属交联剂的方法,增加了压裂液体系的残渣含量,增加了压裂液的摩阻,使得施工难度增加。所以需要采用新的思维研制能满足耐温抗剪切需要的压裂液体系。
碳纳米管是一种无机材料,具有很好的力学性能,如能将碳纳米管引入到压裂液体系中,使碳纳米管在压裂液体系中起到骨架的作用,提高压裂液网络的强度,有效的降低瓜胶网络被破坏的机会,使瓜胶压裂液体系的耐温、抗剪切能力提高。
由于碳纳米管直径和长度与瓜胶的纤维直径和长度接近,在瓜胶体系中加入碳纳米管不会存在尺寸效应而导致瓜胶与碳纳米管分离,两者可以很好的互混。但是由于碳纳米管是一种无机材料,单纯的碳纳米管不能分散在水中。文献报道的增加碳纳米管水分散性的方法是,通过氧化作用,让碳纳米管的表面带上羟基或羧酸基团,这种氧化方法是针对碳纳米管表面的缺陷进行反应,碳纳米管表面的缺陷较少,导致氧化后碳纳米管表面的羟基或羧基数量有限,水分散性能并不高。而碳纳米管增强压裂液性能需要碳纳米管的浓度有一个阙值,不然提高压裂液的性能有限,只是氧化的方法,碳纳米管的分散浓度有限。有的文献采用在碳纳米管的表面包覆水溶性的化合物的方法,增加碳纳米管的水分散性,如CN 109097019A,这种方法采用昂贵的硅基材料包覆在纳米材料上,会增加应用成本。
发明内容
为解决以上至少之一的技术问题,本发明提供一种耐高温碳纳米管杂化压裂液及其制备方法。
为了实现以上目的,本发明采用以下技术方案:
本发明提供一种耐高温碳纳米管杂化压裂液,包括:
0.2wt.%-0.5wt.%稠化剂、0.2wt.%-0.4wt.%交联剂、0.1wt.%-0.3wt.%助排剂、0.1wt.%-0.3wt.%粘土稳定剂、0.1wt.%-0.3wt.%破乳剂、0.01wt.%-0.04wt.%NaHCO3和0.05wt.%-0.1wt.%改性碳纳米管,余量水;
其中,所述稠化剂为瓜胶原粉、羟丙基瓜尔胶、羧甲基羟丙基瓜尔胶中的一种或两种以上的混合物;所述改性碳纳米管为水性丙烯酸树脂包覆的碳纳米管。
本发明的耐高温碳纳米管杂化压裂液克服了无机结构和有机结构的耦合问题,并且利用碳纳米管的纳米特性,增加压裂液的稳定性。
优选地,所述交联剂为有机硼交联剂。瓜胶中的多糖结构比较容易被有机硼交联剂中的硼结构交联,增加网络结构。
优选地,所述助排剂是非离子型氟碳。
优选地,所述粘土稳定剂为KCl或NH4Cl。
优选地,所述破乳剂为非离子型聚氧乙烯聚氧丙烯的嵌段共聚物。
碳纳米管直径只有1-5nm,长度可以达到微米级。瓜胶分子分散在溶液中形成的纤维直径从纳米级别到微米级别不等,长度上也达到了微米,所以碳纳米管在尺寸上与瓜胶纤维差别不大,两者能很好的融合。通过对碳纳米管外壁进行包覆,形成了能有效分散在水中的碳纳米管,且包覆层含有大量的羟基,可与瓜胶分子链上的羟基相容,形成均相的混合。碳纳米管与瓜胶均相混合后,碳纳米管在其中均匀分散,起到骨架连接各条瓜胶纤维链。当整个压裂液体系受到外力的作用时,局部瓜胶的受力可以被快速的分散到整个压裂液网络中,使得压裂液的耐温性能提高。本发明中碳纳米管外围包覆的是一层水性丙烯酸树脂层,该层上的羟基与瓜胶分子上的羟基能通过氢键相互作用。这种多位点的作用可以有效的提升整个体系的抗剪切作用。
优选地,所述水性丙烯酸树脂包覆的碳纳米管通过以下制备方法得到:
将水性丙烯酸树脂溶胀在乙醇中,搅拌下加入碳纳米管粉末,保持温度在40-60℃,3-5小时。
优选地,所述乙醇为95%的乙醇;本领域技术人员了解的,一般使用的95%乙醇为体积含量。
优选地,所述搅拌的速度为2000-3000转/分钟。
优选地,所述水性丙烯酸树脂与碳纳米管的质量比为1:(0.2-0.5)。
本发明第二个方面提供以上耐高温碳纳米管杂化压裂液的制备方法,包括以下步骤:
将改性碳纳米管吸入、分散到容器中,再吸入稠化剂;用液添泵加入粘土稳定剂、破乳剂、助排剂和水,最后加入NaHCO3,混合均匀,得到压裂液基液;在注入井中之前,加入交联剂。
瓜胶分子链全为有机构成,主链是聚甘露糖,由C-C键和C-O键连接,这些键在外力的剪切和高温作用下,会被破坏,使得纯瓜胶压裂液的耐温性能不高,碳纳米管是一种无机材料,具有很强的刚性特征;但是由于直径小,又具有一定的柔韧性,其在瓜胶的纤维体系中能有效的分散。采用碳纳米管增强的压裂液体系,不选用重金属离子,减小了对储层的伤害;现有的高温压裂液体系添加的瓜胶含量在0.55%以上,造成基液黏度高,施工时泵送困难;且造成施工后的破胶也较困难。碳纳米管增强的高温压裂液体系,降低了瓜胶的加量,交联剂使用常规的硼交联体系,有效的降低压裂液对储层的伤害,提升了改造效果。发明的碳纳米管压裂液体系,可以在不改变配方中其他性能的基础上,将压裂液的耐温性能从耐温120摄氏度提升到160摄氏度。
本发明采用非常经济的水性丙烯酸树脂包覆在碳纳米管表面,水溶性的水性丙烯酸树脂极大的增加了碳纳米管的水分散性,得到了一种价格低廉的耐温、抗剪切的碳纳米管杂化高温压裂液体系。
具体实施方式
为了更清楚地说明本发明,下面结合优选实施例对本发明做进一步的说明。本领域技术人员应当理解,下面所具体描述的内容是说明性的而非限制性的,不应以此限制本发明的保护范围。
以下实施例按照此处所述步骤制备耐高温碳纳米管杂化压裂液:
将改性碳纳米管吸入、分散到罐中,再吸入稠化剂;用液添泵加入粘土稳定剂和破乳剂,最后加入NaHCO3,混合均匀,得到压裂液基液;在注入井中之前,加入交联剂。
其中的改性碳纳米管通过以下步骤制备:
将水性丙烯酸树脂溶胀在95%乙醇中,剧烈搅拌下加入碳纳米管粉末,保持温度在40-60℃,3-5小时。
实施例1
本实施例提供了一种耐高温碳纳米管杂化压裂液,其是通过以下步骤制备的:
5g瓜胶原粉、2g NH4Cl、1g非离子型聚氧乙烯聚氧丙烯的嵌段共聚物、0.8g改性碳纳米管、1g非离子型氟碳、0.2g NaHCO3和987g水混合即得到基液,在注入井中之前,加入3g有机硼交联剂。
实施例2
本实施例提供了一种耐高温碳纳米管杂化压裂液,其是通过以下步骤制备的:
4g羟丙基瓜尔胶、1g KCl、3g非离子型聚氧乙烯聚氧丙烯的嵌段共聚物、0.5g改性碳纳米管、3g非离子型氟碳、0.2g NaHCO3和986.3g水混合即得到基液,在注入井中之前,加入2g有机硼交联剂。
实施例3
本实施例提供了一种耐高温碳纳米管杂化压裂液,其是通过以下步骤制备的:
3g羧甲基羟丙基瓜尔胶、3g NH4Cl、2g非离子型聚氧乙烯聚氧丙烯的嵌段共聚物、0.8g改性碳纳米管、1g非离子型氟碳、0.2g NaHCO3和986g水混合即得到基液,在注入井中之前,加入4g有机硼交联剂。
对比例1
本对比例提供了一种压裂液,其是通过以下步骤制备的:
3g羧甲基羟丙基瓜尔胶、3g NH4Cl、2g非离子型聚氧乙烯聚氧丙烯的嵌段共聚物、1g非离子型氟碳、0.2g NaHCO3和986.8g水混合即得到基液,在注入井中之前,加入4g有机硼交联剂。
性能对比
基于油气行业标准SY/T5107-2016《水基压裂液性能评价方法》测试压裂液的基液黏度,压裂液冻胶的耐温性能,其结果如表1所示,由表中数据可知含有本发明改性碳纳米管的压裂液,耐温性能有显著的提高。
表1
对比例2
使用CN106433603A中的改性方法得到的羟基或氨基化碳纳米管配置压裂液,由于所得羟基或氨基化碳纳米管分散性很差,无法得到均匀的溶液。
显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定,对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动,这里无法对所有的实施方式予以穷举,凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。
Claims (10)
1.一种耐高温碳纳米管杂化压裂液,其特征在于,包括:
0.2wt.%-0.5wt.%稠化剂、0.2wt.%-0.4wt.%交联剂、0.1wt.%-0.3wt.%助排剂、0.1wt.%-0.3wt.%粘土稳定剂、0.1wt.%-0.3wt.%破乳剂、0.01wt.%-0.04wt.%NaHCO3和0.05wt.%-0.1wt.%改性碳纳米管,余量水;
其中,所述稠化剂为瓜胶原粉、羟丙基瓜尔胶、羧甲基羟丙基瓜尔胶中的一种或两种以上的混合物;所述改性碳纳米管为水性丙烯酸树脂包覆的碳纳米管。
2.根据权利要求1所述的耐高温碳纳米管杂化压裂液,其特征在于,所述交联剂为有机硼交联剂。
3.根据权利要求1所述的耐高温碳纳米管杂化压裂液,其特征在于,所述助排剂是非离子型氟碳。
4.根据权利要求1所述的耐高温碳纳米管杂化压裂液,其特征在于,所述粘土稳定剂为KCl或NH4Cl。
5.根据权利要求1所述的耐高温碳纳米管杂化压裂液,其特征在于,所述破乳剂为非离子型聚氧乙烯聚氧丙烯的嵌段共聚物。
6.根据权利要求1所述的耐高温碳纳米管杂化压裂液,其特征在于,所述水性丙烯酸树脂包覆的碳纳米管通过以下制备方法得到:
将水性丙烯酸树脂溶胀在乙醇中,搅拌下加入碳纳米管粉末,保持温度在40-60℃,3-5小时。
7.根据权利要求6所述的耐高温碳纳米管杂化压裂液,其特征在于,所述乙醇为95%的乙醇。
8.根据权利要求6所述的耐高温碳纳米管杂化压裂液,其特征在于,所述搅拌的速度为2000-3000转/分钟。
9.根据权利要求6所述的耐高温碳纳米管杂化压裂液,其特征在于,所述水性丙烯酸树脂与碳纳米管的质量比为1:(0.2-0.5)。
10.根据权利要求1-9任一项所述耐高温碳纳米管杂化压裂液的制备方法,包括以下步骤:
将改性碳纳米管吸入、分散到容器中,再吸入稠化剂;用液添泵加入粘土稳定剂、破乳剂、助排剂和水,最后加入NaHCO3,混合均匀,得到压裂液基液;在注入井中之前,加入交联剂。
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