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CN1239670C - 压裂地下岩层的方法 - Google Patents

压裂地下岩层的方法 Download PDF

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CN1239670C
CN1239670C CNB011437294A CN01143729A CN1239670C CN 1239670 C CN1239670 C CN 1239670C CN B011437294 A CNB011437294 A CN B011437294A CN 01143729 A CN01143729 A CN 01143729A CN 1239670 C CN1239670 C CN 1239670C
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alkyl
fluid
active agent
tensio
alkenyl
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CN1389538A (zh
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M·S·达汉纳亚克
杨江
J·H·Y·牛
P-J·德里恩
D·迪诺
李若星
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Abstract

本发明提供了一种用作增稠剂的粘弹性表面活性剂基水性流体体系的使用方法。表面活性剂为两性表面活性剂/两性离子表面活性剂，如二羟基烷基甘氨酸盐、烷基两性乙酸盐或丙酸盐、烷基甜菜碱、烷基酰氨基丙基甜菜碱和由某些蜡、脂肪和油得到的烷氨基单或二丙酸盐。增稠剂与无机水溶性盐或有机添加剂如邻苯二甲酸、水杨酸或其盐组合使用。

Description

压裂地下岩层的方法
发明领域
本发明涉及包含表面活性剂的粘弹性流体的使用方法，具体地说，涉及一种压裂地下岩层的方法。
发明背景
固体颗粒或乳化液滴的悬浮液的水相增稠方法是公知的。加入增稠剂可增加水相的粘性，从而延缓颗粒或液滴的沉降。这种延缓作用用于在悬浮液贮存、使用和/或运输的过程中保持颗粒或液滴于悬浮液中。
高分子增稠剂，如淀粉通过高分子链的缠结而增稠，其目前已用于使悬浮液的水相增粘。这种增稠剂受机械剪切或聚合物链的化学裂解(如通过氧化或水解)的影响而使品质下降，导致粘度减少，使悬浮液的稳定性降低。
业已发现，阳离子表面活性剂在某些条件下会形成棒状胶束。当存在这种棒状胶束时，将赋予流体以粘弹性。但是，阳离子表面活性剂的毒性较高，且生物降解性较差。
发明概述
本发明提供了一种用作悬浮颗粒的增稠剂的粘弹性流体。这种粘弹性流体由两性/两性离子表面活性剂和一种有机酸/盐和/或无机盐组成。
因此，本发明涉及一种粘弹性流体，其包含：
(1)一种水性介质；
(2)使所述水性介质具有粘弹性的有效量的选自两性表面活性剂、两性离子表面活性剂和其混合物的表面活性剂；和
(3)一种选自下述的成分：有机酸、有机酸盐、无机盐以及一种或多种有机酸或有机酸盐与一种或多种无机盐的组合。
在本发明的另一个实施方案中，本发明涉及一种粘弹性流体，其基本上由下述成分组成：
(1)一种水性介质；
(2)一定量的含胺氧化物表面活性剂的表面活性剂；和
(3)一种包含具有至少14个碳原子的疏水基团的阴离子表面活性剂。
术语“粘弹性”是指粘性流体具有弹性，即，当该液体在解除所施加的应力后，至少部分回复到其原始形式。增稠的水性粘弹性流体用作润滑剂中的水基传压流体和传压压裂流体以增加在油生产中的渗透性。
本发明也涉及用于将悬浮的固体颗粒如挖掘副产物分布于包含本发明粘弹性流体的流体中的方法，其中，通过将流体运输至固体颗粒仍然悬浮于流体中的位置并使流体沉积于该位置而使固体颗粒继续悬浮延长的时间。
本发明还涉及用于压裂地下岩层的方法，包括在足以使所述岩层压裂的压力下，通过井眼泵送本发明的粘弹性流体进入地下岩层。
本发明还涉及一种洗涤剂制剂，其含有去污表面活性剂及本发明的粘弹性流体。
本发明还涉及所述粘弹性流体作为漂移控制剂在农业制剂中的用途。就这一方面，本发明涉及一种农业化学品与一定量的本发明粘弹性流体的水性制剂，粘弹性流体的量应足以增加所述制剂的喷雾的平均液滴尺寸。
附图简述
图1显示了对于通过加入5％牛油亚氨基二丙酸二钠(MirataineT2C)和2.25％邻苯二甲酸于水中而制备的粘弹性表面活性剂溶液而言，粘性与剪切速度的关系曲线。
图2显示了图1所述相同的溶液在25℃和50℃时的动态模量G′(储能模量)和G″(损耗模量)。
图3显示了对于通过加入5％牛油氨基二丙酸二钠(Mirataine T2C)和4％氯化铵和1.75-2.0％邻苯二甲酸于水中而制备的粘弹性表面活性剂溶液而言，粘性与剪切速度的关系曲线。
图4显示了对于通过加入4或5％油酰氨基丙基甜菜碱(MirataineBET-O)、3％氯化钾和0.5％邻苯二甲酸于水中而制备的粘弹性表面活性剂溶液而言，粘性与剪切速度的关系曲线。
图5显示了图4所述相同的溶液在25℃和50℃时的动态模量G′(储能模量)和G″(损耗模量)。
发明详述
一般意义的粘弹性性质是公知的，可参见S.Gravsholt，Journalof Coll.and Interface Sci.，57(3)，575(1976)；Hoffmann等，“离子表面活性剂对两性离子表面活性剂溶液粘弹性的影响”，Langmuir，8，2140-2146(1992)；以及Hoffmann等，“不同粘弹性表面活性剂溶液的流变学行为”，Tenside Surf.Det.，31，389-400，1994。在这些参考文献所述确定液体是否具有粘弹性的试验方法中，业已发现下述实验可用来确定水溶液的粘弹性，该实验由下述步骤组成：使溶液涡动，并目视观察是否通过在停止打漩后通过旋涡反冲而产生气泡。气泡反冲表明了粘弹性。另一种有用的实验是在给定的温度下，测量储能模量(G′)和损耗模量(G″)。如果在同一温度下，在某些点或在某一段低于10拉德/秒，优选约0.001至约10拉德/秒，更优选约0.1至约10拉德/秒点的范围内G′大于G″，并且，如果G′大于10-2帕斯卡，则这种流体通常被认为在该温度下具有粘弹性。流变测量如G′和G″值在下述文献中有更详细的讨论：“流变测量”， Encyclopedia of Chemical Technology，vol.1997，第4版。为完整的必要性，上述文献引入本文作为参考。
粘弹性是由于不同类型的胶束形成而引起的，而非由大多数表面活性剂形成的常规球形胶束产生。粘弹性表面活性剂流体会在溶液中形成蠕虫状、棒状或球状胶束。形成较长的球形胶束将产生有用的流变性质。粘弹性表面活性剂溶液显示出剪切薄层行为，并且，尽管施以重复的高剪切仍然保持稳定。比较而言，典型的高分子增稠剂在被施以高剪切时会不可逆地降级。
在本发明的概述及详述中，每个数值应理解为由术语“约”进行修饰(除非已经进行这种修饰表述)，然后再次理解为不进行这种修饰，除非在文中另有说明。
粘弹性表面活性剂可为离子型或非离子型。本发明包含一种基于两性或两性离子表面活性剂的水性粘弹性表面活性剂。两性表面活性剂是一类在某一段pH值范围(例如，通常在弱酸性时)内同时具有正电荷部分和负电荷部分，而在其它pH范围(例如，通常在中等酸性时)仅具有正电荷的表面活性剂；而两性离子表面活性剂则与pH值范围无关总是具有正电荷部分，并在碱性pH值时也具有负电荷部分。
粘弹性流体包含水、表面活性剂和一种选自有机酸、有机酸盐、无机盐和其混合物的水溶性化合物。或者，粘弹性流体可包含水、胺氧化物表面活性剂和一种包含具有至少约14个碳原子的疏水基团的阴离子表面活性剂。粘弹性流体表面活性剂溶液用作压裂流体或水基传压流体。用作压裂流体的粘弹性流体可选择性地含有一种气体如空气、氮气或二氧化碳以提供增能流体或泡沫。
可以最大浓度存在的流体组分是水，即，水通常占粘弹性流体重量百分数的大部分。水在液体中的含量通常大于或等于约50wt％。水可来自任一种来源，只要该来源不含与粘弹性流体的其它组分不相容的污染物(如引起不希望出现的沉淀)。因此，水无需是饮用水，可为微有碱味的水或包含在石油领域中常用水源中的其它物质。
用于本发明的两性离子表面活性剂的实例由下式(I)表示：
Figure C0114372900091
其中，R1表示烷基、烷基芳基烷基、烷氧基烷基、烷基氨基烷基和烷基酰氨基烷基的疏水基团，其中，烷基代表包含约12至约24个碳原子的基团，其可为支链或支链基团，可为饱和或不饱和基团。代表性的长链烷基包括十四烷基(肉豆蔻基)、十六烷基(鲸蜡基)、十八烯基(油基)、十八烷基(硬脂基)、二十二烯基(瓢儿菜基)和牛油、椰油、大豆油及菜籽油的衍生物。优选的烷基和链烯基是具有约16至约22个碳原子的烷基和链烯基。烷基酰氨基烷基的代表性实例是烷基酰氨基丙基，所述烷基如前所述。
R2和R3独立地为脂族基团(即，在与季氮相连的原子处与芳族基团相对照，例如，烷基、链烯基、芳基烷基、羟基烷基、羧基烷基和羟基烷基聚氧亚烷基，如羟乙基-聚氧亚乙基或羟丙基-聚氧亚丙基)，其具有1至约30个原子，优选约1至约20个原子，更优选约1至约10个原子，首选约1至约6个原子，其中，脂族基团可为支链或直链，饱和或不饱和。优选的烷基链为甲基、乙基，优选的芳烷基为苄基，优选的羟基烷基为羟乙基或羟丙基，而优选的羧基烷基为乙酸根和丙酸根。
R4为链长1-4个碳原子的烃基(如亚烷基)。优选亚甲基或亚乙基。
两性离子表面活性剂的具体实例包括下述结构：
Figure C0114372900101
其中，R1具有如前所述的定义。
两性表面活性剂的实例包括由式VI表示的那些：
Figure C0114372900111
其中，R1、R2和R4具有如前所述的定义。
两性表面活性剂的其它具体实例包括下述结构：
其中，R1具有前面所述的定义，X为在酸性介质中与羧酸基团或氢原子缔合的无机阳离子X+，如Na+、K+、NH4 +。
由乙氧基化烷基胺合成二羟基乙氧基化甘氨酸盐的一般化学过程如下：
Figure C0114372900114
终产物也可包含某些未反应原料二羟基乙基烷基胺和少量作为副产物的甘醇酸钠、二甘醇酸钠和氯化钠。类似的方法可用于制备丙氧基化的类似物。
由烷基胺合成烷基亚氨基二丙酸盐的一般化学过程如下：
Figure C0114372900121
终产物也可包含少量的甲醇，未反应的丙烯酸，烷基胺和作为副产物的某些低聚的丙烯酸酯或丙烯酸。
由烷基胺合成烷基酰氨基丙基甜菜碱的一般化学过程如下：
Figure C0114372900122
终产物也可包含少量作为副产物的甘醇酸钠、二甘醇酸钠和氯化钠及甘油。
在本发明的另一个实施方案中，所选择的两性离子表面活性剂为胺氧化物。这种物质具有下述结构：
其中，R1、R2和R3具有如前所述的定义。
与其它组分一起组合使用的表面活性剂的用量应足以形成粘弹性流体，该用量通常以流体重量计是少量的(例如，少于约50wt％)。以流体重量计，表面活性剂的浓度范围为约0.5wt％至约10wt％，优选约0.5wt％至约8wt％，更优选约0.5wt％至约6wt％。对于特别一组参数来说，最佳浓度可通过实验确定。
流体也包含一种或多种选自有机酸、有机酸盐和无机盐的成分。上述成分的混合物也在本发明的范围之内。这种成分的含量通常仅为少量(例如，低于流体重量的约20wt％)。
有机酸通常为磺酸或羧酸，有机酸盐的抗衡阴离子通常为磺酸根或羧酸根。这种有机分子的代表性实例包括各种芳族磺酸盐和羧酸盐，如对甲苯磺酸盐、奈磺酸盐、氯代苯甲酸、水杨酸、邻苯二甲酸等，其中，所述抗衡离子为水溶性的。最优选的是水杨酸盐、邻苯二甲酸盐、对甲苯磺酸盐、羟基萘羧酸盐，例如，5-羟基-1-萘甲酸、6-羟基-1-萘甲酸、7-羟基-1-萘甲酸、1-羟基-2-萘甲酸，优选3-羟基-2-萘甲酸、5-羟基-2-萘甲酸、7-羟基-2-萘甲酸和1，3-二羟基-2-萘甲酸和3，4-二氯苯甲酸盐。有机酸或其盐通常有助于增加粘度，而粘度增加是优选流体的特性。尽管不希望受任何理论的限制，除非在文中另有表述，据认为，有机酸或其盐与胶束的缔合降低了胶束的聚集曲率，因而，促进了虫形或棒形胶束的形成。有机酸或其盐在粘弹性流体中的浓度通常为约0.1wt％至约10wt％，优选约0.1wt％至约7wt％，更优选约.1wt％至约6wt％。
特别适用于粘弹性流体的无机盐包括水溶性钾盐、钠盐和铵盐，如氯化钾和氯化铵。此外，也可以采用氯化钙、溴化钙和卤化锌盐。无机盐有助于增加粘度，这是优选的流体的特性。进而，无机盐还有助于保持流体接触的地质建造的稳定性。建造稳定性，特别是粘土稳定性(通过抑制粘土水合)可在浓度为几个重量百分点下实现，如此，不会因存在无机盐而显著改变流体的密度，除非流体密度变成重要的考虑因素，在此点处，可以使用较重的无机盐。在粘弹性流体中无机盐的重量浓度通常为约0.1％至约30％，优选约0.1％至约10％，更优选0.1％至约8％。除了无机盐之外，或者作为一种代替，也可以采用有机盐，如三甲基铵盐酸盐和四甲基氯化铵。
作为有机盐和无机盐的代替物或作为其部分代替物，我们可以采用中等或长链醇(优选链烷醇)，优选具有5-10个碳原子，或醇的乙氧基化物(优选链烷醇乙氧基化物)，优选具有12-16个碳的醇，和具有1-6，优选1-4个氧乙烯单元。
在所选的表面活性剂为胺氧化物的实施方案中，优选与包含具有至少约14个碳原子疏水基团的阴离子表面活性剂组合使用。适宜的阴离子表面活性剂的实例包括：烷基硫酸盐或磺酸盐，其具有碱金属抗衡离子或烷基羧酸根，其中，烷基代表包含约14-约24个碳原子的基团，其可为支链或直链的，可为饱和或不饱和的，更优选包含约16-约22个碳原子。
对于该实施方案(胺氧化物/阴离子表面活性剂)，胺氧化物与阴离子表面活性剂的重量比为约100∶1至约50∶50。
除了水溶性盐和前述的增稠剂外，用作水力压裂流体的粘弹性流体可包含其它常规成分，它们带来所需的特殊功能，例如，腐蚀抑制剂，降滤失剂等。支撑剂可悬浮于压裂流体中。流体的pH值范围通常从强酸性(如pH值小于约3)至弱碱性(如pH值大于7.0至约8.5，更优选约8.0)，或中等碱性(如pH值约8.5至约9.5)。应避免强碱性pH值(如，pH值大于约10)。
同样可以理解，本领域的技术人员可将上述两性表面活性剂/两性离子表面活性剂与常规阴离子表面活性剂、非离子表面活性剂和阳离子表面活性剂进行组合以得到所需的粘弹性流体。在典型的实施方案中，两性表面活性剂/两性离子表面活性剂通常占所有表面活性剂的大部分，更优选它们基本上为仅包含的表面活性剂。一般而言，粘弹性流体基本上不含有阴离子表面活性剂，例如，包含少于约0.5wt％，更优选少于约0.2wt％，首选少于0.1wt％的阴离子表面活性剂。
为了制备本发明的水性流体，将表面活性剂加至一种水溶液中，所述水溶液中溶解了水溶性无机盐，如氯化钾或氯化铵和/或至少一种有机酸或水溶性有机酸盐，从而选择性地控制颗粒悬浮性质的损失。在流体为水与胺氧化物表面活性剂和阴离子表面活性剂的混合物的实施方案中，可以采用三种组分的简单混合物。由于对溶液进行加热及特殊的搅拌条件通常并不是必需的，因而可以采用本领域中公知的标准混合过程。当然，如果在极冷的条件如在阿拉斯加使用时，应当采用常规的加热过程。业已发现，在某些情形下，最好在与水溶液混合之前向低分子量醇中溶解入增稠剂。低分子量的醇如异丙醇的作用是帮助增稠剂增溶。其它的类似试剂也可采用。进而，如果在处理条件下不希望出现泡沫，则可以采用消泡剂如聚乙二醇来防止在制备粘弹性流体的过程中的不希望出现的泡沫。如果希望出现泡沫或增能气体，则可以加入诸如空气、氮气、二氧化碳等气体。
本发明的流体特别适用于处理在地质建造的挖掘过程中产生的颗粒，例如在建造道路、桥梁、建筑物、矿山、隧道等过程中进行的挖掘、钻孔、爆炸、疏浚、挖隧道等过程中产生的颗粒。将所述颗粒与粘弹性流体混合，从而有效地使颗粒分散于流体中。所述颗粒的粒径范围通常为从细粉至粗砂砾，例如，灰尘、砂子及砂砾。颗粒尺寸会影响挖掘过程废物的悬浮性。例如，小颗粒要比大颗粒悬浮得更好，而非常细的颗粒悬浮得会非常好以至混合物会变得太稠而难以通过泵或类似的装置来输送。挖掘过程废物尺寸的分布也很重要，这是因为，所包含的颗粒具有较宽尺寸范围会比具有大约基本相同尺寸的颗粒更易于悬浮。因而，优选在采用本发明的方法之前对颗粒进行筛选以除去太大而难于悬浮的颗粒，获得更好的颗粒粒径分布。
本发明的粘弹性流体可用于在深度地基建设工业、地下建设工业和在隧道及钻探和在其它土支撑流体应用中进行的钻孔、挖掘和开沟操作过程中对土地或材料的挖掘。挖掘机或系统保持和除去增加的土负载的能力可通过表面活性剂粘弹性流体的悬浮性能及润滑性能加以改善。
在本发明的一个优选实施方案中，表面活性剂可与工业中公知的某些降滤失控制剂组合使用，如水溶性或水分散性聚合物(瓜尔胶和其衍生物、黄原胶、聚丙烯酰胺、淀粉和其衍生物、纤维素衍生物、聚丙烯酸酯、polyDADMAC[聚(二烯丙基二甲基氯化铵)和其组合]、粘土(膨润土和坡缕石)，从而使挖掘流体具有降滤失控制性能并使挖掘壁稳定。
更深入的信息可在下述文献中有述，该文献引入本文作为参考：休斯顿大学，化学工程系，公开号UHCE93-1，题为“在钻井竖井中矿物和聚合物浆液对周边负载传递的影响”，1993年1月公开，以及WO96/23849。
上述用于悬浮固体的方法具有多种用途，特别是在开矿及尾矿处理中使用。US 5,439,317(Bishop等)公开的相关内容引入本文作为参考。其应用之一是在地下洞穴或在等级洞穴以下的矿物加工废物的运输和放置。另一个应用是回填凹坑或采石场，无需使用昂贵且劳动力强度大的设备。此外，该方法可用于放置粘土或其它衬垫以保持液体或防止这些液体进入地下水体系中和/或为类似的目的放置衬垫于堆土中。该方法的另一个应用是由于将一定量地下的固体展开而引起的煤矿着火的熄灭和/或遏制，使火与氧源隔绝。该方法的另一个应用是将固体放置于早先开出的矿洞中以防止表面沉淀。
本发明的水力压裂方法采用了其它的常规技术。US 5,551,516(Norman等)引入本文中。各种物料的油田应用在下述文献中及其引证文献中有述，这些文献均引入本文作为参考：“油田应用”，Encyclopedia of Polymer Science and Engineering，vol.10，pp.328-366(John Wiley & Sons，Inc.，New York，New York，1987)。
水力压裂是用于刺激从地下岩层中生产流体如油、天然气等的各种方法中采用的术语。在水力压裂中，压裂流体在一定的压力和流速通过井眼及对抗层面注入，所述压力和流速应足以克服过度负担压力并引发和/或扩大破裂形成。压裂流体通常带有悬浮于压裂流体支撑剂，如20-40目砂、铝矾土、玻璃珠等，其悬浮于压裂流体中并输送进入裂缝中。然后，支撑剂可抑制当压力释放时地层自身的闭合。填充裂缝的支撑剂提供了可渗透的通道，通过这些通道，地层流体可流至油井并排出。粘弹性流体也广泛地用于砂砾包装处理。
除了上述应用之外，粘弹性流体也可用作工业漂移控制剂或用作流变改性剂以用于个人护理制剂(如清洁剂、调理剂等)及家居清洁剂(如洗涤剂)。本发明粘弹性流体的洗涤剂制剂进一步包含去污表面活性剂。支污表面活性剂和洗涤剂和/或个人护理制剂的其它常规成分的实例公开于US申请08/726,437(1996年10月4日申请)，该文献引入本文作为参考。
通常，去污表面活性剂为阴离子型或非离子型。优选的水溶性阴离子有机表面活性剂包括直链烷基苯磺酸盐，烷基中包含约10至18个碳原子；支链烷基苯磺酸盐，烷基中包含约10至18个碳原子；牛油范围的烷基硫酸盐；椰油范围的烷基甘油基磺酸盐；烷基醚(乙氧基化)硫酸盐，其中，烷基部分包含约12至18个碳原子，其中，平均乙氧基化度为1至12，优选3至9；牛油醇与约3至12，特别是6至9摩尔的环氧乙烷的硫酸化缩合产物；包含约14至16个碳原子的链烯烃磺酸盐。
用于本发明的特别优选的阴离子表面活性剂包括：直链C10-C14烷基苯磺酸盐(LAS)；支链C10-C14烷基苯磺酸盐(ABS)；牛油烷基硫酸盐、椰油烷基甘油基醚磺酸盐；混合C10-C18牛油醇与约1至约14摩尔环氧乙烷形成的硫酸化缩合产物；含10至18个碳原子的高级脂肪酸的混合物。
用于液体、粉末和凝胶应用中的特别优选的非离子表面活性剂包括C10醇与3摩尔环氧乙烷的缩合产物；牛油醇与9摩尔环氧乙烷的缩合产物；椰油醇与5摩尔环氧乙烷的缩合产物；椰油醇与6摩尔环氧乙烷的缩合产物；C12醇与5摩尔环氧乙烷的缩合产物；C12-13醇与6.5摩尔环氧乙烷的缩合产物，以及经汽提除去基本上所有的低级乙氧基化物和非乙氧基化馏分的相同的缩合产物；C12-13醇与2.3摩尔环氧乙烷的缩合产物，以及经汽提除去基本上所有的低级乙氧基化物和非乙氧基化馏分的相同的缩合产物；C12-13醇与9摩尔环氧乙烷的缩合产物；C14-15醇与2.25摩尔环氧乙烷的缩合产物；C14-15醇与4摩尔环氧乙烷的缩合产物；C14-15醇与7摩尔环氧乙烷的缩合产物；C14-15醇与9摩尔环氧乙烷的缩合产物。
粘弹性流体将应用的特别去污应用场合包括用作用于酸性浴室清洁剂的增稠剂，如US 5,639,722(Kong等)所述的那些，以及淋浴凝胶，如US 5,607,678(Moore等)所述的那些，这些文献均引入本文作为参考。粘弹性流体也可用于建筑产品的生产，如基于灰泥、石灰/石灰、石灰/水泥或水泥的建筑产品，如US 5,470,383(Schermann)所述，以及泡沫流体，如US 5,258,137(Bonekamp等)所述，这些文献均引入本文作为参考。具体而言，所述流体可用于改善水泥浆液和灰浆的保水性，以具有更好的泵送性和加工性，并具有最少量的游离水。所述流体也可用作用于酸性(如pH值小于约5)的矿物碳酸盐或氧化物(如氧化铁、氧化铈、二氧化硅悬浮液、二氧化钛、碳酸钙和氧化锆)的水性浆液的增稠剂。US 4,741,781(De Witte)公开的内容引入本文作为参考。
本发明的粘弹性流体也可用于农业传送固体肥料和农药如微量营养素、生物制剂、杀虫剂、除草剂、杀真菌剂和植物生长调节剂的制剂。这种制剂通常为水性悬浮液或溶液，其包含大量的水和农业有效量的农用化学品。粘弹性流体通常与制剂的其它成分合并，其用量应有效地将液滴数减至低于约150微米，即液滴主要对漂流问题负责。
下述实施例进一步说明基于水力流体的水性粘弹性流体表面活性剂的制备和性能，但它们并非对本发明范围的限制，除非另有说明。所有的百分数、浓度、比例、份数等均指重量，除非另有说明。
实施例
实施例1
将5％的氯化铵和3-5％的二羟乙基牛油基甘氨酸盐(Mirataine TM)加至水中，制备粘弹性流体表面活性剂溶液。将该体系进行搅拌直至所有的表面活性剂溶解。通过鼓泡反冲试验观察所有的样品均是粘弹性的。溶液的流变性由Rheometric ARES在25℃下测量。结果示于表1。
表1
  剪切速度(秒-1)  5％氯化铵中的粘度(cps)
 3％表面活性剂  4％表面活性剂  5％表面活性剂
  10  1692.4  2619.8  3774.7
  18  967.7  1490.6  2144
  32  555.5  851.6  1214.3
  56  319.2  483.2  688.1
  100  184.6  278  393.6
  178  107.5  159.3  225.4
实施例2
以与实施例1类似的方式，将0.3％的邻苯二甲酸和2-4％的二羟乙基牛油基甘氨酸盐(Mirataine TM)加至溶液中。通过鼓泡反冲试验观察所有的样品均是粘弹性的。以与实施例1所述相同的方式在25℃下进行流变测量。结果示于表2。
表2
  剪切速度(秒-1)  0.3％邻苯二甲酸中的粘度(cps)
 2％表面活性剂  3％表面活性剂  4％表面活性剂
  10  791.5  1474.6  1968.7
  18  455.3  840.9  1101.5
  32  262.4  490  564.5
  56  152  279.2  361.7
  100  88  160.9  356.6
  178  53  91.6  342.3
实施例3
在高温下通过FANN流变仪进行流变性测量。结果示于表3(4％二羟乙基牛油基甘氨酸盐(Mirataine TM)和0.3％邻苯二甲酸溶液)。
表3
  温度(°F)   100rpm下的粘度(cps)
  82   170
  129   51
  189   30
  239   22
  288   15
实施例4
通过向水中加入5％的牛油亚氨基二丙酸二钠(Mirataine T2C)和2.25％的邻苯二甲酸制备粘弹性表面活性剂溶液。将体系进行搅拌并升温至50℃，直至所有的邻苯二甲酸溶液。通过鼓泡反冲试验观察所有的样品均是粘弹性的。通过Rheometric SR-200在25℃及50℃下对有关粘度和动态模量G′(储能模量)和G″(损耗模量)的流变性进行测量。结果示于图1和图2。
实施例5
以与实施例4类似的方式，将5％的牛油亚氨基二丙酸二钠(Mirataine T2C)和4％的氯化铵及1.75-2.0％的邻苯二甲酸混合在一起。通过鼓泡反冲试验观察所有的样品均是粘弹性的。以与实施例4所述相同的方式在25℃下进行流变测量。结果示于图3。
实施例6
通过向水中加入4-5％的油酰氨基丙基甜菜碱(Mirataine BET-O)和3％的氯化钾和0.5％的邻苯二甲酸制备粘弹性表面活性剂溶液。将体系进行搅拌，直至所有的邻苯二甲酸溶液。由Rheometric ARES在25℃下测量对于稳定粘度和动态模量G′/G″。结果示于图4和5。
实施例7
通过使95.65份的水与4份的euricic酰氨基亚丙基二甲基氧化胺和0.35份的油酰基硫酸钠混合制备粘弹性表面活性剂溶液。加入氢氧化钠调节pH值至8。其温度稳定性通过测量粘度(cps)来确定(在剪切速度为100秒-1下)。结果示于表4。
实施例8
通过使95.50份的水与4份的euricic酰氨基亚丙基二甲基氧化胺和0.50份的油酰基硫酸钠混合制备粘弹性表面活性剂溶液。其温度稳定性通过测量粘度(cps)来确定(在剪切速度为100秒-1下)。结果示于表4。
表4
  温度(°F)   粘度(实施例8)   粘度(实施例7)
  100   282   247
  120   302   293
  140   308   305
  160   168   237
  180   162   166
  200   230   231
  220   119   193
  240   50   63
  250   36   36
  260   30   27
  270   16   10
实施例9
通过使96.1份的水与3.0份的euricic酰氨基亚丙基二甲基氧化胺和0.9份的二十二烷基硫酸钠混合制备粘弹性表面活性剂溶液。加入氢氧化钠调节pH值至9。其温度稳定性通过测量粘度(cps)来确定(在剪切速度为100秒-1下)。结果示于表5。
实施例10
通过使44.8份的水与4.0份的euricic酰氨基亚丙基二甲基氧化胺和1.2份的二十二烷基硫酸钠混合制备粘弹性表面活性剂溶液。加入氢氧化钠调节pH值至9。其温度稳定性通过测量粘度(cps)来确定(在剪切速度为100秒-1下)。结果示于表5。
表5
  温度(°F)   粘度(实施例8)   粘度(实施例7)
  100   175   234
  120   168   226
  140   169   297
  160   256   518
  180   309   454
  200   276   173
  220   140   214
  240   154   284
  260   94   351
  270   52   215
  280   31   90
  290   25   40
  300   17   4

Claims (29)

1、一种处理地下岩层的方法，该方法包括通过井眼泵送粘弹性流体，其中，所述的粘弹性流体包含：
a)一种水性介质；
b)选自两性表面活性剂、两性离子表面活性剂和其混合物的表面活性剂；和
c)一种选自下述的成分：有机酸、有机酸盐、无机盐以及一种或多种有机酸或有机酸盐与一种或多种无机盐的组合；
其中，所述的流体具有粘弹性。
2、根据权利要求1的方法，其中所述处理方法是一种压裂方法，其中所述的泵送步骤是在足以压裂所述地层的压力下进行的。
3、根据权利要求2的方法，其中所述的粘弹性流体还包括一种无机酸，其浓度足以将所述粘弹性流体的pH值降到3或更低。
4、根据前述权利要求任一项的方法，其中，以所述流体重量计，所述表面活性剂的含量为0.5wt％至6wt％。
5、根据权利要求1的方法，其中，所述表面活性剂是两性离子表面活性剂，所述两性离子表面活性剂包括与烷基或羟烷基基团共价键合的季铵亲水部分。
6、根据权利要求5的方法，其中，所述的表面活性剂包含羧酸盐亲水部分。
7、根据权利要求1的方法，其中，所述的成分包含芳族部分，该芳族部分选自磺基部分、磺酸盐部分、羧基部分和羧酸盐部分。
8、根据权利要求7的方法，其中，所述的芳族部分选自水杨酸根离子和邻苯二甲酸根离子、羟基萘甲酸根离子和其混合物。
9、根据权利要求1的方法，所述粘弹性流体还包含悬浮于其中的颗粒状支撑剂。
10、根据权利要求1的方法，所述粘弹性流体还包含一种选自腐蚀抑制剂和降滤失剂和其混合物的添加剂。
11、根据权利要求1的方法，其中所述成分的量为0.1wt％至30wt％。
12、根据权利要求11的方法，其中所述成分的量为0.1wt％至8wt％。
13、根据权利要求5的方法，其中，所述的表面活性剂由下式(I)或式(VI)表示：
Figure C011437290003C1
其中，R1为烷基、链烯基、烷芳基亚烷基、链烯基芳基亚烷基、烷基氨基亚烷基、链烯基氨基亚烷基、烷基酰氨基亚烷基或链烯基酰氨基亚烷基，其中，所述的每一个烷基包含14至24个碳原子，且所述的亚烷基具有1至6个碳原子，可为支链或直链、饱和或不饱和；R2和R3彼此独立地为具有1至30个碳原子的脂族链；和R4为链长1至4个碳原子的烃基。
14、根据权利要求13的方法，其中，R1选自十四烷基、十六烷基和十八烷基。
15、根据权利要求13的方法，其中，R1为由牛油、椰油、大豆油或菜籽油得到的烷基。
16、根据权利要求13的方法，其中，R2和R3彼此独立地为烷基、链烯基、芳烷基、羟基烷基、羧基烷基或羟基烷基-多氧亚烷基，每一个均具有1至10个碳原子。
17、根据权利要求16的方法，其中R2和R3彼此独立地为甲基、乙基、苄基、羟乙基、羟丙基、羧甲基或羧乙基。
18、根据权利要求13的方法，其中，R1为RCONHCH2CH2CH2-，其中，R为含有14至24个碳原子的烷基，该烷基可为支链或直链的，且为饱和或不饱和的且R2和R3分别为β-羟基乙基。
19、根据权利要求18的方法，其中，R2为β-羧基乙基，R4为亚乙基。
20、根据权利要求5的方法，其中，所述的表面活性剂选自二羟乙基甘氨酸盐、链烯基酰氨基烷基甜菜碱和两性咪唑啉衍生的二丙酸盐。
21、根据权利要求20的方法，其中，所述的表面活性剂选自二羟乙基牛油甘氨酸盐、牛油亚氨基二丙酸二钠、或油酰氨基丙基甜菜碱。
22、根据权利要求20的方法，其中所述的表面活性剂是链烯基酰氨基烷基甜菜碱。
23、根据权利要求20到22任一项的方法，其中流体包括0.5％至6％的表面活性剂，和0.1％至6％的选自对甲苯磺酸盐、萘磺酸盐、氯代苯甲酸、水杨酸和邻苯二甲酸的成分与含一种或多种水溶性铵盐的成分的组合。
24、根据权利要求1的方法，其中所述的表面活性剂是胺氧化物表面活性剂和所述成分是含具有至少14个碳原子的疏水性基团的阴离子表面活性剂。
25、根据权利要求24的方法，其中，所述的胺氧化物表面活性剂具有下式
其中，R1为烷基、链烯基、烷芳基亚烷基、链烯基芳基亚烷基、烷基氨基亚烷基、链烯基氨基亚烷基、烷基酰氨基亚烷基或链烯基酰氨基亚烷基，其中，所述的每一个烷基包含14至24个碳原子，可为支链或直链的，饱和或不饱和的，其中，所述的亚烷基具有1至6个碳原子和R2和R3彼此独立地为具有1至30个碳原子的脂族链。
26、根据权利要求24的方法，其中，所述的阴离子表面活性剂为烷基硫酸盐或磺酸盐，其具有碱金属抗衡离子或烷基羧酸根，其中，烷基为包含14至24个碳原子的烷基，可为支链或直链，可饱和或不饱和。
27、根据权利要求24的方法，其中，胺氧化物表面活性剂与阴离子表面活性剂的重量比为100∶1至50∶50。
28、根据权利要求24的方法，包括在大于100°F下进行的压裂步骤。
29、根据权利要求1的方法，其中所述粘弹性流体通过加空气、氮气或二氧化碳增能或发泡。
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NO339836B1 (no) 2017-02-06
DE69833233D1 (de) 2006-04-06
EP0993334B2 (en) 2015-10-07
ATE246957T1 (de) 2003-08-15
US6482866B1 (en) 2002-11-19
DE69817182D1 (de) 2003-09-18
US9249351B2 (en) 2016-02-02
US20020002205A1 (en) 2002-01-03
US6258859B1 (en) 2001-07-10
BR9816159B1 (pt) 2009-01-13
CN101757874B (zh) 2013-07-17
RU2217585C1 (ru) 2003-11-27
CN1263481A (zh) 2000-08-16
EP0993334B1 (en) 2003-08-13
US20130327531A1 (en) 2013-12-12
US20040176478A1 (en) 2004-09-09
NO996089L (no) 2000-02-08
ATE316194T1 (de) 2006-02-15
CN101757874A (zh) 2010-06-30
AU753011B2 (en) 2002-10-03
NO20161010A1 (no) 2000-02-08
ID27732A (id) 2001-04-26
EP0993334A1 (en) 2000-04-19
WO1998056497A1 (en) 1998-12-17
BR9810023A (pt) 2002-01-15
NO20030096L (no) 2000-02-08
NO339843B1 (no) 2017-02-06
US20080200353A1 (en) 2008-08-21
DK0993334T3 (da) 2003-12-08
US20110092398A1 (en) 2011-04-21
RU2198906C2 (ru) 2003-02-20
DE69817182T3 (de) 2016-05-12
DK0993334T4 (en) 2016-01-18
AU8066298A (en) 1998-12-30
US20070249505A1 (en) 2007-10-25
CA2297185A1 (en) 1998-12-17
CA2297185C (en) 2008-12-30
BR9810023B1 (pt) 2009-01-13
NO996089D0 (no) 1999-12-09
DE69817182T2 (de) 2004-06-17
NO20030096D0 (no) 2003-01-09
US7238648B2 (en) 2007-07-03
US6831108B2 (en) 2004-12-14
US6703352B2 (en) 2004-03-09
US20040082484A1 (en) 2004-04-29
CN1389538A (zh) 2003-01-08
US20030040546A1 (en) 2003-02-27

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