CN113929838A - 一种耐高盐自增弹型疏水缔合聚合物的制备及其在压裂液中的应用 - Google Patents
一种耐高盐自增弹型疏水缔合聚合物的制备及其在压裂液中的应用 Download PDFInfo
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Abstract
本发明属于油气增产技术领域,公开了一种耐高盐自增弹型疏水缔合聚合物的制备及其在压裂液中的应用。本发明的聚合物制备方法为:(1)带有聚醚的疏水单体合成:通过油酸和氯化亚砜反应活的中间体油酸酰氯,再由中间体油酸酰氯与烯丙基聚乙二醇反应得到聚醚单体。(2)疏水缔合聚合物合成:将丙烯酰胺、丙烯酸、2‑丙烯酰胺基‑2‑甲基丙磺酸、阳离子疏水单体和聚醚疏水单体APOA按质量比为:50~60:20~30:10~15:3~5:0.5~1.5聚合,聚合温度1~20℃,聚合时间4‑8h,干燥造粉之后得到聚合物粉末。该聚合物的弹性随着矿化度的增加而增加,在30万矿化度下仍然具有优异的弹性和很高的粘度保持率,将其应用在压裂液中,可有效解决传统压裂液耐盐性能差和悬砂能力差等问题。
Description
技术领域
本发明属于油气田开发技术领域,具体涉及一种耐高盐自增弹型疏水缔合聚合物的制备及其在压裂液中的应用。
背景技术
随着油气田开发行业的不断发展,复杂储层开发对压裂液提出了新的要求,耐高温高矿化度、抗剪切、对储层伤害低成为了压裂液新的发展方向。目前压裂液通常分为水基压裂液、油基压裂液、乳化压裂液、泡沫压裂液和VES压裂液。综合对比发现,油基压裂液流变性差且成本高、泡沫压裂液施工不便、乳化压裂液油水比难控制、VES压裂液滤失大且成本过高。而水基压裂液因其使用范围广、低成本及易控制等优点得到了广泛的应用。
水溶性疏水缔合聚合物(HAWSP)是指聚合物亲水性大分子链上带有少量疏水基团的水溶性聚合物,它作为新型聚合物的一种,因其特殊的流变性能受到较多的关注。
目前,国内外对于疏水缔合聚合物进行了广泛的研究,并取得一定成果,如申请号为201511018952.7的《一种疏水缔合聚合物及其制备方法》、申请号为201610969007.3的《一种具有多种环结构侧链的疏水缔合聚合物及其制备方法与它的用途》、申请号为201410076079.6的《水溶性疏水缔合聚合物压裂液体系及其制备方法》等所提供的聚合物均具有一定的抗温耐盐性能,但这些疏水缔合聚合物仍然具有一定缺陷:在高矿化度条件下,粘度降低幅度较大,粘度保持率较低。因此,如何进一步提高疏水缔合聚合物在极端恶劣条件下的性能,是一个极具挑战的问题。
针对上述存在的问题,本发明提供一种耐高盐自增弹型疏水缔合聚合物的制备方法及其在压裂液中的应用。
发明内容
针对上述现有技术,本发明提供一种耐高盐自增弹型疏水缔合聚合物,该聚合物应用在压裂液中可以很好地解决传统压裂液在高矿化度条件下,粘度降低幅度较大,粘度保持率较低等问题。
为了达到上述目的,本发明所采用的技术方案是:提供一种高盐自增弹型疏水缔合聚合物的制备及其在压裂液体系中的应用,聚合物是由丙烯酰胺、丙烯酸、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)、阳离子疏水单体和聚醚疏水单体APOA按重量比为:50~60:20~30:10~15:3~5:0.5~1.5聚合而成的一种疏水缔合聚合物。其具体结构式如下:
x、y、z、m、n是单体摩尔比x为60%~70%,y为20%~30%,z为2%~8%,m为1%~3%,n为0.1%~0.5%。
聚醚疏水单体的合成步骤如下:
(1)将油酸溶于二氯甲烷中,以1:1.15的摩尔比缓慢滴加氯化亚砜溶液,在冰浴条件下回流反应8小时,将生成尾气通入NaOH溶液中处理,反应结束后冷却,用旋转蒸发仪进行旋蒸除去有机溶剂二氯甲烷,抽滤得到淡黄色固体,真空干燥至恒重,最终得到中间体油酸酰氯;
(2)将第一步反应得到的中间体油酸酰氯和烯丙基聚乙二醇-1000(APEG-1000)以1:1.1~1.2的摩尔比反应得到聚醚单体;首先,将APEG-1000加入三颈圆底烧瓶中,加入无水乙醇溶液进行溶解,待完全溶解后,转移到冰浴条件下,用恒压漏斗缓慢滴加含中间体油酸酰氯的无水乙醇混合溶液,滴加完成之后,在充分搅拌反应48h,反应结束后用旋转蒸发仪真空干燥蒸馏除去溶剂无水乙醇,对粗产物进行重结晶、提纯,最后用真空旋转蒸发仪除去溶剂,即可得到高纯度的含聚醚的疏水单体;
疏水缔合聚合物合成步骤如下:
(1)在去离子水中加入丙烯酰胺、丙烯酸、2-丙烯酰胺基-2-甲基丙磺酸、阳离子疏水单体N,N-二甲基烯丙基十八烷基铵和聚醚疏水单体APOA,质量百分数为50%~60%的丙烯酰胺、20%~30%的丙烯酸、10%~15%的2-丙烯酰胺基-2-甲基丙磺酸、3%~5%的N,N-二甲基烯丙基十八烷基铵、0.5%~1.5%的APOA配成单体浓度为25%~30%的水溶液,同时加入占总单体浓度0.5%~1%的十二烷基硫酸钠(SDS),搅拌至澄清溶液;
(2)待溶液充分混合均匀后,通氮气30min,除去水中的溶解氧;
(3)以2,2-偶氮二异丁基脒二盐酸盐(V50)为引发剂,该引发剂占总单体浓度的0.1%~0.3%,在温度为5℃冰水浴条件下,进行自由基水溶液聚合,反应6~8小时即可得到所需的疏水缔合聚合物,最后将得到的疏水缔合聚合物剪碎,用无水乙醇浸泡烘干,打成粉末,即得到压裂液所用疏水缔合聚合物。
在上述技术方案的基础上,本发明还可以做如下改进。
进一步,该疏水缔合聚合物可以作为稠化剂在压裂中应用,包含该聚合物的压裂液包括以下质量百分比的组分:聚合物稠化剂0.2wt%,非金属交联剂0.015wt%,破胶剂0.05wt%,黏土稳定剂0.5wt%,余量为水。
进一步,表面活性剂交联剂为十二烷基硫酸钠。
进一步,黏土稳定剂为氯化胆碱、氯化钾、氯化铵的一种或几种。
进一步,破胶剂为过硫酸铵胶囊和/或过流酸铵。。
本发明的有益效果是:
(1)本发明提供一种耐高盐自增弹型疏水缔合聚合物的制备方法,该方法操作方便,具有良好的经济价值和广阔的市场前景。
(2)本发明提供了一种含有聚醚的长链疏水单体的制备方法。
(3)本发明中聚醚疏水单体的原材料芥酸、
油酸等均在植物中提取,属于天然油脂,分布广泛易提取。
(4)本发明提供的疏水缔合聚合物由于聚合物内部的氢键作用、静电桥作用、疏水缔合作用等分子间作用力,使得聚合物溶液中存在较大的弹性。与此同时,通过控制聚合反应的条件,加入部分分子量调节剂,使得制备的聚合物分子量较小,在较低浓度具有较强的疏水缔合作用,进而使其具有优异的弹性,从而可以很好地解决传统疏水缔合聚合物压裂液成本高且悬砂能力差的技术问题。
(5)本发明的疏水缔合聚合物应用到压裂液中,在静态悬砂过程中,展现出优异的悬砂性能,是一种理想的高弹耐盐疏水缔合聚合物压裂液。
(6)本发明的疏水缔合聚合聚合物具有优异的耐盐性能,且弹性随着矿化度的增加而增加,在30万矿化度下仍具有优异的弹性和较高的粘度保持率。
附图说明
图1是本发明实施例3中疏水缔合聚合物的微观结构;
图2是室温条件下本发明实施例5中的静态悬砂实验图;
图3是本发明实施例6所得聚合物溶液在不同的质量浓度NaCl溶液下的表观粘度曲线;
图4是本发明实施例7所得聚合物溶液在不同的质量浓度KCl溶液下的表观粘度曲线;
图5是本发明实施例8所得聚合物溶液在不同的质量浓度CaCl2溶液下的表观粘度曲线;
图6是本发明实施例9所得聚合物溶液的触变性曲线;
图7是本发明实施例10所得聚合物溶液的触变性曲线;
图8是本发明实施例11所得聚合物溶液的触变性曲线;’
图9是本发明实施例12所得聚合物溶液的储能模量,损耗模量与角频率的实验关系图;
图10是本发明实施例13所得聚合物溶液的储能模量,损耗模量与角频率的实验关系图;
图11是本发明实施例14所得聚合物溶液的储能模量,损耗模量与角频率的实验关系图。
具体实施方式
实施例1:
含有聚醚的疏水单体的合成
(1)将油酸溶于二氯甲烷中,以1:1.15的摩尔比缓慢滴加氯化亚砜溶液,在冰浴条件下回流反应8小时,将生成尾气通入NaOH溶液中处理,反应结束后冷却,用旋转蒸发仪进行旋蒸除去有机溶剂二氯甲烷,抽滤得到淡黄色固体,真空干燥至恒重,最终得到中间体油酸酰氯;
(2)将第一步反应得到的中间体油酸酰氯和烯丙基聚乙二醇-1000(APEG-1000)以1:1.1~1.2的摩尔比反应得到聚醚单体;首先,将APEG-1000加入三颈圆底烧瓶中,加入无水乙醇溶液进行溶解,待完全溶解后,转移到冰浴条件下,用恒压漏斗缓慢滴加含中间体油酸酰氯的无水乙醇混合溶液,滴加完成之后,在充分搅拌反应48h,反应结束后用旋转蒸发仪真空干燥蒸馏除去溶剂无水乙醇,对粗产物进行重结晶、提纯,最后用真空旋转蒸发仪除去溶剂,即可得到高纯度的含聚醚的疏水单体;
实施例2:
含有聚醚的疏水单体的合成
(1)将芥酸溶于二氯甲烷中,以1:1.15的摩尔比缓慢滴加氯化亚砜溶液,在冰浴条件下回流反应8小时,将生成尾气通入NaOH溶液中处理,反应结束后冷却,用旋转蒸发仪进行旋蒸除去有机溶剂二氯甲烷,抽滤得到淡黄色固体,真空干燥至恒重,最终得到中间体芥酸酰氯;
(2)将第一步反应得到的中间体芥酸酰氯和烯丙基聚乙二醇-1000(APEG-1000)以1:1.1~1.2的摩尔比反应得到聚醚单体;首先,将APEG-1000加入三颈圆底烧瓶中,加入无水乙醇溶液进行溶解,待完全溶解后,转移到冰浴条件下,用恒压漏斗缓慢滴加含中间体芥酸酰氯的无水乙醇混合溶液,滴加完成之后,在充分搅拌反应48h,反应结束后用旋转蒸发仪真空干燥蒸馏除去溶剂无水乙醇,对粗产物进行重结晶、提纯,最后用真空旋转蒸发仪除去溶剂,即可得到高纯度的含聚醚的疏水单体;
实施例3:
(1)在200ml烧杯中加入30g丙烯酰胺、4g丙烯酸、6g 2-丙烯酰胺基-2-甲基丙磺酸、2g N,N-二甲基烯丙基十八烷基铵和0.5g聚醚单体APOA,配成单体浓度为30%的水溶液,同时加入占总单体浓度1%的十二烷基硫酸钠(SDS),搅拌至澄清溶液。
(2)待溶液充分混合均匀后,通氮气30min,除去水中的溶解氧。
(3)以2,2-偶氮二异丁基脒二盐酸盐(V50)为引发剂,该引发剂占总单体浓度的0.2%,在5℃冰水浴引发条件下,进行自由基水溶液聚合,反应6小时即可得到所需的的疏水缔合聚合物,最后将得到的疏水缔合聚合物剪碎,用无水乙醇浸泡烘干,打成粉末,即得到高弹耐盐疏水缔合聚合物。
实施例4:
(1)在200ml烧杯中加入30g丙烯酰胺、4g丙烯酸、6g 2-丙烯酰胺基-2-甲基丙磺酸、2g N,N-二甲基烯丙基十八烷基铵和0.4g聚醚单体APOA,配成单体浓度为30%的水溶液,同时加入占总单体浓度1%的十二烷基硫酸钠(SDS),搅拌至澄清溶液。
(2)待溶液充分混合均匀后,通氮气30min,除去水中的溶解氧。
(3)以2,2-偶氮二异丁基脒二盐酸盐(V50)为引发剂,该引发剂占总单体浓度的0.2%,在5℃冰水浴引发条件下,进行自由基水溶液聚合,反应5小时即可得到所需的的疏水缔合聚合物,最后将得到的疏水缔合聚合物剪碎,用无水乙醇浸泡烘干,打成粉末,即得到高弹耐盐疏水缔合聚合物。
实施例5:
压裂液体系悬砂能力测定
取实例4中的疏水缔合聚合物,用去离子水配制成0.3wt%的聚合物溶液,选取30目陶粒为支撑剂,计算该陶粒在压裂液中自由沉降速度表示其携砂性能。配制压裂液置于规格为100mL的量筒中,放置20h(附图2),计算出沉降速率。
实施例6:
取实例4中的疏水缔合聚合物,用去离子水配制成0.3wt%的聚合物溶液,加入不同质量分数的NaCl,磁力搅拌器搅拌2h,使盐充分混合在溶液中,静置12h。使用六速粘度计测定聚合物溶液粘度。所得结果见附图3。
实施例7:
取实例4中的疏水缔合聚合物,用去离子水配制成0.3wt%的聚合物溶液,加入不同质量分数的KCl,磁力搅拌器搅拌2h,使盐充分混合在溶液中,静置12h。使用六速粘度计测定聚合物溶液粘度。所得结果见附图4。
实施例8:
取实例4中的疏水缔合聚合物,用去离子水配制成0.3wt%的聚合物溶液,加入不同质量分数的CaCl2,磁力搅拌器搅拌2h,使盐充分混合在溶液中,静置12h。使用六速粘度计测定聚合物溶液粘度。所得结果见附图5。
实施例9:
取实例4中的疏水缔合聚合物,用去离子水配制成0.3wt%的聚合物溶液,使用HAAKE RS600流变仪测量触变性表征了聚合物缔合结构的形成和破坏。上下曲线之间的面积反映了聚合物的触变性。所得结果见附图6。
实施例10:
取实例4中的疏水缔合聚合物,用去离子水配制成0.3wt%的聚合物溶液,加入2%质量分数的NaCl,磁力搅拌器搅拌2h,使盐充分混合在溶液中,静置12h。使用HAAKE RS600流变仪测量触变性表征了聚合物缔合结构的形成和破坏。上下曲线之间的面积反映了聚合物的触变性。所得结果见附图7。
实施例11:
取实例4中的疏水缔合聚合物,用去离子水配制成0.3wt%的聚合物溶液,加入30%质量分数的NaCl,磁力搅拌器搅拌2h,使盐充分混合在溶液中,静置12h。使用HAAKERS600流变仪测量触变性表征了聚合物缔合结构的形成和破坏。上下曲线之间的面积反映了聚合物的触变性。所得结果见附图8。
实施例12:
取实例4中的疏水缔合聚合物,用去离子水配制成0.3wt%的聚合物溶液,加入30%质量分数的NaCl,磁力搅拌器搅拌2h,使盐充分混合在溶液中,静置12h。使用HAAKERS600流变仪测量聚合物储能模量,损耗模量与角频率的关系,表征聚合物的粘弹性。所得结果见附图9。
实施例13:
取实例4中的疏水缔合聚合物,用去离子水配制成0.3wt%的聚合物溶液,加入30%质量分数的NaCl,磁力搅拌器搅拌2h,使盐充分混合在溶液中,静置12h。使用HAAKERS600流变仪测量聚合物储能模量,损耗模量与角频率的关系,表征聚合物的粘弹性。所得结果见附图10。
实施例14:
取实例4中的疏水缔合聚合物,用去离子水配制成0.3wt%的聚合物溶液,加入30%质量分数的NaCl,磁力搅拌器搅拌2h,使盐充分混合在溶液中,静置12h。使用HAAKERS600流变仪测量聚合物储能模量,损耗模量与角频率的关系,表征聚合物的粘弹性。所得结果见附图11。
Claims (5)
3.如权利要求2所述含醚的疏水单体的制备方法依次包括以下步骤:
(1)将油酸溶于二氯甲烷中,以1:1.15的摩尔比缓慢滴加氯化亚砜溶液,在冰浴条件下回流反应8小时,将生成尾气通入NaOH溶液中处理,反应结束后冷却,用旋转蒸发仪进行旋蒸除去有机溶剂二氯甲烷,抽滤得到淡黄色固体,真空干燥至恒重,最终得到中间体油酸酰氯;
(2)将第一步反应得到的中间体油酸酰氯和烯丙基聚乙二醇以1:1.1~1.2的摩尔比反应得到聚醚单体;首先,将烯丙基聚乙二醇加入三颈圆底烧瓶中,加入无水乙醇溶液进行溶解,待完全溶解后,转移到冰浴条件下,用恒压漏斗缓慢滴加含中间体油酸酰氯的无水乙醇混合溶液,滴加完成之后,在充分搅拌反应48h,反应结束后用旋转蒸发仪真空干燥蒸馏除去溶剂无水乙醇,对粗产物进行重结晶、提纯,最后用真空旋转蒸发仪除去溶剂,即可得到高纯度的含聚醚的疏水单体APOA;
进一步地,在本次发明较佳的实施例中,油酸可以用芥酸替换;
进一步地,在本次发明较佳的实施例中,聚醚单体中乙氧基团的数目a可以为5至30。
4.根据权利要求1所述的耐高盐自增弹型疏水缔合聚合物,其制备包括以下步骤:
(1)在去离子水中加入丙烯酰胺、丙烯酸、2-丙烯酰胺基-2-甲基丙磺酸、阳离子疏水单体N,N-二甲基烯丙基十八烷基铵和聚醚疏水单体APOA,质量百分数为50%~60%的丙烯酰胺、20%~30%的丙烯酸、10%~15%的2-丙烯酰胺基-2-甲基丙磺酸、3%~5%的N,N-二甲基烯丙基十八烷基铵、0.5%~1.5%的聚醚单体APOA配成单体浓度为25%~30%的水溶液,同时加入占总单体浓度0.5%~1%的十二烷基硫酸钠(SDS),搅拌至澄清溶液;
(2)待溶液充分混合均匀后,通氮气30min,除去水中的溶解氧;
(3)以2,2-偶氮二异丁基脒二盐酸盐(V50)为引发剂,该引发剂占总单体浓度的0.1%~0.3%,在温度为5℃冰水浴条件下,进行自由基水溶液聚合,反应6~8小时即可得到所需的疏水缔合聚合物,最后将得到的疏水缔合聚合物剪碎,用无水乙醇浸泡烘干,打成粉末,即得到压裂液所用疏水缔合聚合物。
5.权利要求1中任一项疏水缔合聚合物可在压裂液中应用。
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