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CN101675143B - 对通过流体输送颗粒的控制 - Google Patents

对通过流体输送颗粒的控制 Download PDF

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CN101675143B
CN101675143B CN2008800136822A CN200880013682A CN101675143B CN 101675143 B CN101675143 B CN 101675143B CN 2008800136822 A CN2008800136822 A CN 2008800136822A CN 200880013682 A CN200880013682 A CN 200880013682A CN 101675143 B CN101675143 B CN 101675143B
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张克卫
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Abstract

用于诸如石油和管道工业等工业的水性浆液组合物，其包含颗粒、水性载体流体、使颗粒表面疏水的化合物和少量油。通过在制备浆液期间或之前使颗粒的表面疏水来制备浆液。一旦放入井筒中，油的添加大大增强了疏水改性颗粒的聚集潜力。

Description

对通过流体输送颗粒的控制
领域 
本发明涉及流体组合物，及其在水力压裂处理之后控制支撑剂回流中的用途，以及在未很好地固化的地层中减少随着流体产生的地层砂中的用途。 
背景 
水力压裂操作广泛地应用于石油工业以提高油气的产量。在水力压裂操作中，通过井筒在足以引起压裂的压力下将压裂液注入地层以提高油气的产量。 
通常，被称为支撑剂的颗粒悬浮在压裂液中并作为浆液被输送至裂缝处。支撑剂包括砂、陶粒、玻璃球、铝土矿(氧化铝)、树脂包被的砂、合成高分子小球等等。其中，砂是迄今为止最为常用的支撑剂。 
常用的压裂液包括水性流体和包括烃、甲醇、液态二氧化碳的非水性流体。最常用的压裂液是包括水、盐水、含聚合物或粘弹性表面活性剂的水和泡沫流体的水性流体。 
在压裂处理的最后阶段，使压裂液流回地表而将支撑剂留在裂缝中，以防止裂缝在水力压裂压力解除后闭合。填充了支撑剂的裂缝提供了高传导性的通道，所述通道使得油和/气更有效地通过其渗入井筒。支撑剂停留在裂缝之后形成的支撑剂填充层的传导性在提高油气的产量中起重要作用。 
然而，常见的是，大量的支撑剂随着回流出油井的流体被带出裂缝并进入井筒。该过程被称为支撑剂回流。支撑剂回流是高度不期望的，因为其不仅减少了留在裂缝中的支撑剂的量从而导致传导性较低的通道，还导致了明显的操作难度。由于其对油井生产率和设备的不利影响，这长期困扰着石油工业。 
已经尝试了许多方法以解决支撑剂回流的问题。常用的方法为使 用所谓的“树脂包被支撑剂”。树脂包被支撑剂的外表面具有附着的树脂包衣，使得支撑剂颗粒在合适的条件下互相结合在一起，形成有渗透性的屏障并减少支撑剂回流。 
树脂包被支撑剂的基质包括砂、玻璃球和诸如贝壳或种子的有机材料。所用树脂包括环氧树脂、脲醛树脂、酚醛树脂、糠醇树脂和糠醛树脂。一旦支撑剂处于适当的位置上，就能够通过通常称为活化剂的化学粘合剂的增孔(overflush)将树脂包被的支撑剂预固化或者固化。 
已经使用了不同的粘合剂。美国专利第3,492,147和3,935,339号公开了使用不同树脂将固体颗粒包衣的组合物和方法。待包衣的颗粒包括砂、坚果壳、玻璃球和铝小球。所用树脂包括脲醛树脂、酚醛树脂、环氧树脂、糠醇树脂以及聚酯或烷基树脂。树脂能够是纯净形式或包含固化剂、偶联剂或其它添加剂的混合物。例如第5,643,669、5,916,933、6,059,034和6,328,105号美国专利中描述了用于支撑剂的树脂和树脂混合物的其它实例。 
然而，树脂包被支撑剂的使用有明显的局限性。例如，树脂包被支撑剂比普通砂贵得多，特别是考虑到压裂处理经常在单个油井中使用成吨的支撑剂。通常，当地层温度低于60℃时，需要活化剂以使树脂包被支撑剂结合在一起。这增加了成本。 
因此，树脂包被支撑剂的高成本限制了其仅在某些类型的油井中使用，或只在压裂处理的最终阶段使用，其又被称为支撑剂的“收尾”，其中将最后数吨支撑剂泵送入裂缝中。对于经济上不够可行的油井，树脂包被支撑剂的应用经常变得成本过高而不可行。 
在油气开采过程中，特别是未很好固化的地层中，通常为砂的小颗粒经常随着产出流体流入井筒。这是因为在没有很好地固化的地层中，地层砂结合在一起的结合强度不足以经受流过的流体施加的力，并容易被流出油井的产出流体带走。 
产生的砂侵蚀地表和地下的设备，并要求在能够处理油气之前将其移除。已经尝试了不同的方法以减少地层砂的产生。所用的方法之一是通过井筒中的筛子所保留的砾石层过滤产出流体，其中颗粒被砾石层捕获。这种技术被称为砾石过滤。然而，这种技术比较耗时而且 昂贵。砾石和筛子能够在较短的时间内被砂堵塞或侵蚀。 
已经在某些情况下使用的另一种方法是向地层注入多种树脂以增强地层砂的结合。然而，这种方法导致不确定性并且有时产生不期望的结果。例如，由于控制化学反应的不确定性，树脂会自己固结在井筒中，而不是在未很好固化的生产层中。使用树脂组合物中遇到的另一问题是树脂的保存期限通常很短。例如，如果在混合树脂后推迟了使用树脂的操作，则能够导致产生昂贵的废弃物。 
因此，亟需划算的组合物和能够在压裂处理之后控制支撑剂回流的方法。还亟需降低来自未很好固化地层的地层砂的产生的组合物和方法。 
概述 
在一实施方案中，本发明涉及水性浆液组合物，其包含水、颗粒、使颗粒表面疏水的化合物和油。 
在另一实施方案中，本发明涉及控制油气生产地层中的砂的方法，其包括以下步骤：混合水、颗粒和使颗粒表面疏水的化合物，将混合物泵送入地层。 
发明详述 
在自然、工业实践以及日常生活中，到处都可以观察到水中的疏水相互作用导致的聚集现象。通常，不被理论所限制，疏水相互作用是指水中两个或更多个非极性颗粒之间的吸引力。当疏水相互作用变得足够强时，疏水颗粒聚到一起以进一步减少表面能，基本上使颗粒桥接在一起并导致形成颗粒聚集体，这被称为疏水聚集体。附着在疏水颗粒表面的微泡也趋向于将颗粒桥接在一起也是已知的。 
在本发明中应用疏水聚集体的概念以开发控制支撑剂的回流以及减少油井生产中地层砂的产生的组合物和方法。与将注意力集中在通过在覆盖于颗粒表面的树脂之间形成化学键使得支撑剂或砂颗粒粘合的常规方法不同，本发明中，注意力集中在通过强烈的疏水力或微泡桥接颗粒来制备颗粒聚集体。此外，本发明组合物引起的颗粒的疏水 表面降低了颗粒和水之间的摩擦，使它们更难被流出油井的流体带走。 
通常，本发明只需要有限量的化学剂并且施工作业是简单的。 
有不同的方式实施本发明。例如，在压裂操作过程中，将天然疏水的并能够被水轻易地湿润的诸如砂的支撑剂与包含化学剂的流体混合，所述化学剂又称为疏水剂，其使砂的表面疏水。能够将疏水剂简单地添加至被泵送至井下的包含砂和压裂液的砂浆液中。能够根据所用的疏水剂和应用条件使用不同的压裂液(水性或非水性流体)。通常优选水性流体。水、盐水或又称为光滑水(slick-water)的包含少量减摩剂的水是特别受关注的压裂液。 
能够将疏水剂应用于整个支撑阶段或诸如支撑阶段的最后部分即收尾的部分支撑阶段。或者，能够先将砂疏水化并干燥然后再将其用于制备浆液并泵送入裂缝。 
已经发现，当将少量包括烃油和硅油在内的油与包含疏水化的砂的水性浆液混合时，明显增强了疏水聚集。其可能的解释是油在疏水砂中的集中可能进一步增强了砂粒间的桥接。 
能够以多种方式使用本发明。例如，在压裂操作中，将诸如砂的支撑剂与水基浆液中的疏水剂混合，并将其泵送入裂缝，然后通过油或含少量油的水的增孔，以增强砂粒间的桥接。类似地，能够在收尾阶段使用相同的操作。或者，能够将包含疏水剂的浆液泵送入裂缝形成支撑剂充填层，所述支撑剂充填层能够通过油或包含于地层中的凝析油(condensate)被进一步固化。或者将预疏水化的砂用作支撑剂，随后用包含少量油的水冲洗。或者将预疏水化的砂用作支撑剂，所述支撑剂能够通过油或包含于地层中的凝析油被进一步固化。或者将预疏水化的砂用于收尾，随后用包含少量油的水冲洗。在所有这样的操作中，能够将诸如氮气、二氧化碳或空气的气体混合入流体中。 
有不同的预处理固体表面使其疏水的方法。例如，一种方法可将优选为砂的支撑剂与包含适当疏水剂的流体完全混合一段时间。支撑剂颗粒干燥后，能够将它们用于压裂操作。能够使用不同的流体。不同的疏水剂可能需要不同的条件以与固体表面相互作用。当使用水性流体时，流体的pH值也可能起作用。 
除了在水力压裂处理中控制支撑剂回流，本发明还可用于减少油井生产中地层砂的产生。在大部分情况下，当油井开始产生水时，砂的产量大量增加。地层砂通常是亲水性的，或水润湿的，因此易被流动的水相带走。能够根据所用的疏水剂和操作条件使用不同的水性或非水性运送流体。根据本发明，有不同的方法处理地层以减少地层砂的产生。例如，能够将包含合适量的疏水剂的流体，优选水性流体，注入未很好地固化的地层。砂粒变得疏水之后，其趋向于聚集在一起。疏水表面也减少了水性流体施加的拖拽力，这使得其更难被地层流体带走。如果水相包含一定量的油，则能够进一步增强砂粒间的疏水聚集。或者，能够先将包含疏水剂的流体注入未很好固化的地层，随后注入小体积的油或包含流体的油。在所有的这些应用中，能够将诸如氮气、二氧化碳或空气的气体混合入流体中。 
此外，能够将本发明的组合物和方法用于砾石层操作，其中将包含疏水化的砂的浆液添加至井筒中以补救砂的产生。 
有多种类型的用于砂的疏水剂能够用于本发明中。例如，已知许多有机硅化合物，包括有机硅氧烷、有机硅烷、氟代有机硅氧烷和氟代有机硅烷化合物常用于使各种表面疏水。例如，参见美国专利第4,537,595、5,240,760、5,798,144、6,323,268、6,403,163、6,524,597和6,830,811号，这些文献并入本文作为参考。 
有机硅烷是含有硅碳键的化合物。有机硅氧烷是含有Si-O-Si键的化合物。聚硅氧烷是这样的化合物，其中元素硅和氧在分子骨架中交替，即重复Si-O-Si键。最简单的聚硅氧烷是聚二甲基硅氧烷。 
聚硅氧烷化合物能够被具有不同碳数的多种有机取代基修饰，所述取代基可含有赋予期望特性的N、S或P部分。例如，阳离子聚硅氧烷是这样的化合物，其中在聚硅氧烷链的中间或末端连接一个或两个有机阳离子基团。有机阳离子基团通常可以含有羟基基团或含有N或O的其它官能团。最常见的有机阳离子基团是烷基胺衍生物，包括仲、叔和季胺(例如季盐聚硅氧烷，包括单-和二-季盐聚硅氧烷、酰胺基季盐聚硅氧烷、咪唑啉季盐聚硅氧烷以及羧基季盐聚硅氧烷)。 
类似地，聚硅氧烷能够被有机两性基团修饰，其中在聚硅氧烷链 的中间或末端连接一个或多个有机两性基团，并且所述有机两性基团包括甜菜碱聚硅氧烷和磷酸酯基甜菜碱聚硅氧烷。 
类似地，聚硅氧烷能够被有机阴离子基团修饰，其中在聚硅氧烷链的中间或末端连接一个或多个有机阴离子基团，包括硫酸盐聚硅氧烷、磷酸盐聚硅氧烷、羧酸盐聚硅氧烷、磺酸盐聚硅氧烷、硫代硫酸盐聚硅氧烷。有机硅氧烷化合物还包括烷基硅氧烷，包括六甲基环三硅氧烷、八甲基环四硅氧烷、十甲基环五硅氧烷、六甲基二硅氧烷、六乙基二硅氧烷、1，3-二乙烯基-1，1，3，3-四甲基二硅氧烷、八甲基三硅氧烷、十甲基四硅氧烷。 
有机硅烷化合物包括烷基氯硅烷，例如甲基三氯硅烷、二甲基二氯硅烷、三甲基氯硅烷、十八烷基三氯硅烷；烷基烷氧基硅烷化合物，例如甲基-、丙基-、异丁基-和辛基三烷氧基硅烷，以及氟代有机硅烷化合物，例如2-(全氟正辛基)-乙基三乙氧基硅烷和全氟辛基二甲基氯硅烷。 
能够用于使颗粒表面疏水的有机硅化合物之外的其它类型的化合物为某些氟取代的化合物，例如某些包括阳离子氟代有机化合物的氟代有机化合物。 
关于有机硅化合物的进一步信息能够在Silicone Surfactants(硅酮表面活性剂)(Randal M.Hill，1999)及其中的参考文献中，以及在美国专利第4,046,795、4,537,595、4,564,456、4,689,085、4,960,845、5,098,979、5,149,765、5,209,775、5,240,760、5,256,805、5,359,104、6,132,638和6,830,811号中以及加拿大专利第2,213,168号中找到，这些文献并入本文作为参考。 
有机硅烷能够用下列通式表示 
RnSiX(4-n)                           (I) 
其中R是具有1至50个碳原子的有机基团，其可以带有赋予期望特性的含N、S或P部分的官能团，X是卤素、烷氧基、酰氧基或胺，并且n值为0至3。有机硅烷的实例包括： 
CH3SiCl3、CH3CH2SiCl3、(CH3)2SiCl2、(CH3CH2)2SiCl2、(C6H5)2SiCl2、(C6H5)SiCl3、(CH3)3SiCl、CH3HSiCl2、(CH3)2HSiCl、CH3SiBr3、(C6H5)SiBr3、(CH3)2SiBr2、(CH3CH2)2SiBr2、(C6H5)2SiBr2、(CH3)3SiBr、CH3HSiBr2、(CH3)2HSiBr  、Si(OCH3)4、CH3Si(OCH3)3、CH3Si(OCH2CH3)3、CH3Si(OCH2CH2CH3)3、CH3Si[O(CH2)3CH3]3、CH3CH2Si(OCH2CH3)3、C6H5Si(OCH3)3、C6H5CH2Si(OCH3)3、C6H5Si(OCH2CH3)3、CH2＝CHCH2Si(OCH3)3、(CH3)2Si(OCH3)2、(CH2＝CH)Si(CH3)2Cl、(CH3)2Si(OCH2CH3)2、(CH3)2Si(OCH2CH2CH3)2、(CH3)2Si[O(CH2)3CH3]2、(CH3CH2)2Si(OCH2CH3)2、(C6H5)2Si(OCH3)2、(C6H5CH2)2Si(OCH3)2、(C6H5)2Si(OCH2CH3)2、(CH2＝CH)2Si(OCH3)2、(CH2＝CHCH2)2Si(OCH3)2、(CH3)3SiOCH3、CH3HSi(OCH3)2、(CH3)2HSi(OCH3)、CH3Si(OCH2CH2CH3)3、(C6H5)2Si(OCH2CH2OCH3)2、(CH3)2Si(OCH2CH2OCH3)2、(CH2＝CH)2Si(OCH2CH2OCH3)2、(CH2＝CHCH2)2Si(OCH2CH2OCH3)2、(C6H5)2Si(OCH2CH2OCH3)2、CH3Si(CH3COO)3、3-氨基三乙氧基硅烷、甲基二乙基氯硅烷、丁基三氯硅烷、二苯基二氯硅烷、乙烯基三氯硅烷、甲基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三(甲氧基乙氧基)硅烷、甲基丙烯酰氧基丙基三甲氧基硅烷、环氧丙氧基丙基三甲氧基硅烷、氨基丙基三乙氧基硅烷、二乙烯基二-2-甲氧基硅烷、乙基三丁氧基硅烷、异丁基三甲氧基硅烷、己基三甲氧基硅烷、正辛基三乙氧基硅烷、二己基二甲氧基硅烷、十八烷基三氯硅烷、十八烷基三甲氧基硅烷、十八烷基二甲基氯硅烷、十八烷基二甲基甲氧基硅烷以及包括3-(三甲氧基甲硅烷基)丙基二甲基十八烷基氯化铵、3-(三甲氧基甲硅烷基)丙基二甲基十八烷基溴化铵、3-(三甲基乙氧基甲硅烷基丙基)二癸基甲基氯化铵、三乙氧基甲硅烷基大豆丙基二甲基氯化铵(triethoxysilyl soyapropyl dimonium chloride)、3-(三甲基乙氧基甲硅烷基丙基)二癸基甲基溴化铵、3-(三甲基乙氧基甲硅烷基丙基)二癸基甲基溴化铵、三乙氧基甲硅烷基大豆丙基二甲基溴化铵(triethoxysilyl soyapropyl dimonium bromide)在内的硅烷季铵盐、(CH3O)3Si(CH2)3P+(C6H5)3Cl、(CH3O)3Si(CH2)3P+(C6H5)3Br-、、 (CH3O)3Si(CH2)3P+(CH3)3Cl-、(CH3O)3Si(CH2)3P+(C6H13)3Cl-、(CH3O)3Si(CH2)3N+(CH3)2C4H9Cl、(CH3O)3Si(CH2)3N+(CH3)2CH2C6H5Cl-、(CH3O)3Si(CH2)3N+(CH3)2CH2CH2OHCl-、(CH3O)3Si(CH2)3N+(C2H5)3Cl-、(C2H5O)3Si(CH2)3N+(CH3)2C18H37Cl-。 
在可用于本发明的不同的有机硅氧烷化合物中，实例为被有机两性或阳离子基团修饰的聚硅氧烷，其包括有机甜菜碱聚硅氧烷和有机季盐聚硅氧烷。一类甜菜碱聚硅氧烷或季盐聚硅氧烷用以下通式表示： 
Figure G2008800136822D00081
其中R1至R6以及R8至R10中每一基团均代表含1至6个碳原子的烷基，通常为甲基基团，R7对于甜菜碱聚硅氧烷代表有机甜菜碱基团，或者对于季盐聚硅氧烷代表有机季盐基团，并且具有不同数目的碳原子，并且可包含羟基基团或其它含有N、P或S的官能团，并且m和n为1至200。例如，一类季盐聚硅氧烷是当R7由下列基团表示： 
Figure G2008800136822D00082
其中R1、R2、R3是具有1至22个碳原子的烷基基团或具有2至22个碳原子的烯基基团。R4、R5、R7是具有1至22个碳原子的烷基基团或具有2至22个碳原子的烯基基团；R6是-O-或NR8基团，R8是具有1至4个碳原子的烷基或羟基烷基基团或氢；Z是具有至少4个碳原子的二价烃基团，其可具有羟基基团并且可插入氧原子、氨基基团或酰胺基团；x是2至4；R1、R2、R3、R4、R5、R7可相同或不同，并 且X-是无机或有机阴离子，其包括Cl-和CH3COO-。有机季盐基团的实例包括[R-N+(CH3)2-CH2CH(OH)CH2-O-(CH2)3-](CH3COO-)，其中R是含有1至22个碳的烷基基团或苄基基团并且CH3COO-是阴离子。有机甜菜碱的实例包括-(CH2)3-O-CH2CH(OH)(CH2)-N+(CH3)2CH2COO-。这样的化合物是可商购的。甜菜碱聚硅氧烷共聚多元醇是实例之一。应当理解，阳离子聚硅氧烷包括由通式(II)代表的化合物，其中R7代表其它有机胺衍生物，其包括有机伯、仲和叔胺。 
有机修饰的聚硅氧烷的其它实例包括二甜菜碱聚硅氧烷和二季盐聚硅氧烷，其中两个甜菜碱或季盐基团与硅氧烷链相连。一类二甜菜碱聚硅氧烷和二季盐聚硅氧烷能够以下列通式表示： 
其中基团R12至R17均代表含有1至6个碳原子的烷基，通常为甲基基团，R11和R18基团对于二甜菜碱聚硅氧烷均代表有机甜菜碱基团或者对于二季盐聚硅氧烷均代表有机季盐基团，并且具有不同数目的碳原子，并且可以含有羟基基团或其它含有N、P或S的官能团，并且m是1至200。例如，一类二季盐聚硅氧烷是当R11和R18由下列基团表示： 
其中R1、R2、R3、R4、R5、R6、R7、Z、X-和x与上文的定义相同。这样的化合物是可商购的。Quaternium 80(INCI)是商业产品的实例之 一。 
本领域技术人员应当理解，阳离子聚硅氧烷包括由通式(III)表示的化合物，其中R11和R18代表其它有机胺衍生物，其包括有机伯、仲和叔胺。对于本领域技术人员，显然有不同的单-和二-季盐聚硅氧烷、单-和二-甜菜碱聚硅氧烷和其它有机修饰的聚硅氧烷化合物能够用于使固体表面疏水并且可用于本发明。这些化合物广泛用于个人护理和其它产品，例如在美国专利第4,054,161、4,654,161、4,891,166、4,898,957、4,933,327、5,166,297、5,235,082、5,306,434、5,474,835、5,616,758、5,798,144、6,277,361、6,482,969、6,323,268和6,696,052号中所讨论的，这些文献并入本文作为参考。 
能够用于本发明组合物的有机硅化合物的另一实例是氟代有机硅烷或氟代有机硅氧烷化合物，其中硅烷或硅氧烷化合物中至少部分有机基团被氟化。适当的实例为氟化的氯硅烷或氟化的烷氧基硅烷，其包括2-(全氟正辛基)乙基三乙氧基硅烷、全氟辛基二甲基氯硅烷、(CF3CH2CH2)2Si(OCH3)2、CF3CH2CH2Si(OCH3)3(CF3CH2CH2)2Si(OCH2CH2OCH3)2和CF3CH2CH2Si(OCH2CH2OCH3)3和(CH3O)3Si(CH2)3N+(CH3)2(CH2)3NHC(O)(CF2)6CF3Cl-。其它能够使用但不那么优选的化合物为氟代的非有机硅化合物的化合物，例如某些氟代有机化合物。 
下文提供了根据本发明的组合物和方法的若干非限制性实施例。 
实施例1 
向1000ml的水中添加300g美国筛网20/40目的压裂砂，所述水中含有2ml的含有20vol％Tegopren 6924和80vol％乙二醇单丁醚的溶液和1ml的TEGO甜菜碱810，Tegopren 6924为来自Degussa公司的二季盐聚二甲基硅氧烷，TEGO甜菜碱810为癸酰基/癸酰胺基丙基甜菜碱，是来自Degussa公司的两性烃类表面活性剂。将浆液摇匀，然后静置使砂沉淀。缓慢倾斜时，沉淀的砂倾向于作为凝聚的块移动。添加1ml粘度为200cp的硅油后，将其混合入浆液中并摇匀，目测观察到砂粒彼此粘在一起形成强烈的桥接。 
将溶液倒出，将砂在室温下过夜干燥以用于进一步试验。 
实施例2 
将200g根据实施例1预处理的砂置于失水室中以形成砂袋，并用水润湿。然后，使300ml的水从顶部通过砂袋进行过滤。当水滴慢于每五秒钟一滴时，停止计时。使用未处理的砂进行相同的试验作为对照。预处理的砂的超过6轮的平均过滤时间为2分5秒，而未处理的砂为5分钟。 
实施例3 
将200g根据实施例1预处理的砂置于失水室中以形成砂袋，并用煤油润湿。然后，使300ml的煤油从顶部通过砂袋进行过滤。当煤油滴慢于每五秒钟一滴时，停止计时。使用未处理的砂进行相同的试验作为对照。预处理的砂的超过5轮的平均过滤时间为3分2秒，而未处理的砂为3分28秒。 
实施例4 
向两个玻璃瓶(200ml)中均加入100ml的水和25g的美国筛网30/50目压裂砂。第一份样品用作对照。向第二份样品中添加2ml的含有20％Tegopren 6924和80％乙二醇单丁醚的溶液和0.05ml的煤油。将浆液摇匀然后静置使砂沉淀。缓慢倾斜时，沉淀的砂倾向于作为凝聚的块移动。目测观察到砂粒粘在一起，彼此形成强烈的桥接。 
实施例5 
向两个玻璃瓶(200ml)中均加入100ml的水和25g的美国筛网30/50目压裂砂。第一份样品用作对照。向第二份样品中添加2ml的含有20％Tegopren 6924和80％乙二醇单丁醚的溶液和0.05ml的压裂油。将浆液摇匀然后静置使砂沉淀。缓慢倾斜时，沉淀的砂倾向于作为凝聚的块移动。目测观察到砂粒粘在一起，彼此形成强烈的桥接。 

Claims (50)

1.水性浆液组合物，其包含
水；
颗粒；
使所述颗粒的表面疏水的化合物；和
油；
其中所述油选自烃油、硅油、烃油和硅油二者、煤油或压裂油；
其中所述化合物选自有机硅烷、有机硅氧烷或氟代有机化合物。
2.如权利要求1所述的组合物，其中所述颗粒选自砂、树脂包被的砂、合成高分子小球、陶瓷、碳酸盐、铝土矿、页岩和煤颗粒。
3.如权利要求1所述的组合物，其中所述颗粒是地层颗粒。
4.如权利要求1所述的组合物，其中所述氟代有机化合物为氟代有机硅烷或氟代有机硅氧烷。
5.如权利要求1所述的组合物，其中所述化合物是具有下列通式的有机硅烷
RnSiX(4-n)
其中R是具有1至50个碳原子的有机基团，X是卤素、烷氧基、酰氧基或胺基，并且n值为1至3。
6.如权利要求5所述的组合物，其中所述有机硅烷选自：
CH3SiCl3、CH3CH2SiCl3、(CH3)2SiCl2、(CH3CH2)2SiCl2、(C6H5)2SiCl2、(C6H5)SiCl3、(CH3)3SiCl、CH3HSiCl2、(CH3)2HSiCl、CH3SiBr3、(C6H5)SiBr3、(CH3)2SiBr2、(CH3CH2)2SiBr2、(C6H5)2SiBr2、(CH3)3SiBr、CH3HSiBr2、(CH3)2HSiBr、Si(OCH3)4、CH3Si(OCH3)3、CH3Si(OCH2CH3)3、CH3Si(OCH2CH2CH3)3、CH3Si[O(CH2)3CH3]3、CH3CH2Si(OCH2CH3)3、C6H5Si(OCH3)3、C6H5CH2Si(OCH3)3、C6H5Si(OCH2CH3)3、CH2＝CHCH2Si(OCH3)3、(CH3)2Si(OCH3)2、(CH3)2Si(OCH2CH3)2、(CH3)2Si(OCH2CH2CH3)2、(CH3)2Si[O(CH2)3CH3]2、(CH3CH2)2Si(OCH2CH3)2、(C6H5)2Si(OCH3)2、(C6H5CH2)2Si(OCH3)2、(C6H5)2Si(OCH2CH3)2、(CH2＝CH)2Si(OCH3)2、(CH2＝CHCH2)2Si(OCH3)2、(CH3)3SiOCH3、CH3HSi(OCH3)2、(CH3)2HSi(OCH3)、CH3Si(OCH2CH2CH3)3、CH3Si(CH3COO)3、甲基二乙基氯硅烷、丁基三氯硅烷、乙烯基三氯硅烷、乙烯基三乙氧基硅烷、甲基丙烯酰氧基丙基三甲氧基硅烷、环氧丙氧基丙基三甲氧基硅烷、氨基丙基三乙氧基硅烷、乙基三丁氧基硅烷、异丁基三甲氧基硅烷、己基三甲氧基硅烷、正辛基三乙氧基硅烷、二己基二甲氧基硅烷、三氯十八烷基硅烷、3-(三甲氧基甲硅烷基)丙基二甲基十八烷基氯化铵以及三乙氧基甲硅烷基大豆丙基二甲基氯化铵。
7.如权利要求1所述的组合物，其中所述化合物是(C6H5)2Si(OCH2CH2OCH3)2、(CH3)2Si(OCH2CH2OCH3)2、(CH2＝CH)2Si(OCH2CH2OCH3)2、(CH2＝CHCH2)2Si(OCH2CH2OCH3)2、(C6H5)2Si(OCH2CH2OCH3)2或乙烯基三(甲氧基乙氧基)硅烷。
8.如权利要求1所述的组合物，其中所述化合物是具有下列通式的有机硅氧烷
Figure FSB00001069563400021
其中R1至R6以及R8至R10中每一基团均代表含有1至6个碳原子的有机基团，R7对于有机甜菜碱聚硅氧烷代表有机甜菜碱基团，或者对于有机季盐聚硅氧烷代表有机季盐基团，并且m和n是1至200。
9.如权利要求8所述的组合物，其中所述化合物是有机甜菜碱聚硅氧烷。
10.如权利要求9所述的组合物，其中所述化合物是有机甜菜碱聚硅氧烷，并且m和n的值是1至100。
11.如权利要求10所述的组合物，其中所述化合物是有机甜菜碱聚硅氧烷，其中R1至R6以及R8至R10中每一基团均为甲基基团，并且m和n的值是1至100。
12.如权利要求8所述的组合物，其中所述化合物是有机季盐聚硅氧烷。
13.如权利要求12所述的组合物，其中所述化合物是有机季盐聚硅氧烷，并且m和n的值是1至100。
14.如权利要求13所述的组合物，其中所述化合物是有机季盐聚硅氧烷，并且R1至R6以及R8至R10中每一基团均为甲基基团，并且m和n的值是1至100。
15.如权利要求1所述的组合物，其中所述化合物是具有下列通式的有机硅氧烷
Figure FSB00001069563400031
其中R12至R17均代表含有1至6个碳原子的有机基团，R11和R18对于二甜菜碱聚硅氧烷均代表有机甜菜碱基团，或者对于二季盐聚硅氧烷均代表有机季盐基团，并且m是1至200。
16.如权利要求15所述的组合物，其中所述化合物是二甜菜碱聚硅氧烷。
17.如权利要求16所述的组合物，其中所述化合物是二甜菜碱聚硅氧烷，并且m的值是1至100。
18.如权利要求17所述的组合物，其中R12至R17中每一基团均代表甲基基团，并且m是1至100。
19.如权利要求15所述的组合物，其中所述化合物是二季盐聚硅氧烷。
20.如权利要求19所述的组合物，其中所述化合物是二季盐聚硅氧烷，并且m的值是1至100。
21.如权利要求20所述的组合物，其中R12至R17中每一基团均代表甲基基团，并且m是10至100。
22.如权利要求1至21中任一权利要求所述的组合物，其包含气体。
23.如权利要求22所述的组合物，其中所述气体选自空气、氮气、二氧化碳、甲烷及其混合物。
24.如权利要求1所述的组合物，其中所述油的量为功能上有效的量。
25.如权利要求1所述的组合物，其中所述化合物是有机硅烷，且所述油是烃油。
26.如权利要求1所述的组合物，其中所述化合物是有机硅氧烷，且所述油是烃油。
27.在产油气地层中控制支撑剂回流的方法，其包括以下步骤：将水、颗粒、使所述颗粒的表面疏水的化合物和油或含水的油混合，将混合物泵送入所述地层。
28.如权利要求27所述的方法，其中所述颗粒选自砂、树脂包被的砂、陶瓷、合成高分子小球以及铝土矿颗粒。
29.如权利要求27所述的方法，其中所述颗粒是砂或陶瓷颗粒。
30.如权利要求27所述的方法，其中所述化合物选自有机硅烷、有机硅氧烷和氟代有机化合物。
31.如权利要求27所述的方法，其中所述化合物是有机硅烷。
32.如权利要求27所述的方法，其中所述化合物是有机硅氧烷。
33.如权利要求30所述的方法，所述氟代有机化合物为氟代有机硅烷或氟代有机硅氧烷。
34.如权利要求30所述的方法，其中所述化合物是具有下列通式的有机硅烷
RnSiX(4-n)
其中R是具有1至50个碳原子的有机基团，X是卤素、烷氧基、酰氧基或胺，并且n值为1至3。
35.如权利要求30所述的方法，其中所述化合物是具有下列通式的有机聚硅氧烷
Figure FSB00001069563400061
其中R1至R6以及R8至R10中每一基团均代表含有1至6个碳原子的有机基团，R7对于有机甜菜碱聚硅氧烷代表有机甜菜碱基团，或者对于有机季盐聚硅氧烷代表有机季盐基团，并且m和n是1至200。
36.如权利要求35所述的方法，其中所述颗粒是砂。
37.如权利要求30所述的方法，其中所述化合物是具有下列通式的有机硅氧烷
Figure FSB00001069563400062
其中R12至R17均代表含有1至6个碳原子的有机基团，R11和R18对于二甜菜碱聚硅氧烷均代表有机甜菜碱基团，或者对于二季盐聚硅氧烷均代表有机季盐基团，并且m是1至200。
38.如权利要求37所述的方法，其中所述颗粒是砂。
39.如权利要求27所述的方法，其包括在气体的存在下将所述混合物进行剪切的步骤。
40.如权利要求39所述的方法，其中所述气体选自空气、氮气、二氧化碳、甲烷及其混合物。
41.如权利要求27所述的方法，其包括以下步骤：使所述颗粒与含有使所述颗粒疏水的所述化合物的介质接触，从所述介质中分离所述颗粒；将所述疏水颗粒与水和油混合；以及将混合物泵送入所述地层。
42.如权利要求41所述的方法，其包括在气体的存在下将所述混合物进行剪切的步骤。
43.如权利要求41所述的方法，其中所述气体选自空气、氮气、二氧化碳、甲烷及其混合物。
44.如权利要求41所述的方法，其中所述化合物是具有下列通式的有机聚硅氧烷
Figure FSB00001069563400071
其中R1至R6以及R8至R10中每一基团均代表含有1至6个碳原子的有机基团，R7对于有机甜菜碱聚硅氧烷代表有机甜菜碱基团，或者对于有机季盐聚硅氧烷代表有机季盐基团，并且m和n是1至200。
45.如权利要求44所述的方法，其中所述颗粒是砂。
46.如权利要求41所述的方法，其中所述化合物是具有下列通式的有机硅氧烷
Figure FSB00001069563400081
其中R12至R17均代表含有1至6个碳原子的有机基团，R11和R18对于二甜菜碱聚硅氧烷均代表有机甜菜碱基团，或者对于二季盐聚硅氧烷均代表有机季盐基团，并且m是1至200。
47.如权利要求46所述的方法，其中所述颗粒是砂。
48.如权利要求27所述的方法，其中在泵送所述混合物之后将所述油引入所述地层。
49.如权利要求48所述的方法，其中所述油是烃油或硅油。
50.如权利要求27所述的方法，其中所述油是烃油或硅油。
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