CN113912774A - 一种压裂用聚合物粘土稳定剂及其制备方法 - Google Patents
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Abstract
本发明公开一种压裂用聚合物粘土稳定剂及其制备方法,该粘土稳定剂由丙烯酰胺、阴离子单体、阳离子单体共聚,以巯基壳聚糖为链转移剂,得到端基为壳聚糖的两性离子聚合物。其中丙烯酰胺、阴离子单体和阳离子单体分别占单体总摩尔量的10~60%、5~25%和20~79%,引发剂添加量占单体总重量的0.4~1.2%,巯基壳聚糖的脱乙酰度达到80%以上,分子量在1000至5000之间,添加量占单体总重量的5~15%。本发明制备的压裂用聚合粘土稳定剂能够有效抑制粘土的膨胀,与压裂液中其他添加剂具有良好的配伍性,适用于低渗透致密油气储层的压裂施工。
Description
技术领域
本发明涉及一种压裂用聚合物粘土稳定剂及其制备方法,属于石油开采中压裂施工技术领域。
背景技术
我国致密油气资源丰富,目前致密油储层改造主要采用水力压裂施工,在这种大规模的压裂过程中,大量水溶液与粘土接触,使粘土发生膨胀、分散及运移,进而降低储层渗透率或堵塞储层通道。因此有必要使用粘土稳定剂来提高作业液体的防膨率,降低粘土分散运移,提高储层渗透率。
常用的粘土稳定剂可分为无机粘土稳定剂和有机粘土稳定剂。无机粘土稳定剂包括盐类和无机阳离子聚合物;有机粘土稳定剂包括阳离子表面活性剂和有机阳离子聚合物。其中,有机阳离子聚合物稳定粘土的能力超过无机盐类、无机阳离子聚合物和阳离子表面活性剂类粘土稳定剂,且具有用量少、效能高、吸附能力强、受pH值影响小、对地层适应性强等优点,是近几年来国内外重点研究和应用的对象。
但是,有机阳离子聚合物相对分子量大,容易在地层孔隙通道中形成栓塞,从而堵塞地层,加重对低渗透油层渗透率的伤害。同时聚合物分子链长,含有大量的阳离子中心,在与阴离子型添加剂接触后,由于阴阳离子间存在静电吸附作用,易降低压裂液的配伍性及防膨效果,严重的甚至出现浑浊、絮凝分层现象,大大限制了其应用。因此,需要研制低相对分子量、保护地层不受伤害、生物降解性好,且与其他处理剂配伍性好的粘土稳定剂。
发明内容
本发明的目的是克服现有不足,提供一种防膨性能优异,生物相容性及配伍性良好的压裂用聚合物粘土稳定剂。
壳聚糖是甲壳素脱乙酰基的产物,是天然多糖中唯一的碱性氨基多糖物质。壳聚糖是多个氨基葡萄糖通过β-1,4-糖苷键连接而成的直链状高分子。壳聚糖分子中均含有酰胺基以及氨基、羟基,随着氨基的质子化,表现出阳离子型聚电解质的作用,同时,壳聚糖具有良好的生物降解性和生物相容性。本发明将壳聚糖引入到粘度稳定剂中,以提高稳定剂的生物相容性。
为实现上述目的,本发明具体通过如下技术方案予以实现。
一种压裂用聚合物粘土稳定剂,其特征在于,由丙烯酰胺、阴离子单体、阳离子单体共聚并在聚合物链端基接入巯基壳聚糖而合成,具体由以下方法制备得到:
在反应器中依次加入丙烯酰胺单体、阴离子单体、阳离子单体和蒸馏水,搅拌至单体溶解后将溶液温度控制在30-40℃,用NaOH调节体系pH值至5~7,再调节水量使总单体质量百分浓度为20~30%;向溶液中通高纯氮气20-40分钟,缓慢滴加引发剂,当溶液温度升至45-55℃后,滴加巯基壳聚糖水溶液,滴加完后继续反应1-3小时,得到透明的聚合物产品;将产物用甲醇多次洗涤,在35-45℃真空干燥,取出造粒,得到淡黄色颗粒的含壳聚糖的压裂用聚合物粘土稳定剂;
所述丙烯酰胺单体添加量占单体总摩尔量的10~60%;
所述阴离子单体包括丙烯酸、甲基丙烯酸和2-丙烯酰胺-2-甲基丙磺酸中一种或几种的混合物,添加量占单体总摩尔量的5~25%;
所述阳离子单体包括二甲基二烯丙基氯化铵、三甲基烯丙基氯化铵、丙烯酰氧乙基三甲基氯化铵和甲基丙烯酰氧乙基三甲基氯化铵中一种或几种的混合物,添加量占单体总摩尔量的20~79%;
所述引发剂为过硫酸铵/亚硫酸氢钠或焦亚硫酸钠氧化还原引发剂、偶氮类引发剂或过氧化物类引发剂中一种或几种的混合物,引发剂添加量占单体总重量的0.4~1.2%;
所述巯基壳聚糖的脱乙酰度达到80%以上,分子量在1000至5000之间,添加量占单体总重量的5~15%。
本发明还提供给了上述压裂用聚合物粘土稳定剂的一种指标方法,包括以下几个步骤:
在反应器中依次加入丙烯酰胺单体、阴离子单体、阳离子单体和蒸馏水,搅拌至单体溶解后将溶液温度控制在30-40℃,用NaOH调节体系pH值至5~7,再调节水量使总单体质量百分浓度为20~30%;向溶液中通高纯氮气20-40分钟,缓慢滴加引发剂,当溶液温度升至45-55℃后,滴加巯基壳聚糖水溶液,滴加完后继续反应1-3小时,得到透明的聚合物产品;将产物用甲醇多次洗涤,在35-45℃真空干燥,取出造粒,得到淡黄色颗粒的含壳聚糖的压裂用聚合物粘土稳定剂。
本发明的有益效果在于,使用巯基壳聚糖作为链转移剂终止聚合反应,一方面在保证充足的阳离子点位的情况下降低聚合物分子量,保持良好防膨性能的同时保护地层不受伤害,另一方面,壳聚糖的加入使粘土稳定剂具备良好的生物相容性和生物降解性,对环境友好;另外,两性离子聚合物,可以使粘土稳定剂吸附在粘土颗粒表面形成致密的水化层,进一步增强防膨性能,聚合物内阴阳离子之间形成网状结构,降低粘土稳定剂与压裂液中阴离子添加剂之间的静电吸附作用,与压裂液中其他添加剂具有良好的配伍性。
具体实施方式:
下面结合具体实施例对本发明技术方案作进一步说明。
实施例1
在250ml三口烧瓶中,加入13.24g丙烯酰胺,2.68g丙烯酸,40.13g二甲基二烯丙基氯化铵溶液(质量百分比60%)和一定量的蒸馏水,搅拌均匀,待单体完全溶解后,将溶液温度控制在35℃,用NaOH溶液调节体系pH值至6.5,再补充蒸馏水至溶液总重量为200g。向溶液中通高纯氮气30min,加入过硫酸铵200mg,将40mg亚硫酸氢钠配制成溶液,缓慢滴加之后开始聚合升温,当温度达到50℃后,滴入含3g分子量为2000巯基壳聚糖的水溶液,继续反应3个小时,将产物用甲醇多次洗涤,在40℃下真空干燥12个小时,取出造粒,得到淡黄色颗粒的含壳聚糖的压裂用聚合物粘土稳定剂。
实施例2
在250ml三口烧瓶中,加入17.46g丙烯酰胺,2.95g丙烯酸,8.48g2-丙烯酰胺-2-甲基丙磺酸,18.52g三甲基烯丙基氯化铵溶液(质量百分比60%)和一定量的蒸馏水,搅拌均匀,待单体完全溶解后,将溶液温度控制在35℃,用NaOH溶液调节体系pH值至6.5,再补充蒸馏水至溶液总重量为200g。向溶液中通高纯氮气30min,加入过硫酸铵100mg,偶氮二异丁基脒盐酸盐200mg,将20mg亚硫酸氢钠配制成溶液,缓慢滴加之后开始聚合升温,当温度达到50℃后,滴入含6g分子量为5000巯基壳聚糖的水溶液,继续反应3个小时,将产物用甲醇多次洗涤,在40℃下真空干燥12个小时,取出造粒,得到淡黄色颗粒的含壳聚糖的压裂用聚合物粘土稳定剂。
实施例3
在250ml三口烧瓶中,加入8.56g丙烯酰胺,1.48g甲基丙烯酸,49.95g丙烯酰氧乙基三甲基氯化铵溶液(质量百分比80%)和一定量的蒸馏水,搅拌均匀,待单体完全溶解后,将溶液温度控制在35℃,用NaOH溶液调节体系pH值至6.5,再补充蒸馏水至溶液总重量为200g。向溶液中通高纯氮气30min,加入过硫酸铵220mg,过氧化叔丁基10mg,将30mg焦亚硫酸钠配制成溶液,缓慢滴加之后开始聚合升温,当温度达到50℃后,滴入含2.5g分子量为3000巯基壳聚糖的水溶液,继续反应3个小时,将产物用甲醇多次洗涤,在40℃下真空干燥12个小时,取出造粒,得到淡黄色颗粒的含壳聚糖的压裂用聚合物粘土稳定剂。
实施例4
在250ml三口烧瓶中,加入13.43g丙烯酰胺,6.05g丙烯酸,4.35g2-丙烯酰胺-2-甲基丙磺酸,32.71g甲基丙烯酰氧乙基三甲基氯化铵溶液(质量百分比80%)和一定量的蒸馏水,搅拌均匀,待单体完全溶解后,将溶液温度控制在35℃,用NaOH溶液调节体系pH值至6.5,再补充蒸馏水至溶液总重量为200g。向溶液中通高纯氮气30min,加入过硫酸铵300mg,偶氮二异丁咪唑啉盐酸盐100mg,将50mg亚硫酸氢钠配制成溶液,缓慢滴加之后开始聚合升温,当温度达到50℃后,滴入含5g分子量为1000巯基壳聚糖的水溶液,继续反应3个小时,将产物用甲醇多次洗涤,在40℃下真空干燥12个小时,取出造粒,得到淡黄色颗粒的含壳聚糖的压裂用聚合物粘土稳定剂。
实施例5
在250ml三口烧瓶中,加入4.65g丙烯酰胺,3.75g甲基丙烯酸,4.52g2-丙烯酰胺-2-甲基丙磺酸,58.75g二甲基二烯丙基氯化铵溶液(质量百分比60%),19.72g三甲基烯丙基氯化铵溶液(质量百分比60%)和一定量的蒸馏水,搅拌均匀,待单体完全溶解后,将溶液温度控制在35℃,用NaOH溶液调节体系pH值至6.5,再补充蒸馏水至溶液总重量为200g。向溶液中通高纯氮气30min,加入过硫酸铵400mg,偶氮二异丁基脒盐酸盐100mg,过氧化叔丁基40mg,将60mg亚硫酸氢钠配制成溶液,缓慢滴加之后开始聚合升温,当温度达到50℃后,滴入含7.5g分子量为4000巯基壳聚糖的水溶液,继续反应3个小时,将产物用甲醇多次洗涤,在40℃下真空干燥12个小时,取出造粒,得到淡黄色颗粒的含壳聚糖的压裂用聚合物粘土稳定剂。
实施例6
1、防膨性能测试
将实施例1-5制备的粘土稳定剂,按照中华人民共和国石油天然气行业标准《SY/T5971-2016油气田压裂酸化及注水用粘土稳定剂性能评价方法》测定防膨率,结果如表1所示:
表1 粘土稳定剂的防膨性能测试结果
由表1可知,实施例1-5制备的粘土稳定剂具有良好的防膨性能。
2、配伍性测试
将实施例1-5制备的粘土稳定剂与常用的市售稠化剂复配(0.5%稠化剂与0.5%粘土稳定剂),评价配伍性,并与现有常用有机阳离子聚合物粘土稳定剂进行对比,结果如表2所示:
表2 粘土稳定剂的配伍性评价结果
由表2可知,实施例1-5中制备的粘土稳定剂与常用阴离子型增稠剂复配后无絮凝现场出现,配伍性良好。
Claims (2)
1.一种压裂用聚合物粘土稳定剂,其特征在于,由以下方法制备得到:
在反应器中依次加入丙烯酰胺单体、阴离子单体、阳离子单体和蒸馏水,搅拌至单体溶解后将溶液温度控制在30-40℃,用NaOH调节体系pH值至5~7,再调节水量使总单体质量百分浓度为20~30%;向溶液中通高纯氮气20-40分钟,缓慢滴加引发剂,当溶液温度升至45-55℃后,滴加巯基壳聚糖水溶液,滴加完后继续反应1-3小时,得到透明的聚合物产品;将产物用甲醇多次洗涤,在35-45℃真空干燥,取出造粒,得到淡黄色颗粒的含壳聚糖的压裂用聚合物粘土稳定剂;
所述丙烯酰胺单体添加量占单体总摩尔量的10~60%;
所述阴离子单体包括丙烯酸、甲基丙烯酸和2-丙烯酰胺-2-甲基丙磺酸中一种或几种的混合物,添加量占单体总摩尔量的5~25%;
所述阳离子单体包括二甲基二烯丙基氯化铵、三甲基烯丙基氯化铵、丙烯酰氧乙基三甲基氯化铵和甲基丙烯酰氧乙基三甲基氯化铵中一种或几种的混合物,添加量占单体总摩尔量的20~79%;
所述引发剂为过硫酸铵/亚硫酸氢钠或焦亚硫酸钠氧化还原引发剂、偶氮类引发剂或过氧化物类引发剂中一种或几种的混合物,引发剂添加量占单体总重量的0.4~1.2%;
所述巯基壳聚糖的脱乙酰度≥80%,分子量为1000~5000,添加量占单体总重量的5~15%。
2.一种如权利要求1所述的压裂用聚合物粘土稳定剂的制备方法,其特征在于,包括以下几个步骤:
在反应器中依次加入丙烯酰胺单体、阴离子单体、阳离子单体和蒸馏水,搅拌至单体溶解后将溶液温度控制在30-40℃,用NaOH调节体系pH值至5~7,再调节水量使总单体质量百分浓度为20~30%;向溶液中通高纯氮气20-40分钟,缓慢滴加引发剂,当溶液温度升至45-55℃后,滴加巯基壳聚糖水溶液,滴加完后继续反应1-3小时,得到透明的聚合物产品;将产物用甲醇多次洗涤,在35-45℃真空干燥,取出造粒,得到淡黄色颗粒的含壳聚糖的压裂用聚合物粘土稳定剂。
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