CN108485639A - 一种两性离子聚合物稠化剂及其制备方法 - Google Patents
一种两性离子聚合物稠化剂及其制备方法 Download PDFInfo
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- CN108485639A CN108485639A CN201810404291.9A CN201810404291A CN108485639A CN 108485639 A CN108485639 A CN 108485639A CN 201810404291 A CN201810404291 A CN 201810404291A CN 108485639 A CN108485639 A CN 108485639A
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
- C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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Abstract
本发明公开了一种两性离子聚合物稠化剂及其制备方法,其组成和摩尔质量百分比如下:丙烯酰胺:70%‑90%;阳离子单体:5%‑15%;阴离子单体:5%‑15%;本稠化剂采用含羧基的单体和含可抑制黏土水化膨胀的阳离子单体构筑,兼具阴离子与阳离子聚合物的综合性能。
Description
技术领域
本发明涉及一种油气开采用两性离子聚合物稠化剂技术领域。
背景技术
随着油气勘探开发不断向纵深发展,低渗、低压、高温深层油气藏的勘探与开发变得越来越重要,压裂作为该类油气藏增产的技术手段越来越受到重视。压裂液作为压裂施工的工作液,是影响压裂施工成效的主要因素。
目前主要使用的压裂液为水基压裂液,由稠化剂、交联剂、助剂及水配制而成,其中的主剂为稠化剂。根据稠化剂的不同,可将现有的主要压裂液体系分为如下3类:植物胶压裂液体系、黏弹性表面活性剂压裂液( VES)体系和合成聚合物压裂液体系,以植物胶压裂液为主。植物胶压裂液使用的稠化剂主要为胍胶及其改性产品,该类稠化剂增稠能力强,可交联性好,但需在碱性条件下交联,原料依赖进口,价格不稳定,同时存在残渣多、易造成地层伤害等问题;VES 压裂液体系克服了植物胶压裂液对地层伤害大的缺点,但其耐温性能较差,不能满足高温储层压裂施工要求;合成聚合物压裂液具有稠化剂结构较易调控的特点,是水基压裂液技术的重要发展方向之一,已经成为国内外研究热点。早期采用的合成聚合物稠化剂为聚丙烯酰胺、甲叉基聚丙烯酰胺在一定程度上解决了聚合物高效增黏的问题,但其耐温耐盐性以及剪切稳定性仍然不尽人意,未能获得大量应用。
近年来,为了获得性能优良的合成聚合物压裂液,科技工作者开展了基于丙烯酰胺共聚物的聚合物压裂液研究。例如,CN102206484公开了一种以疏水缔合聚合物为稠化剂的酸性疏水缔合物压裂液,该酸性疏水缔合物压裂液适合碱敏储层、强水敏储层的压裂改造,具有良好的延缓交联性能、携砂性能好、易破胶返排、对地层伤害小及低摩阻、低残渣、防膨效果好等优点,但其耐温性也仅适用于130℃油气藏;CN102702424公开了以丙烯酰胺(AM)/2-丙烯酰胺基-2-甲基丙磺酸(AMPS) /甲基丙烯酰氧乙基三甲基氯化铵(DMC)两性离子聚合物为稠化剂的压裂液,该压裂液能实现酸携砂工艺,可适用于高含碱敏性矿物储层的酸加砂改造,但其耐温性仅适用120℃油气藏,且原料成本较高; CN104194763A公开了一种阴离子聚合物稠化剂、压裂液及其制备方法,提出的丙烯酰胺(AM)/丙烯酸(AA)/丙烯酸十八酯(ODA)共聚而成的阴离子聚合物稠化剂,只适用于130℃以下油气藏;CN104177534公开了一种阳离子聚合物稠化剂、压裂液及其制备方法,提出的丙烯酰胺(AM)/二甲基二烯丙基氯化铵(DMDAAC)阳离子聚合物稠化剂也仅适用于160℃油气藏; CN104449643A公开了油田压裂液用耐高温聚合物稠化剂及其制备方法与应用,提出的提出以丙烯酰胺与烯类单体的共聚物为稠化剂,配制的压裂液耐温性能达到180℃。US4959163公布了一种两性离子聚合物压裂液稠化剂,提出采用反相乳液聚合防范制备AM、AMPS 和甲基丙烯酰氧丙基二甲基-2-羟丙基硫酸铵 ( MAPDMDHPAS) 三元共聚物稠化剂, 采用该两性聚合物配制的压裂液具有较好的耐高温性能且抗盐能力较强.
综上所述,目前大多数压裂液为碱性压裂液,仅适用于150℃以下的储层环境,缺乏能耐受180℃以上的低伤害高温压裂液,已有的可耐高温压裂液也存在稠化剂加量及体系pH较高(稠化剂加量≥1%,pH>5)等问题。两性离子聚合物耐盐性好,可抑制地层中的黏土矿物因水化膨胀与运移产生的地层伤害,具备低伤害压裂液的结构与性能特征,但目前有关两性离子聚合物压裂液的研究与应用工作少,涉及的两性离子聚合物的阴离子结构采用AMPS 的含磺酸基单体获得,产品成本高,不利于推广应用。酸性聚合物压裂液可消除碱性条件交联导致高黏土含量地层的碱敏微粒运移产生的储层二次伤害,可获得更好的压裂效果。因此,采用含羧基的单体构筑低成本两性离子聚合物稠化剂,在此基础上研发耐高温的两性离子聚合物压裂液具有十分重要的意义。
发明内容
本发明旨在针对上述现有技术所存在的缺陷和不足,提供一种两性离子聚合物稠化剂,本稠化剂采用含羧基的单体和含可抑制黏土水化膨胀的阳离子单体构筑,兼具阴离子与阳离子聚合物的综合性能。
本发明还提供了该稠化剂的制备方法。
本发明是通过采用下述技术方案实现的:
一种两性离子聚合物稠化剂,其特征在于:组成和摩尔质量百分比如下:丙烯酰胺:70%-90%;阳离子单体:5%-15%;阴离子单体:5%-15%。
所述的阴离子单体为丙烯酸(AA)、甲基丙烯酸(MAA)、衣康酸、3-丙烯酰胺基-3-甲基丁酸(AMB)中的任一种或多种。
所述的阳离子单体为二烯丙基二甲基氯化铵(DADMAC)、丙烯酰氧乙基三甲基氯化铵(DAC)、甲基丙烯酰氧乙基三甲基氯化铵(DMC)、丙烯酸-N,N-二甲氨基乙酯(DMAEA)、甲基丙烯酸-N,N-二甲氨基乙酯(DMAEMA)中的任一种或多种。
所述的稠化剂是由丙烯酰胺、丙烯酸和甲基丙烯酰氧乙基三甲基氯化铵共聚而成。
两性离子聚合物稠化剂的制备方法,其特征在于步骤如下:
(1)在容器内加入丙烯酰胺、阳离子单体、阴离子单体及去离子水,搅拌均匀后置于恒温反应器内;摩尔质量百分比为:丙烯酰胺:70%-90%;阳离子单体:5%-15%;阴离子单体:5%-15%;
(2)通入氮气鼓泡20min,加入引发剂引发聚合,当反应液变黏稠、气泡变小时停止通氮气;
(3)聚合4-6h后得到胶体状产物,经造粒、干燥、粉碎后得到聚合物稠化剂;
其中,反应温度为45℃-55℃,所用的引发剂为过硫酸铵、过硫酸钾、过硫酸钠、亚硫酸氢钠中的一种或任意比例组成的混合物,其用量为占单体总质量的0.05%-0.12%。
与现有技术相比,本发明所达到的有益效果如下:
(1)本发明所提供的稠化剂两性离子聚合物,采用含羧基的单体和含可抑制黏土水化膨胀的阳离子单体构筑,兼具阴离子与阳离子聚合物的综合性能。与现有的采用含磺酸基的单体制备的两性离子聚合物压裂液稠化剂相比,具有原料来源广、成本低等优势。
(2)本发明提供的稠化剂能在酸性条件下与其配套的有机钛复合交联剂交联,消除了胍胶及其衍生物等压裂液因在碱性条件交联导致的高黏土含量地层的碱敏微粒运移产生的储层伤害。
附图说明
下面将结合说明书附图和具体实施方式对本发明作进一步的详细说明,其中:
图1是PADA稠化剂基液黏度随温度的变化关系图;
图2是PADA/有机钛复合交联剂压裂液的粘度随温度的变化图;
图3是PADA/有机钛复合交联剂压裂液的粘度随温度和剪切时间的变化图;
图4是pH值对PADA/有机钛复合交联剂压裂液耐温抗剪切性能的影响图;
图5是NaCl浓度对PADA/有机钛复合交联剂压裂液耐温抗剪切性能的影响图。
具体实施方式
下面通过实施例对本发明进行具体描述。有必要在此指出的是以下实施例只用于对本发明作进一步说明,不能理解为对本发明保护范围的限制,该领域的技术熟练人员根据上述发明内容对本发明做出的一些非本质的改进和调整,仍属于本发明的保护范围。
实施例1:两性离子聚合物稠化剂的制备及性能评定
1、两性离子聚合物稠化剂PADA的制备:
(1)两性离子聚合物PADA的原料配方:
丙烯酰胺90%,丙烯酸5%,甲基丙烯酰氧乙基三甲基氯化铵5%(以摩尔质量百分比为计),引发剂为过硫酸铵,占单体总质量的0.08%。
(2)两性离子聚合物PADA的制备方法:
1)在250ml三口瓶内加入定量的去离子水、丙烯酰胺(AM),搅拌均匀后,继续向其中滴加一定量的丙烯酸(AA)和甲基丙烯酰氧乙基三甲基氯化铵(DMC),其摩尔质量比为AM:AA:DMC=90:5:5;
2)搅拌均匀后置于45℃反应器内;
3)通入氮气鼓泡20min,加入引发剂引发聚合,当反应液变黏稠、气泡变小时停止通氮气;
(4)聚合4-5h后得到白色透明胶体,取出烘干造粒,得到聚合物稠化剂PADA。
2、两性离子聚合物稠化剂PADA的耐温性测定:
实验测定了0.6%稠化剂PADA基液粘度随温度的变化规律,在起始温度30℃、升温速率3℃/min、剪切速率170s-1的条件下测定稠化剂基液黏度随温度的变化关系,实验仪器为哈克RV20旋转流变仪,实验结果如图1.由图1可以看出稠化剂基液黏度随温度升高而下降,当温度升高到180℃时,基液黏度仍达到38mPa·s,表现出良好的增粘性能和耐温性能。
实施例2:有机钛复合交联剂的制备
1)向 250 m L 干燥的三口烧瓶中按照一定顺序加入一定质量分数乙二醇、丙三醇、乳酸、戊二醛和钛酸丁酯,
2)放入85℃恒温水浴锅中,以一定速度搅拌反应3.5h后,得到有机钛复合交联剂。
该有机钛复合交联剂是以酞酸丁酯为主剂,多元醇和多元酸为配体,醇为溶剂,在此基础上又引入了能与酰胺基团能发生交联反应的醛类化合物。常温下,PADA与有机钛形成交联结构,高温下,酰胺基又与活性羰基发生交联,重新稳定交联结构,从而进一步提高压裂液冻胶的耐温性和耐剪切性。
实施例3:压裂液的制备
1.压裂液配方:
两性离子聚合物稠化剂0.6% ;有机钛复合交联剂1.5%-1.8%;pH调节剂盐酸0.05%-0.2%;助排剂SD2-10含量为0.25%;余量为水(以质量百分比为计)。
2.压裂液的制备方法:
1)将一定量的两性离子聚合物稠化剂加入去离子水中,搅拌至全溶;
2)向其中加入占稠化剂基液总量0.25%的助排剂,搅拌至全溶;
3)调节溶液pH为3-4;
3)向其中加入占稠化剂基液总量 1.5%-1.8%有机钛复合交联剂,搅拌2min左右而得。
本发明所制备的压裂液冻胶挑挂性能好,弹性佳。
实施例4:高温压裂流变性能测定
选取实例1中的稠化剂,实例2中的交联剂,按照实例3的压裂液制备方法,称取0.6g稠化剂溶入100ml去离子水,搅拌至全溶,待稠化剂完全溶胀后取50ml,向其中加入0.12g助排剂SD2-10,搅拌至全溶,再向其中加入0.8g有机钛复合交联剂,搅拌2-3min左右至可完全挑挂。将压裂液装入哈克RV20旋转流变仪中。
在起始温度30℃、升温速率3℃/min的条件下测定压裂液冻胶黏度随温度的变化关系如图2。由图2可以看出,当温度升至200℃时,压裂液冻胶粘度仍在50mPa·s以上,说明获得的该压裂液耐温可达200℃。
控制升温速度为3℃/min、起始温度为30℃,升温至180℃后恒温,在剪切速率为170 s-1下连续剪切90min,测得压裂液粘度随时间的变化如图3.可以看出,在180℃、170s-1的条件下剪切90min后黏度仍在72mPa·s以上;还可看出,在60min-70min、120min-140min时间段出现了粘度反弹,可表明其出现了二次交联的现象。说明该压裂液具有良好的耐温抗剪切性能。
实例5:pH值对压裂液性能的影响
选取实例1中的稠化剂,实例2中的交联剂,按照实例3的压裂液制备方法,在稠化剂溶液浓度为0.6%,助排剂含量为基液总量的0.25%,交联剂加量为1.5%的条件下,加pH调节剂改变交联pH配制压裂液,将压裂液装入哈克RV20旋转流变仪中。考察pH值对压裂液性能的影响,结果见表1和图4。由图及表可以看出,pH=2时,该压裂液体系的成胶时间为5min,压裂液黏度较低,耐温抗剪切性能较差,在180℃、170s-1的条件下剪切90min后,黏度在30mPa·s以下;pH=3时,压裂液的成胶时间为2min,压裂液耐温抗剪切性能好,在180℃、170s-1的条件下剪切90min后,黏度在100mPa·s以上;pH=4-5时,压裂液在180℃、170s-1的条件下剪切90min后,黏度在50-70mPa·s;pH>6时,基液与交联剂不交联。说明用本发明提供的两性离子聚合物稠化剂可在酸性条件下与其配套有机钛复合交联剂交联,形成性能良好的压裂液体系。
实施例6:压裂液的耐盐性能
选取实例1中的稠化剂,实例2中的交联剂,按照实例3的压裂液制备方法,配制不同NaCl浓度的压裂液,将其装入哈克RV20旋转流变仪中,考察不同NaCl浓度下的聚合物压裂液耐温抗剪切性能,结果见图5。从图中可以看出,随着NaCl浓度的增大,压裂液起始黏度逐渐下降,当NaCl浓度大于1.5%后,压裂液黏度下降不再明显。在180℃、170s-1剪切90min后,加入不同浓度NaCl的压裂液黏度差距不大,均大于50mPa·s,而NaCl浓度为1.5%的压裂液剪切90min后黏度大于不加NaCl的压裂液,这是因为稠化剂分子链同时带有阴、阳离子基团,加入一定量的NaCl后由于正负电荷的协同作用可能使大分子链伸展,压裂液黏度增大。由此可以说明,本发明提供的压裂液体系具有良好的耐盐性能。
实施例7:压裂液的破胶性能
向实施例4的压裂液体系中加入含量为为0.02%-0.08%的过硫酸铵,在密闭条件下经180℃处理5h后,得到破胶液,测得其黏度小于5mPa·s,表面张力小于28mN/m,压裂液的破胶性能良好。
表1 是pH值对PADA/有机钛复合交联剂压裂液成胶性能的影响。
Claims (5)
1.一种两性离子聚合物稠化剂,其特征在于:组成和摩尔质量百分比如下:其组成和摩尔质量百分比如下:丙烯酰胺:70%-90%;阳离子单体:5%-15%;阴离子单体:5%-15%。
2.根据权利要求1所述的一种两性离子聚合物稠化剂,其特征在于:所述的阴离子单体为丙烯酸、甲基丙烯酸、衣康酸、3-丙烯酰胺基-3-甲基丁酸中的任一种或多种。
3.根据权利要求1或2所述的一种两性离子聚合物稠化剂,其特征在于:所述的阳离子单体为二烯丙基二甲基氯化铵、丙烯酰氧乙基三甲基氯化铵、甲基丙烯酰氧乙基三甲基氯化铵、丙烯酸-N,N-二甲氨基乙酯、甲基丙烯酸-N,N-二甲氨基乙酯中的任一种或多种。
4.根据权利要求3所述的一种两性离子聚合物稠化剂,其特征在于:所述的稠化剂是由丙烯酰胺、丙烯酸和甲基丙烯酰氧乙基三甲基氯化铵共聚而成。
5.两性离子聚合物稠化剂的制备方法,其特征在于步骤如下:
(1)在容器内加入丙烯酰胺、阳离子单体、阴离子单体及去离子水,搅拌均匀后置于恒温反应器内;摩尔质量百分比为:丙烯酰胺:70%-90%;阳离子单体:5%-15%;阴离子单体:5%-15%;
(2)通入氮气鼓泡20min,加入引发剂引发聚合,当反应液变黏稠、气泡变小时停止通氮气;
(3)聚合4-6h后得到胶体状产物,经造粒、干燥、粉碎后得到聚合物稠化剂;
其中,反应温度为45℃-55℃,所用的引发剂为过硫酸铵、过硫酸钾、过硫酸钠、亚硫酸氢钠中的一种或任意比例组成的混合物,其用量为占单体总质量的0.05%-0.12%。
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CN111778008A (zh) * | 2020-08-06 | 2020-10-16 | 陕西森瑞石油技术开发有限公司 | 适用于一体化压裂工艺的压裂液稠化剂制备方法及应用 |
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