CN103502386B - 增稠的粘弹性流体及其用途 - Google Patents
增稠的粘弹性流体及其用途 Download PDFInfo
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- CN103502386B CN103502386B CN201280022032.0A CN201280022032A CN103502386B CN 103502386 B CN103502386 B CN 103502386B CN 201280022032 A CN201280022032 A CN 201280022032A CN 103502386 B CN103502386 B CN 103502386B
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Abstract
本发明一般性涉及一种粘弹性流体、增稠的酸组合物等以及使用所述胶凝的组合物的方法。本发明的增稠的组合物可有用地用于增产和/或改变地下地层的渗透率的方法中,用于钻井液、完井液、修井液、酸化液、压裂、砾石充填等中。
Description
发明领域
本发明一般性涉及增稠的粘弹性组合物及其用途。本发明的凝胶由包含芥酰胺基丙基羟基丙基磺基甜菜碱的胶凝剂增稠。
发明背景
本发明一般性涉及粘弹性组合物、增稠的酸凝胶以及该增稠凝胶的用途。例如,酸增稠的溶液可有用地用于清洁配制剂如硬质表面清洁剂、抽水马桶清洁剂、工业清洁剂等中,以及油田应用如井增产中。这些以及其他用途是本领域技术人员所知晓的。
本发明组合物尤其可用于油田应用中。烃通过钻探穿透含烃地下地层从而为油提供到达表面的分流道的井而获得。为了使油由所述地层到达井眼,在地层和井眼间必须存在流道。该流道通过地层岩石且具有足够尺寸和数量的孔隙以允许引导油流运动通过该地层。
油产量下降的一个常见原因是地层损害,这堵塞了岩石孔隙且阻碍油流至井眼,最终阻碍其流至表面。该损害通常由在井眼中故意注入其他流体而导致。即使在钻井后,一些钻井液仍保留在井眼附近的地层区域中,其可脱水并在井眼上形成涂层。该涂层的自然效果是降低了油从所述地层沿井眼方向运动的渗透率。
当地层孔隙的尺寸小以至于油仅非常缓慢地朝井眼迁移时,这构成油产量下降的另一原因。在这两种情况下,均希望改善地层的低渗透率。
井增产是指用于提高含烃地层的渗透率的各种技术。通常使用三种常规井增产技术。第一种包括将化学品注入井眼中以与渗透性破坏材料如井眼涂层反应并将其溶解。第二种方法需要将化学品经由井眼注入地层中以与小部分地层反应并将其溶解,由此产生烃流动至井眼的替代流道。这些替代流道重新引导油流绕过地层的低渗透性区域或损害区域。第三种技术(通常称为压裂)包括在足以使地层实际破裂的压力下将化学品注入地层中,由此形成大的流道,其中烃可更容易地经由该大流道由所述地层运动至井眼。
本申请的增稠的粘弹性流体还用于水力压裂、砾石充填和本领域技术人员已知的其他井增产技术中。此外,本发明的酸增稠的流体可有用地用于各种家用和工业清洁剂中,包括但不限于洗涤剂组合物、抽水马桶清洁剂、硬质表面清洁剂、油脂分割组合物等。
发明简述
本发明一般性涉及一种粘弹性流体、增稠的酸组合物等以及所述胶凝组合物的使用方法。本发明的增稠的组合物可有用地用于增产和/或改变地下地层的渗透率的方法中,用于钻井液、完井液、修井液、酸化液、压裂、砾石充填等中。此外,本发明的酸增稠组合物也可用于清洁配制剂、水基涂料、洗涤剂配制剂、个人护理配制剂、水基沥青配制剂等中。
发明详述
本发明一般性涉及粘弹性组合物或流体,以及所述流体/组合物的使用方法。本发明的增稠的组合物可有用地用于增产和/或改变地下地层的渗透率的方法中,用于钻进液、完井液、修井液、酸化液、砾石充填、压裂等中。此外,本发明的增稠的组合物也可用于清洁配制剂、水基涂料、洗涤剂配制剂、个人护理配制剂、水基沥青配制剂等中。
粘弹性是钻井液、修井液或完井液和增产液中所需的流变特征,其可由流体改性剂如聚合物试剂和表面活性剂胶凝剂提供。粘弹性流体为具有弹性行为和粘性行为的那些。弹性定义为材料对所施加的应力的瞬时应变(形变)响应。在应力移除后,材料回复其未形变的平衡状态。该类行为与固体有关。另一方面,粘性行为定义为由所施加的应力所导致的连续形变。不久后,形变速率(通常为剪切速率或应变速率)变得稳定。在应力移除后,材料不回复其初始的未形变状态。该类行为与液体有关。粘弹性流体的行为可如粘性流体或弹性固体那样,或者为二者的组合,这取决于施加在该体系上的应力和观察的时间标度。粘弹性流体在施加应力后立即显示出弹性响应。在初始的弹性响应后,应变松弛且流体开始以粘性方式流动。据信流体的弹性行为非常有助于固体颗粒的传输。
粘弹性流体的粘度也可随所施加的应力或应变速率而变化。在剪切形变的情况下,非常常见的是流体粘度随剪切速率或剪切应力的增大而降低。该行为通常称为“剪切稀化”。由表面活性剂所导致的流体粘弹性自身可体现为剪切稀化行为。例如,当该流体通过泵或者处于旋转钻头的附近时,所述流体处于高剪切速率环境下且粘度低,从而导致低摩擦压力并节约泵送能量。当剪切应力降低时,流体回复至较高粘度的状态。这是因为粘弹性行为是由流体中的表面活性剂聚集所导致的。这些聚集体调节流体的状态并在不同的剪切应力下形成不同的聚集形状。因此,可存在具有如下行为的流体:在低剪切速率下为高粘度流体,而在较高剪切速率下为低粘度流体。低剪切速率下的高粘度对固体传输而言是好的。
粘弹性流体的弹性部分自身也可体现在屈服应力值中。这允许与具有相同表观粘度的粘性流体相比,粘弹性流体将不溶性物质如砂或钻屑悬浮更长的时间。过高的屈服应力对钻井而言是不好的,因为这可使得钻头的重启非常困难且导致所谓的“卡钻(stuckpipe)”情况。
粘弹性流体在油井钻探应用中的另一功能是改变渗透率。从油藏中二次采油包括借助人工装置补充油藏中固有的天然能量以采油。例如,当油储存在多孔岩石中时,通常通过驱动加压流体如盐水经由一个或多个钻孔(注入井)进入油藏地层中以迫使油运动至可将其采出的井眼处而采油。然而,岩石通常具有高渗透率区域和低渗透率区域。注入的盐水可指进通过高渗透率区域,从而留下处于低渗透率区域中的未开采的油。
本发明的含水粘弹性流体包含至少一种胶凝剂和/或具有如下通式的粘弹性表面活性剂:
其中R1为具有约17至约29个碳原子,在另一实施方案中为约18至约21个碳原子的饱和或不饱和烃基。在一个实施方案中,R1为衍生自具有约1至约140,在另一实施方案中为约30至约90,在另一实施方案中为40至约70的碘值的天然脂肪或油的脂肪族脂族基团。R1可限于单一链长或者可为混合链长,例如衍生自天然脂肪和油或石油原料那些基团。实例为牛油烷基、硬化牛油烷基、菜籽油烷基、硬化菜籽油烷基、妥尔油烷基、硬化妥尔油烷基、椰油烷基、油基、瓢儿菜基(erucyl)或大豆油烷基。R2和R3各自独立地选自具有1至约6个碳原子,在另一实施方案中具有1-4个碳原子,在又一实施方案中具有1-3个碳原子的直链或支化的烷基或羟基烷基。R4选自H、OH、具有1至约4个碳原子的烷基或羟基烷基;在另一实施方案中,为乙基、羟基乙基、OH或甲基。对其余取代基而言,k为2-20,在另一实施方案中为2-12,在又一实施方案中为2-6,在又一实施方案中为2-4的整数;m为1-20,在另一实施方案中为1-12,在又一实施方案中为1-6,在又一实施方案中为1-3的整数;且n为0-20,在另一实施方案中为0-12,在又一实施方案中为0-6,在又一实施方案中为0-1的整数。
本文所公开并描述的胶凝剂为可单独添加的表面活性剂或者其可用作本发明含水增稠组合物中的主要组分。本发明所设想的胶粘剂实例包括但不限于选自如下组的那些:芥酰胺基丙基羟基丙基磺基甜菜碱、芥酰胺基丙基羟基乙基磺基甜菜碱、芥酰胺基丙基羟基甲基磺基甜菜碱及其混合物等。芥酰胺基丙基羟基丙基磺基甜菜碱(也称为芥酰胺基羟基丙基磺基甜菜碱)为可有用地用于本发明粘弹性流体中的胶凝剂的实例。
在制备本发明胶凝剂的示例性方法中,使芥酰胺基丙基羟基丙基磺基甜菜碱、N-(3-二甲氨基丙基)芥酰胺与3-氯-2-羟基-1-丙磺酸钠(HOPAX,“CHOPSNA”)在SCA40B乙醇(助溶剂1)、去离子水(助溶剂2)、丙二醇(助溶剂3)和NaOH存在下于N2下反应。将所述反应混合物在搅拌下加热至112-115℃,直至游离胺和胺盐的含量均在1%以下。如果胺盐含量在1%以上,则进行NaOH调节。在证实游离胺和胺盐符合规格之后,将所述反应混合物冷却至65℃并减压。然后向批料中添加水以溶解所有的盐。最终水浓度范围通常为约15-25%,在另一实施方案中为15-17.5%。
为了获得最佳性能,在本发明组合物的制备和应用中使用数种溶剂。第一种溶剂为二元醇或多元醇,其可为低聚物或聚合物。实例包括但不限于乙二醇、丁二醇、二甘醇、聚丙二醇、聚乙二醇、甘油、丙二醇、四亚甲基二醇、四甲基乙二醇和三亚甲基二醇等。丙二醇(例如1,2-丙二醇)为优选的二醇。
还使用第二种助溶剂,例如醇。所述可在本文中用作助溶剂的醇通常为一元醇且可为链烷醇或醇烷氧基化物。非限制性实例为甲醇、乙醇和丁醇。在一个实施方案中,乙醇为可有用地用于本发明上下文中的醇的实例。
水为第三种溶剂。
助溶剂的相对量和添加顺序对防止反应物料胶凝、溶解所述盐以实施无过滤方法、防止在产物中形成小的上层乙醇相以及使产物的熔点降至最低而言是重要的。就此而言,通常最先添加二醇,例如丙二醇以避免批料潜在胶凝。丙二醇的添加量通常为约10重量%至约16重量%;在另一实施方案中为约12重量%至约15重量%;在另一实施方案中为13重量%或14重量%。
第二种助溶剂,例如乙醇以约16重量%至约22重量%,在另一实施方案中为约17重量%至约21重量%,在另一实施方案中为18重量%、19重量%或20重量%的量添加。
乙醇+丙二醇的总重量%为约25重量%至约40重量%;在另一实施方案中为约30-35重量%;在又一实施方案中为31重量%、32重量%、33重量%或34重量%。乙醇与丙二醇的重量对重量之比可在约1.0至2.2之间变化以避免批料胶凝和形成上层乙醇液相。乙醇与丙二醇的总量相对于所用的N-(3-二甲氨基丙基)芥酰胺的量保持恒定。如果从所述溶液中移除丙二醇,则最终产物的熔点为~20℃,但通过添加丙二醇降至~12℃。
第三种溶剂—水的最终浓度范围通常为约15-25%,在另一实施方案中为15-17.5%。在一个实施方案中,使用约15%的最终批料溶液的最低含水量以确保所有盐均溶解(副产物氯化钠和过量的CHOPSNa)。此外,批料中的乙醇相对于水过少可导致批料胶凝。名义上乙醇与水的重量对重量之比范围通常为约1.0至1.175以避免潜在的胶凝状况。
本发明的粘弹性流体在延长的时间内不经历相分离且显示出高热稳定性。
在一个实施方案中,本发明涉及一种可用作压裂液的含水粘弹性流体以及一种压裂地下地层的方法。该流体在产油油藏区域中产生通道或裂缝,从而通过提供从油藏岩石至井眼的高渗透性通道而提高油产量。在低渗透率区域中,通常在超过上覆岩层重量的压力下泵入压裂液,由此在所述地层岩石中产生裂隙和裂缝。向所述流体中添加支撑剂(例如颗粒状物质),从而通过将引发的裂隙和裂缝支撑开而防止引发的裂缝在泵送阶段结束后闭合。向所述流体中添加胶凝剂以输送该类支撑剂并降低流体滤失。在具有较高渗透率的区域中,可使用不同方法,但通常使用流体增稠剂。
相对于目前用作井下流体的胶凝剂的聚合物(例如多糖),本文所公开的粘弹性组合物提供了若干优点。例如,当用于井下流体时,本文所述的胶凝剂在地层上产生较少的残留物,所述残留物可在井下工艺期间和之后导致地层损害。与通常必须水合的聚合物相比,还更容易地制备胶凝的流体,且所述胶凝的流体可设计成在地层温度或其他因素如氧化剂或酸下“破坏”。也可通过使用溶剂如烃、醇或者甚至由地层采出的油而“破坏”所述胶凝的流体。取决于链长,下文所述的胶凝剂可在宽温度范围内使用,且可有助于从地层中取出油。
为了选择性改变地下岩层的渗透率,可首先将本发明的粘弹性组合物与水以及不同种类和量的有机和无机盐混合以形成粘弹性压裂液,然后以有效降低所述地层的多个渗透性区域的渗透率的量将其注入所述岩层中。所述流体中的粘弹性组合物的浓度可为约0.5重量%至约10重量%,优选为约2重量%至约8重量%,更优选为约3重量%至约5重量%。
在另一实施方案中,本发明涉及一种含水的酸增稠组合物,其以下文所述的水溶液形式包含一种或多种胶凝剂和酸。本文所公开并描述的增稠的酸凝胶可有利地用作酸化液。世界上的大部分烃储量可见于已知具有极低渗透率的碳酸盐岩石结构中。在许多砂岩油藏中,岩石结构可由碳酸盐粘结在一起,或者碳酸盐结垢可由于从溶液中释放出二氧化碳(由压力降所导致)而聚集在采出井附近。可聚集在采出井周围的另一类结垢为铁垢,尤其是铁氧化物和氢氧化物。低渗透率、钻井损害和结垢的聚集均妨碍油流动至采出井,且用于打开井眼周围的通道以提高流速的常规方法是注入酸(称为酸化或酸增产)。
存在两种酸处理方法:压裂酸化,即在压裂压力以上的速率下注入酸以腐蚀所得的裂缝面;和基质酸化,其中在压裂压力以下的速率下注入酸以溶解岩石中的流道或者除去结垢或钻井造成的损害。酸处理用于所有类型的油井中且偶尔用于水井中:其可用于打开裂缝或消除新钻的井中的损害或者恢复产量下降的旧井。将酸泵入井中,在所述井中,其根据如下反应与碳酸钙反应:
CaCO3+2HCl→CaCl2+CO2+H2O
氯化钙(CaCl2)可高度溶于水中且所述酸腐蚀岩石中的通道,由此改善油或气至采出井的流动。氢氯酸与碳酸盐岩立即反应且倾向于形成通过所述岩石的少数大通道(称为“蚓孔(wormhole)”),而不是打开孔结构。酸渗透距离限于至多数英尺。
由于当与碳酸盐岩接触时,氢氯酸反应非常快,因此出于降低反应速率、允许酸更远地渗入地层中或者在井眼周围更均匀地反应的目的,开发了许多产品。氢氯酸的反应可通过使所述酸根据本发明胶凝而延缓。此外,已显示本发明的酸增稠凝胶用高达约13-17%的碳酸钙增稠,此时所述凝胶相分离导致快速稀化。
乙酸的反应由于反应产物(二氧化碳)的累积降低了反应速率而自然变慢。由于二氧化碳渗至地层中或者被油、水或烃气吸收,乙酸的反应继续进行。
通常在紧临钻井之后且开采开始之前,将碳酸盐油藏中的烃井酸化,且通常每2-3年实施重复处理。
本发明的增稠的酸凝胶也可用于基质压裂中,其中通过将悬浮于含水流体中的砂(称为支撑剂)以高于压裂压力的速率注入井中而产生裂缝。当移除注入压力时,砂保持就位,从而支撑开裂缝。因为所述酸与岩石的快反应速率可导致裂缝坍塌,因此极不寻常的是随后用乙酸处理支撑开的裂缝。然而,可由于在裂缝面上从支撑剂悬浮液中滤出凝胶而导致损害,且这可显著降低油或气流动至所述裂缝的速率。
油井通常垂直向下钻入油藏中且通过油藏的产油带。油流入垂直井眼中。近年来,在水平方向上经由油藏由垂直井眼钻出井已广泛采用。在许多情况下,水平井将烃产量提高数个数量级。由水平井积聚钻井泥浆滤饼和细岩石颗粒所造成的钻井损害的消除是一个非常昂贵的工艺,这是因为需要使用专家技术(如通过盘管注入酸)以避免井口设备的腐蚀并防止氢氯酸在其达到水平井的远端之前浪费。酸处理或地层酸化的目的是消除尽可能多的沿烃流道的地层损害。因此,有效的处理必须消除尽可能多的沿整个流道的损害。本发明的流体和技术允许所述酸最大地渗透,从而导致更有效的处理。
最后,当油藏由于天然油藏压力降低而耗尽时,可注入水或二氧化碳气体以进一步恢复油层中现存油量的百分比。将水或气体经由一定比例的井(注入井)注入油藏中,由此将油推动至采出井。在一些油藏中,水的注入速率低,因此采油速率低。利用本发明酸凝胶的酸处理可用于提高注入井的注入。
相对于目前用作井下流体的胶凝剂的聚合物(例如多糖),本文所公开的胶凝剂具有若干优点。例如,当用作井下流体的胶凝剂时,本文所述的化合物在地层上导致更少的残留物,所述残留物可在井下工艺期间和之后导致地层损害。
与通常必须水合的聚合物相比,还更容易地制备胶凝的流体,且所述胶凝的流体可设计成在地层温度或其他因素如氧化剂下“破坏”。也可通过使用溶剂如烃、醇或者甚至由地层采出的油而“破坏”所述胶凝的流体。取决于链长,下文所述的胶凝剂可在宽温度范围内使用,且可有助于从地层中取出油。
为了选择性改变地下岩层的渗透率,可首先将一种或多种胶凝剂与所需浓度的含水酸组合物混合以形成增稠的酸性粘弹性流体,然后以有效改变所述地层的渗透率的量将其注入所述岩层中。任选地,所述酸流体中的胶凝剂浓度可为约0.5重量%至约10重量%,优选为约2重量%至约8重量%,更优选为约4重量%至约6重量%。还重要的是所述胶凝剂包含小于约1%的游离脂肪酸以获得最佳性能。
也可使用螯合剂以在储存期间在较高温度下稳定所述产物。优选的螯合剂为膦酸盐,如由SolutiaTM以商品名销售的膦酸盐。优选的产品为2010。螯合剂可在制备本发明胶凝剂组合物的方法期间或在其后的任何时间点添加。
取决于所需的粘度,胶凝剂组合物的浓度优选为约1%至约10%,更优选为约3%至8%,最优选为约4%至约6%。
已显示本发明的胶凝剂有效增稠0-15%的HCl酸溶液。
本发明的组合物也可包含无机盐(例如含有碱金属盐、碱土金属盐和/或铵盐的盐水)以及其他粘度改性添加剂(例如纤维素)。用该类试剂胶凝的盐水有利地用作水转向剂、推进流体、压裂液、钻井泥浆、砾石充填流体、钻井液、修井液和完井液等。
本发明的胶凝酸组合物还可用于清洁和消毒配制剂、水基涂料(例如漆)、洗涤剂配制剂、个人护理配制剂、水基沥青体系、混凝土、建筑产品(例如灰浆、灰泥、接合复合物等)、农业漂移控制剂中,用于油井增产应用等中。
当用于增产应用中时,本发明的增稠流体可任选包含润滑剂、腐蚀抑制剂和各种其他添加剂。
润滑剂可包括有机硫、磷、硼或羧酸的金属或胺盐。典型的该类盐为如下物质的胺盐:1-22个碳原子的羧酸,包括芳族和脂族酸;含硫的酸,如烷基和芳族磺酸等;含磷的酸,如磷酸、亚磷酸、次膦酸、酸式磷酸酯以及类似的硫同系物如硫代磷酸和二硫代磷酸以及相关的酸性酯;巯基苯并噻唑;含硼的酸,包括硼酸、酸式硼酸盐等;以及月桂酸。
腐蚀抑制剂可包括碱金属亚硝酸盐、硝酸盐、磷酸盐、硅酸盐和苯甲酸盐。典型的合适有机抑制剂包括烃基胺和羟基取代的烃基胺中和的酸化合物,如中和的磷酸盐和烃基磷酸酯、中和的脂肪酸(例如具有8至约22个碳原子的那些)、中和的芳族羧酸(例如4-叔丁基苯甲酸)、中和的环烷酸和中和的烃基磺酸盐。也可使用烷基化琥珀酰亚胺的混合盐酯。腐蚀抑制剂也可包括链烷醇胺,如乙醇胺、二乙醇胺、三乙醇胺和相应的丙醇胺以及吗啉、乙二胺、N,N-二乙基乙醇胺、α-和γ-甲基吡啶、哌嗪和异丙基氨基乙醇。
增产液也可包括用于特定应用的添加剂以优化所述流体的性能。实例包括着色剂;染料;除臭剂如香茅;杀菌剂和其他抗微生物剂;螯合剂如乙二胺四乙酸钠盐或次氮基三乙酸;防冻剂如乙二醇和类似的聚氧亚烷基多元醇;消泡剂如含聚硅氧烷的试剂以及剪切稳定剂如市售的聚氧亚烷基多元醇。也可添加抗磨剂、摩擦改性剂、防滑剂和润滑剂。还包括极压添加剂如磷酸酯和二硫代磷酸二烷基酯锌。
本发明的增稠酸凝胶也可有用地用于清洁和消毒配制剂、水基涂料(例如漆)、洗涤剂配制剂、个人护理配制剂、水基沥青体系、混凝土、建筑产品(例如灰浆、灰泥、接合复合物等)、农业漂移控制剂中,用于其他油井增产应用和油田应用等中。
现在借助下文实施例阐述本发明。
实施例1—合成芥酰胺基丙基羟基丙基磺基甜菜碱(Armovis EHS)
制备Armovis EHS的无过滤反应顺序总结如下:
在N
2
下向2L压力额定的反应容器中添加:
1.500g N-(3-二甲氨基丙基)芥酰胺
2.260g3-氯-2-羟基-1-丙磺酸钠(HOPAX“CHOPSNA”)
3.285.0g SCA40B乙醇(助溶剂1)
4.160.0g去离子水(助溶剂2)
5.195g丙二醇(助溶剂3)
6.6.0g50%NaOH。
将所述混合物加热至112-115℃并充分搅拌约6小时,然后取样以证实游离胺和胺盐含量均在1%以下。如果胺盐含量在1%以上,则需要进行NaOH调节。在证实游离胺和胺盐符合规格之后,将所述反应混合物冷却至65℃并减压。然后,向所述批料中添加水以溶解所有盐。最终水浓度范围为15-17.5%。在~65℃下,将最终溶液排至收集容器中。所述物料为浅黄色液体。
关于助溶剂(乙醇、丙二醇和水)的注释:
所述助溶剂的相对量和添加顺序对防止反应物料胶凝、溶解所述盐以实施无过滤方法、防止在产物中形成小的上层乙醇相以及使产物的熔点降至最低而言是重要的。
1.最先添加丙二醇以避免所述批料的潜在胶凝。
2.乙醇与丙二醇的重量对重量之比范围可在约1.0至2.2之间变动以避免批料胶凝且形成上层乙醇液相。乙醇与丙二醇的总量相对于所用的N-(3-二甲氨基丙基)芥酰胺的量保持恒定。
3.如果移除丙二醇或者乙醇与丙二醇的重量对重量之比升至2.2以上,则可形成上层乙醇液相。
4.1.0以下的乙醇与丙二醇的重量对重量之比可导致批料胶凝。
5.如果从所述溶液中移除PG,则产物熔点为~20℃。通过添加PG,熔点降至~12℃。
6.最终批料溶液的最低含水量为~15%以确保所有盐均溶解(副产物氯化钠和过量的CHOPSNa)。
7.批料中的乙醇相对于水过少可导致所述批料胶凝。名义上乙醇与水的重量对重量之比范围为~1.0至1.175以避免潜在的胶凝状况。
典型的批料具有如下组成:
注释:
1.氯化钠由无机氯含量计算。
2.CHOPSNa以钠与无机氯化物分析值之差计算。
3.活性以%固体-游离胺%-胺盐%-氯化钠%-CHOPSNa%计算。
实施例2—制备Armovis EHS凝胶(VES)和流变学测试的一般程序:
将含4-8重量%盐的盐水溶液搅入500ml不锈钢掺合机中。向该溶液中,将特定量(体积)的Armovis EHS浓缩物(40-50重量%,处于含乙醇、丙二醇和水的混合溶剂体系中)添加至所述盐水溶液中。将所得混合物在掺合机中于2000-3000rpm下搅拌3分钟。然后,将所得凝胶在1000rpm离心15分钟以除去气泡。使用Grace Instrument流变仪(型号M5600)在恒定剪切速率和不同温度下评价流变性能。施加400psi的压力以使试样的蒸发最小化,尤其是在高温下。
地下地层的压裂需要使增稠的流体通过井眼和地层以引发裂缝并使其扩展至地层中。使用高粘性流体以防止流体滤失并将支撑剂携带至裂缝中。过去使用聚合物制备增稠的流体,然而对聚合物基压裂液观察到若干缺点:1)其是剪切敏感的。合成聚合物基压裂液是剪切稀化的非牛顿流体。在高剪切速率下,粘度低,且在剪切速率降低之后不再积累。2)其不耐盐。所述聚合物通常从高盐度的溶液中沉淀出,且可导致严重的地层损害。3)生物高分子的热稳定性不是很高。此外,需要生物杀伤剂或氧清除剂以防止生物降解。4)必须使用破乳剂以破坏所述凝胶的粘度。然而,尽管使用破乳剂,破坏效率通常也极低。为了克服所有这些缺点,必须制备表面活性剂基压裂液以获得用于地下地层的清洁得多的体系。所述流体通常在4-8%KCl或NH4Cl溶液中制备以稳定粘土/页岩地层。
实施例3-6显示了Armovis EHS浓度对用于压裂液的不同流体的流变性能的影响。
实施例3
实施例4
实施例5
实施例6
钻井液和完井液通常在CaCl2、CaBr2、ZnBr2等溶液中制备。盐浓度取决于井深度。井越深,则流体越重,这是因为其必须对地下地层施加足够的流体静压。此外,流体应足够粘稠以防止井漏(loss circulation)并将钻屑携带至表面。实施例7-9示意了本发明的Armovis EHS在钻井液和完井液中的应用。
实施例7
实施例8
ZnBr2溶液为该类重盐水(17.2ppg)且通常用于深井中。然而,在将表面活性剂与ZnBr2溶液混合之前,在高温下未观察到良好的流变性能。EHS为在ZnBr2盐水体系中显示出良好粘度的唯一VES体系。
实施例7表明处于20重量%ZnBr2中的本发明Armovis EHS在高达250°F下获得了非常粘稠的凝胶。
实施例9
大多数油藏是非均质的且渗透率逐层变化。在酸化处理期间,所述酸流至具有高渗透率的区域中,这是因为所述区域的阻力较小。仅有限量的酸流至低渗透性区域或受损区域中。注入酸的该非均匀分布可导致主要的经济损失。可有效解决该问题的方法是使用酸转向技术。近年来,已将表面活性剂基酸有效用作一种转向体系。在所述酸与碳酸盐岩石反应后,pH增大且废酸中的二价阳离子[Ca(II)和Mg(II)]浓度提高。这两个因素导致表面活性剂分子形成长棒状胶束,这显著提高了所述溶液的表观粘度且迫使所述酸流至低渗透性区域中。
实施例10—显示了本发明Armovis EHS在HCl酸化应用终点时对碳酸盐油藏的增产用途。
使用原料Armeen以制备本发明的Armovis EHS。未反应的胺似乎对所述表面活性剂体系的流变性能具有不利影响。
实施例11—显示了胺杂质Armeen对用于酸化液中的胶凝剂体系的流变性能的影响。
所述凝胶包含30%CaCl2、6%Armovis EHS和x%ArmeenAPA-E的百分比为Armeen浓度与Armovis EHS的活性浓度的百分比。
Claims (14)
1.一种含水粘弹性流体,其包含至少一种胶凝剂组合物,其中所述胶凝剂组合物包含至少一种如下通式的粘弹性表面活性剂:
其中R1为具有17至29个碳原子的饱和或不饱和烃基;R2和R3各自独立地选自具有1至6个碳原子的直链或支化的烷基或羟基烷基;R4选自H、OH、具有1至4个碳原子的烷基或羟基烷基;k为2-20的整数;m为1-20的整数;且n为0-20的整数;和
包含水、一元醇和多元醇的溶剂体系,
其中所述一元醇为乙醇且所述多元醇为丙二醇;其中所述胶凝剂组合物中的所述一元醇与所述多元醇的重量对重量之比为1.0至2.2,所述胶凝剂组合物的含水量为15重量%或更高,且乙醇与水的重量对重量之比为1.0至1.175。
2.根据权利要求1的流体,其中R1为具有18至21个碳原子的饱和或不饱和烃基;R2和R3各自独立地选自具有1至3个碳原子的直链或支化烷基或羟基烷基;R4选自H、具有1至3个碳原子的烷基或羟基烷基;k为2-6的整数;m为1-6的整数且n为0-6的整数。
3.根据权利要求1的流体,其包含10重量%至16重量%的丙二醇和16重量%至22重量%的乙醇;其中乙醇+丙二醇的总重量%为30重量%至35重量%。
4.一种井增产液,其包含0.5%至10%的权利要求1的含水粘弹性流体。
5.根据权利要求4的井增产液,其为压裂液、基质酸化液、完井酸化液、压裂酸化液或损害消除酸化液。
6.一种酸化液,其包含至少一种酸和有效量的权利要求1的粘弹性流体。
7.根据权利要求6的酸化液,其中所述酸选自无机酸、有机酸及其混合物。
8.根据权利要求7的酸化液,其中所述酸选自氢氯酸、氢氟酸、乙酸、甲酸、氨基磺酸、氯乙酸及其混合物。
9.一种酸化地下地层的方法,其包括将权利要求6的酸化液注入所述地层中。
10.根据权利要求9的方法,其中所述地层为油气藏或水藏。
11.根据权利要求10的方法,其中所述酸化液以等于或高于矿藏压裂压力的速率注入所述矿藏中。
12.一种含水压裂液,其包含有效量的权利要求1的粘弹性流体。
13.一种压裂地下地层的方法,其包括在足以压裂所述地层的压力下将权利要求12的含水压裂液经由井眼泵入地下地层中的步骤。
14.一种含水粘弹性流体,其包含至少一种胶凝剂组合物,其中所述胶凝剂组合物包含至少一种如下通式的粘弹性表面活性剂:
其中R1为具有17至29个碳原子的饱和或不饱和烃基;R2和R3各自独立地选自具有1至6个碳原子的直链或支化的烷基或羟基烷基;R4选自H、OH、具有1至4个碳原子的烷基或羟基烷基;k为2-20的整数;m为1-20的整数;且n为0-20的整数,
15-25重量%水,
16重量%至22重量%的乙醇,和
10重量%至16重量%丙二醇;
乙醇+丙二醇的总重量%为30-35重量%,其中乙醇与丙二醇的重量对重量之比为1.0至2.2,乙醇与水的重量对重量之比为1.0至1.175。
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