CN1708632B - 利用延迟的酸酸压裂被井筒穿透的地下地层的方法 - Google Patents

利用延迟的酸酸压裂被井筒穿透的地下地层的方法 Download PDF

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CN1708632B
CN1708632B CN200380102285.XA CN200380102285A CN1708632B CN 1708632 B CN1708632 B CN 1708632B CN 200380102285 A CN200380102285 A CN 200380102285A CN 1708632 B CN1708632 B CN 1708632B
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约翰·斯蒂尔
基思·迪斯穆克
韦恩·弗雷尼尔
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Abstract

本发明提供了一种酸压裂的方法，其中酸是通过固体酸-前体的水解在裂缝处产生的，该固体酸-前体选自一种或一种以上的丙交酯、乙交酯、聚乳酸、聚乙醇酸、聚乳酸和聚乙醇酸的共聚物、乙醇酸和其它含有羟基、羧酸或羟基羧酸的部分的共聚物、乳酸和其它含有羟基、羧酸或羟基羧酸的部分的共聚物。所述固体酸-前体可以与固体酸-反应性物质混合一加速水解，和/或进行涂覆以减缓水解。本发明还提供了加速水解的水溶性化合物。所述方法保证了酸与远离井筒的断裂面进行接触。

Description

利用延迟的酸酸压裂被井筒穿透的地下地层的方法 
发明背景 
本发明涉及注入固体酸-前体的方法，该固体酸-前体在注入之后溶解在水中产生酸。更具体地，本发明涉及在酸压裂(压裂酸化)中在远离井筒的裂缝中原位(in-situ)产生酸的方法。 
在酸压裂中，酸充填远离井筒的裂缝中，在那里它与裂缝面反应，从而刻蚀出有差别的流动路径，所述流动路径：a)产生差异使得在压裂压力释放时相对的裂缝面不匹配，从而裂缝不能完全闭合，及b)为产生的流体提供从远离裂缝的部分沿裂缝面至井筒的流动路径，该流体从裂缝的远处沿裂缝面向井筒流动。通常，通过在表面形成酸性流体并在超过压裂压力下从表面和井筒下泵送酸性流体，将酸性流体充填至所需的位置。在此常规操作期间，一般会遇到两个主要问题。 
首先，在泵送操作中，酸与井筒的含铁部件如套管(casing)、衬管(liner)、挠性油管(coiled tubing)等接触。酸对此类材料是有腐蚀性的，尤其在高温下。这意味着：为了不限制在酸注入期间能使用的酸的数量和/或接触时间，必须向注入的流体中加入防腐剂。另外，酸腐蚀产生铁的化合物，如氯化铁。特别是，在存在硫或硫化物时，这些铁的化合物会产生沉淀，并且会妨碍流体中其它组分的稳定性或有效性，因此需要向流体加入铁控制剂或铁螯合剂(sequestering agents)。 
其次，和通常的情况一样，如果本发明使用酸来处理显著远离井筒的部分，这将十分难以实现，因为如果从表面沿着井筒注入酸并与地层接触，酸将自然地与它接触的第一反应性物质发生反应。取决于井的性质和处理性质，第一接触的和/或第一反应的物质可能是滤饼，可能是形成无套管的(或裸眼(openhole))井筒壁的地层表面，或可能是近井筒地层或对流体有极高渗透性的地层的一部分。在许多情况下，这可能不是操作者想要用酸处理的地层(基岩)物质。情况最好时也会浪费酸；情况最坏时会使得处理无效，或者甚至是有害的。通常，温度越高，酸的反应性越强，该问题也越严重。 
过去，操作者处理这些问题中，有几种方法。一种方法是将酸与不希 望发生反应的物质隔离。例如，这可以通过如下方法实现：a)将酸置于乳状液(称为“乳化酸”)的内相中，然后使得或让乳状液在需要发生反应的时间和位置转相，或者使得酸缓慢传送通过相界，或者b)通过例如美国专利6,207,620所述的方法包胶该酸，然后在需要时或需要处释放该酸。这些方法存在一些问题。尽管乳化酸使用普遍并且是有效的，但它们需要另外的添加剂和专门设备及专有技术，并且难以控制。包胶的酸的问题是：酸释放的时间和地点难以控制。由涂层的物理或化学降解导致酸释放。对包胶材料的物理破坏，或者在制备期间的不完全或不充分的涂覆会引起酸过早释放。 
第二种方法是延迟酸的形成。Templeton等在“Higher pH AcidStimulation Systems”，SPE论文7892,1979中描述了在油田中作为原位的酸产生剂(acid generator)的酯如甲酸甲酯和乙酸甲酯的水解。他们还描述了在油田中一氯乙酸铵与水反应生成乙醇酸和氯化铵。但是，这些酸前体是液体，它们一与水接触，就会非常迅速地发生反应。 
因此，在酸压裂中，需要从固体原位延迟、控制释放酸的新方法。 
发明内容
本发明的一个实施方案是使用固体酸-前体的酸压裂方法，用于通过水解和溶解提供酸的控制释放。该固体酸-前体是丙交酯、乙交酯、聚乳酸、聚乙醇酸、聚乳酸和聚乙醇酸的共聚物、乙醇酸和其它含有羟基、羧酸或羟基羧酸的部分的共聚物、乳酸和其它含有羟基、羧酸或羟基羧酸的部分的共聚物、或前述物质的混合物。为了增加固体酸-前体的溶解和水解速率，该固体酸-前体可以和与酸反应的第二固体混合，该第二固体为氢氧化镁、碳酸镁、白云石(碳酸钙镁)、碳酸钙、氢氧化铝、草酸钙、磷酸钙、偏磷酸铝、多磷酸钠锌钾玻璃和多磷酸钠钙镁玻璃。该第二固体称为“固体酸-反应性物质”。在本发明的实施方案中，固体酸-前体颗粒为珠、带、板(platelet)、纤维或其它形状，任选以相同的或单独的颗粒中与固体酸-反应性物质混合。当它们混合在相同的颗粒中时，固体酸-前体可以包裹着固体酸-反应性物质。可以涂覆或包胶固体酸-前体(包括在它与其它物质混合或含有其它物质时)本身以减缓或延迟水解。在其它实施方案中，可以将可溶性液体如酯、二酯、酐、内酯、氢氧化钠、氢氧化钾、酰胺、胺、碳酸盐、碳酸氢盐、 醇、烷醇胺、氢氧化铵，及其混合物加入压裂液中以加快固体酸-前体的水解。在其它的实施方案中，该流体还包含支撑剂。在另外的实施方案中，该流体还包含增粘剂。在又一实施方案中，该流体还含有支撑剂和增粘剂。在另外的实施方案中，该流体含有酸，例如盐酸、氢氟酸、氟化氢铵、甲酸、乙酸、乳酸、乙醇酸、氨基多羧酸、多氨基多羧酸(polyaminopolycarboxylicacid)，一种或多种这些酸的盐、一种或多种这些酸或盐的混合物。 
附图说明
图1示出了方解石在各种有机酸中的溶解性。 
具体实施方式
与常规的酸压裂不同，当其在井筒表面制备或注入井筒时，本发明的方法中使用的压裂液通常不含酸。 
当需要时或在需要处，可在井下产生的酸的优良来源是某些有机酸的固体环状二聚体或固体聚合物，其在已知和可控的温度、时间和pH值的条件下水解。我们称这些固体物质为“酸-前体”，并且我们将在井下酸的形成称为“延迟产生酸”。合适的固体酸-前体的一个实例是乳酸的固体环状二聚体(称为“丙交酯”)，其熔点为95-125℃(与光学活性有关)。另一实例是乳酸的聚合物(有时称聚乳酸(或“PLA”)，或聚乳酸酯(polylactate)或聚丙交酯)。另一个实例是乙醇酸的固体环状二聚体(称为“乙交酯”)，其熔点大约为86℃。还有一实例是乙醇酸(羟基乙酸)的聚合物，也已知为聚乙醇酸(“PGA”)或聚乙交酯。另一实例是乳酸和乙醇酸的共聚物。这些聚合物和共聚物都为聚酯类。 
Cargill Dow，Minnetonka，MN，USA生产固体环状乳酸二聚物(称为″丙交酯″)，并由其生产不同分子量和结晶度的乳酸聚合物或聚乳酸酯，通用商品名为NATUREWORKSTM PLA。尽管在本发明的实施方案中可以使用任何聚丙交酯(由任何制造商采用任何方法制得的)，任何结晶度、任何分子量的材料，但目前从Cargill Dow购买的PLA的分子量高达约100,000。PLA聚合物在室温下是固体，并且经水水解形成乳酸。这些从Cargill Dow购买的PLA通常具有大约120℃至约170℃的晶体熔化温度，但也可购买其它的PLA。从Bio-Invigor，北京和台湾可购买到分子量达500000的聚(d，l-丙交酯)。Bio-Invigor还供应聚乙醇酸(也称为聚乙交酯)和各种乳酸和乙醇酸的共聚物，常称为“polyglactin”或聚(丙交酯-共-乙交酯)，所有这些材料的水解反应速率由分子量、结晶度(晶体和非晶物质的比例)、物理形态(固体的尺寸和形状)决定，在聚丙交酯的情况中，还由两种光学异构体的量决定。(自然产生的l-丙交酯形成部分结晶聚合物；合成的d，l-丙交酯形成非晶聚合物。)非晶区比晶体区更容易水解。较低的分子量、较小的结晶度和较大的表面-质量比都会引起更快的水解。升高温度、加入酸或碱，或加入与水解产物反应的物质可加快水解。 
均聚物更易结晶；共聚物趋向为非晶，除非它们是嵌段共聚物。可以通过均聚物的制造方法，以及共聚物的制造方法、丙交酯和乙交酯的比例和分布来控制结晶度的范围。可以将聚乙交酯制成多孔形态。水解前一些聚合物在水中溶解得非常缓慢。 
适合用作固体酸-前体的其它材料是那些在美国专利4,848,467、4,957,165和4,986,355中描述的羟基乙酸(乙醇酸)与自身或者与其它含有羟基、羧酸或羟基羧酸的部分的聚合物。 
已经发现，通过加入某些化学试剂可以加速本发明固体酸-前体的溶解。这些试剂很容易与固体酸-前体反应，并使得少量物质从固体酸-前体表面除去。虽然不受理论约束，但相信固体酸-前体的未触动(intact)表面是相对不溶的，但当该表面由于少量物质的除去而受到破坏时，则随后从该表面溶解其它物质将会比较容易。仅需要少量的加速剂(“促进剂”)来启动此溶解过程；之后无需任何添加的试剂就可以进行下去。另一方面，如果有其它的试剂存在，由于它易于与固体酸-前体反应，因此它会加速连续的溶解过程。这就是“促进剂”的机理。注意，促进剂不会消耗全部生成的酸；而是通过破坏固体酸-前体的表面结构，更多的酸产生得更快。在试剂为固体时，由于两种固体之间的化学作用不充分，它不能加速最初的溶解，但一旦固体酸-前体开始溶解(例如温度升高的结果)，该固体酸-反应性物质将加快随后的溶解。注意到地层本身是固体促进剂。另外，可以延迟促进剂的作用，例如，当它们是缓慢溶解的固体时，或者当它们化学键合在液体化学药品上时，该化学药品必须水解以释放所述试剂。一种固体酸-前体可能是另一种促进剂；例如，PGA加速了PLA的水解。通过这些方法控制固体酸-前体的溶解速率和时间。 
为了加速固体酸-前体的溶解，可以将水不溶性固体酸-可溶性或酸-反应性物质与固体酸-前体混合或结合，该水不溶性固体酸-可溶性或酸-反应性物质为，例如，但不限于氢氧化镁、碳酸镁、白云石(碳酸钙镁)、碳酸钙、氢氧化铝、草酸钙、磷酸钙、偏磷酸铝、多磷酸钠锌钾玻璃和多磷酸钠钙镁玻璃，该固体酸-前体为，例如乳酸或乙醇酸的环状酯二聚体，或者乳酸或乙醇酸的均聚物或共聚物。将这些混合物加入压裂液中。在预选的位置和时间在压裂中至少一部分的固体酸-前体以可控制的速率缓慢水解，以释放酸。除了与地层的裂缝面反应以外，这些酸还和至少部分酸-反应性物质(如果它们存在的话)反应以及溶解。这将加速固体酸-前体的溶解并产生超出与固体酸-反应性物质反应所需数量的酸。结果是固体酸-前体和酸-反应性固体物质中至少部分溶解。通常大部分或全部最初加入的固体物质在处理结束时不再存在。但是，不需要水解所有的固体酸-前体或溶解所有的固体酸-反应性物质。所有余留下来的固体将有利地充当支撑剂。注意，常常不需要额外的固体酸-反应性物质来加速固体酸-前体的水解，因为地层本身是酸反应性的。然而，可以选择比地层反应性更高的固体酸-反应性物质，或者可以更紧密地与固体酸-前体接触的固体酸-反应性物质。 
通过加入某些可溶性液体添加剂也可以加速酸压裂中固体酸-前体的溶解。这些促进剂可以是酸、碱，或者酸或碱的原料。在低温下(例如在低于约135℃下)这些添加剂特别有用，相对于操作者在压裂处理之后欲将井投入生产的时间，在该温度下固体酸-前体水解缓慢。水解释放有机酸的可溶性液体添加剂的非限制性实例是酯(包括环状酯)、二酯、酐、内酯和酰胺。对于给定的处理，通过简单的实验室水解实验很容易确定对压裂液的pH和地层的温度，以合适的速率进行水解的化合物类型及其适合的量。其它适合的可溶性液体添加剂是简单的碱。(称为“液体”，是因为在实践中更容易并且更安全地将它们作为水溶液而不是作为固体加入压裂液)。合适的碱为氢氧化钠、氢氧化钾和氢氧化铵。其它合适的可溶性液体添加剂是醇盐、水溶性碳酸盐和碳酸氢盐、醇(例如，但不限于甲醇和乙醇)、烷醇胺和有机胺(例如单乙醇胺和甲胺)。其它合适的可溶性液体添加剂是酸，例如，但不限于盐酸、氢氟酸、氟化氢铵、甲酸、乙酸、乳酸、乙醇酸、氨基多羧酸(例如，但不限于羟乙基亚氨基二乙酸)、多氨基多羧酸(例如，但不限于羟乙基乙二胺三乙酸)、有机酸的盐(包括偏盐(partial salts))(例如，铵盐、钾盐或钠 盐)，以及这些酸或盐的混合物。(氟化氢铵与水接触，部分水解形成HF，因此在这里称为酸。)有机酸可以当作它们的盐来使用。在腐蚀性的酸可能与可腐蚀金属接触时，加入防腐剂。 
一种或多种固体酸-前体和一种或多种固体酸-反应性物质(如果它们都存在的话)的混合物可以是单独组分的单独颗粒的纯物理状态的混合物。也可以这样制造混合物，使一种或多种固体酸-前体和一种或多种固体酸-反应性物质存在各颗粒中；这称为“结合混合物”。可以通过非限制性实施例，通过用固体酸-前体涂覆酸-反应性物质，或者通过加热物理状态的混合物直到固体酸-前体熔化、充分混合、冷却和粉碎来制备该混合物。例如，在工业上通常进行共挤出(co-extrude)聚合物与无机填料如滑石或碳酸盐，从而使它们具有不同的光学性质、热和/或机械性能。聚合物和固体的这类混合物一般称为“填充聚合物(filled polymer)”。在任何情况下，混合物中组分的分布优选为尽可能均匀。可以根据情形调节这些组分的选择和相对量，以控制固体酸-前体水解速率和固体酸-反应性物质的溶解速率。最重要的因素是进行处理的温度、含水流体或将与混合物接触的流体的组成，以及产生酸所需的时间和速率。 
固体酸-前体或固体酸-前体和固体酸-反应性物质的混合物可以制成各种固体形状，包括但不限于纤维状、珠状、膜状、带状和板状。可以涂覆固体酸-前体或固体酸-前体和固体酸-反应性物质的混合物以减缓水解。合适的涂料包括polycaprolate(乙交酯和ε-己内酯的共聚物)和硬脂酸钙，两者都是憎水的。Polycaprolate本身缓慢水解。通过任何方式在固体酸-前体或固体酸-前体和固体酸-反应性物质的混合物的表面上产生憎水层可以延迟水解。注意，涂覆在此可以指包胶，或者仅仅通过化学反应或通过形成或加上另一种材料的薄膜来改变表面。延迟固体酸-前体水解并释放酸的另一种合适的方法是：任选用憎水涂层将固体酸-前体悬浮在油中或乳状液的油相中。在水和固体酸-前体接触前，不会发生水解和酸的释放。用于延迟酸的生成的方法可以与包含固体酸-反应性物质的方法结合使用以加速酸的产生，因为这样可以合乎要求地延迟酸的产生，然后再加快酸的产生。 
本发明的实施方案的组合物和方法的优势在于：对于给定的油田处理，可以从许多可得的材料中容易地选择合适的固体酸-前体和固体酸-反应性物质。在特定温度下，并与特定组成的流体或多种流体(例如pH，以及其它 组分的浓度和性质，特别是电解质的浓度和性质)接触时，从具有特定化学和物理洗性质的特定固体酸-前体或固体酸-前体和固体酸-反应性物质的特定组合物(包括涂层，如果存在的话)产生酸的速率容易通过简单的方法来确定：即在处理条件下将酸-前体暴露于该流体或该多种流体中，然后监测酸的释放。固体酸-反应性物质(如果包含固体酸-反应性物质的话)的溶解速率可以通过类似的因素(例如通过固体酸-反应性物质的选择、各物质的比例、粒径、固体酸-反应性物质的煅烧和涂覆)来控制，并且通过相似的实验可以快速并很容易地进行测定。自然地，选择固体酸-前体：a)以所需的速率产生酸(需要时在适当的延迟之后)和b)与流体的其它组分相容且不干扰它们的功能。选择酸-反应性物质，酸-反应性物质加速酸的产生至适当的程度且与流体的其它组分的功能相容。 
固体酸-前体颗粒，或者混合物颗粒在原位，即在(有意地或不经意地)充填它们的位置自破坏。该位置可以是在井筒、孔眼(perforation)、压裂中的处理流体的部分悬浮液；或者作为井筒或裂缝壁上的滤饼的组成；或者在地层本身的空隙中。该方法可以使用在碳酸岩和砂岩中。在使用中，尽管该颗粒意图用于压裂中，但结束时它们可以在其它位置，在那里由于它们阻碍流体流动，因而通常是不合要求的，因而要求在全部位置自破坏。在裂缝中除去大部分颗粒，其中产生的酸腐蚀裂缝的表面。 
在使用混合物时，混合物的各组分的粒径可以相同或不同。几乎所有的粒径都可以采用。控制因素包括：a)设备性能，b)产生裂缝的宽度，c)自破坏所需的速率和时间。在实验室中，在给定温度下很容易测量给定流体中的自破坏速率。优选粒径为支撑剂和防滤失剂(fluid loss additive)的粒径，因为操作者通常使设备和实验适合这些粒径。 
这些材料的特别优势在于：固体酸-前体和产生的酸是无毒的且是生物可降解的。固体酸-前体常常用作自溶解的缝合材料(suture)。 
本发明的固体酸-前体可用于在酸压裂中以各种方法延迟酸的产生，在这些方法中，美国专利6,207,620描述了使用包胶的酸，在此全部引入。 
在酸压裂处理中使用带有或不带促进剂的固体酸-前体特别有效。酸压裂是这样一种过程，其中将酸性流体在足够高的压力下注入地层以裂解岩石；然后酸腐蚀裂缝的表面，使得沿裂缝面形成导向的流动路径，该流动路径在压力释放并且裂缝面受力重新闭合在一起之后仍存在。在酸压裂中 存在各种潜在的严重问题。首先，酸，特别是强酸与它们遇到的第一物质反应。和在基岩的酸化处理中一样，在酸压裂处理中，这意味着：裂缝一旦形成或扩大，或者一旦形成或遇到高渗透率区，(两者都可能发生在井筒附近，)酸就会与井筒附近的新鲜基岩表面接触或者在流体中与井筒附近的高渗透率区接触，并与之反应。然后大部分或全部的酸反应发生在井筒附近，或者在井筒附近的高渗透区内或附近，极少量的酸或没有酸到达远离井筒或远离高渗透区的裂缝部分。因此，在远离井筒或任何高渗透区之外沿着裂缝面不会形成蚀刻的流动路径。其次，酸一旦和部分基岩物质开始反应，就倾向于形成对后来跟随流动的酸阻力最小的“孔洞(wormholes)”或通道。如果发生其中之一或两者都发生，那么在压力释放时，裂缝封合，则从地层至裂缝，再到井筒，将不会形成产生流体的令人满意的流动路径。固体酸-前体解决了这些问题。因为开始注入时，流体不是充分酸性的，所以它不会与接触的第一地层物质反应；而是进一步进入增长的裂缝中，其中酸在释放时随后发生反应。另外，由于酸-前体是固体材料，在体积大时会有助于打开裂缝，直到发生不均匀的蚀刻，但之后当它水解后，固体酸-前体不再存在，而在其体积小时，酸-前体不会妨碍生产中流体从地层流动进入井筒。 
因此，本发明的一个实施方案是用压裂液中存在的固体酸-前体酸压裂的方法。这可以用几种方式进行。有时固体酸-前体包含在不同的常规的酸压裂处理中(其中流体含有酸，例如HCl、HF、有机酸，或其混合物)。最初存在的酸趋向于消耗在井筒附近或地层的高渗透区，但固体酸-前体会进一步被携带进入裂缝并在原位产生酸，该酸会腐蚀离井筒较远的裂缝面。最常见的是，在处理中固体酸-前体是唯一的酸源。任选地，从由固体酸-前体产生酸的压裂处理中，可以包含支撑剂以帮助保持裂缝张开，直到固体酸-前体水解并融化。 
在酸压裂中，通常需要大量的固体酸-前体。通常要求固体酸-前体快速溶解(只要在极接近井筒的地方不发生过多的溶解)，因为如果颗粒溶解太慢，就可能引起地层的溶解，而不是不均匀蚀刻裂缝面。在颗粒到达裂缝之前就被截留的情况中应该在某些地方加入防腐剂，在该地方颗粒的溶解会产生与金属组分接触的酸。向流体或颗粒中加入合适量的缓冲剂，以抵消由固体酸-前体的早期水解产生的酸的作用。 
在一个重要实施方案中，在压裂处理中使用固体酸-前体(带有或没有附加的固体酸-反应性物质)，其中它仅仅是酸源；固体酸-前体在水解前也可充当支撑剂。(通常在酸压裂中不使用支撑剂，尽管它可以使用，且该使用在本发明的范围内。)将固体酸-前体泵送至井中，并在一定温度下水解成活性酸，然后与岩石的表面反应。如成本最低的水压裂一样进行该处理，其中以高速泵送含有极少量或不含增粘剂的低浓度(例如大约0.05kg/L)固体酸-前体或混合物高速(例如高达大约3500L/min或更高)。也可以如更常规的压裂处理一样进行该处理，其中固体酸-前体或混合物含有增粘剂并具有更高的浓度，例如高达大约0.6kg/L。通常用于压裂、压裂充填(frac-packing)和砾石充填的增粘剂为聚合物或粘弹性表面活性剂。在这种情况下，固体酸-前体或混合物充当支撑剂，并优选为珠状，粒径范围通常为水力压裂中支撑剂常用的粒径范围。当使用大量的固体酸-前体或混合物的颗粒时，使用比常规酸压裂中所用的粘性更高的流体可能是必要的。相对于常规支撑剂的密度，更低密度的固体酸-前体或混合物是有利的，因为需要的增粘剂的量较少。固体酸-前体或混合物也可充当破裂剂(breaker)或增粘剂，从而增强清除能力，并补偿可能由增粘剂带来的任何损害。(已知酸损害或破坏合成聚合物和生物聚合物，该聚合物和生物聚合物用于稠化钻井液、完井液和增产液的。还已知酸损害或破坏胶束/囊泡(vesicle)结构，该胶束/囊泡结构是由粘弹性表面活性剂，或者在一些情况下由表面活性剂本身形成的。)在另一实施例中，至少一部分固体酸-前体或混合物是纤维状。已知纤维有助于输送更圆的颗粒，减少或消除对增粘的需要。 
在其它因素中，每单位面积产生的裂缝所用的固体酸-前体或混合物的量取决于温度和所需酸的量。优选的浓度范围为约0.42至约5ppg(约0.05至约0.6kg/L之间)。最优选的范围为约0.83至约2.5ppg(约0.1至约0.3kg/L之间)。 
尽管本发明的方法的基本优点之一是：极少需要或不需要转向(diversion)，以从孔洞或高渗透性区转向处理期间产生的酸，但是仍采用转向剂(diverter)从已经存在的高渗透性矿脉(streak)、岩穴(vug)或天然裂缝中转向含有固体酸-反应性物质的流体。 
除了蚀刻裂缝面增加裂缝导流能力之外，从固体酸-前体产生的酸起到了许多其它的有效功能，例如作为聚合物的破裂剂或破裂剂辅助剂，或者 粘弹性表面活性剂(如果它们存在的话)的增稠剂，作为防滤失剂的溶解剂，或者作为垢(scale)或细屑的溶解剂，等等。 
在本发明中可使用许多颗粒形状。在最简单的实施方案中，采用一定尺寸的颗粒、珠、纤维、板或带(或其它形状)的固体酸-前体。制备包含固体酸-前体和酸可溶性材料的颗粒也在本发明的范围内，例如共挤出用于所述功能的颗粒、纤维、板或带等形状的碳酸钙和固体酸-前体的混合物。也可以使用用固体酸-前体涂覆的碳酸钙(或其它固体酸-反应性材料)。也可利用在压裂中颗粒的浓度或在压裂中颗粒堆积紧密度，通过影响反应物和产物的局部浓度、对流和其它的因素来控制酸的生成速率和颗粒的溶解速率。制备包含固体酸-前体和酸可溶性材料的颗粒也在本发明的范围内，例如共挤出颗粒、纤维、板、带或其它形状的固体酸-反应性物质和固体酸-前体的混合物(任选之后再粉碎)。也可以使用用固体酸-前体涂覆的碳酸钙或其它固体酸-反应性材料。 
当在酸压裂中使用固体酸-前体或固体酸-前体和固体酸-反应性物质的混合物时，在含有或不含可溶性促进剂的情况下，该固体酸-前体或固体酸-前体和固体酸-反应性物质的混合物最初对流体中的其它任何组分都是惰性的，因此可用通常的方式制备并使用其它流体。也可以包含在油田处理流体中使用的任何添加剂，条件是，使用时它们与固体酸-前体和/或固体酸-反应性物质和/或可溶性液体促进剂相容，或者不干扰其性能，反之亦然。如果流体包含会影响固体酸-前体或固体酸-前体和固体酸-反应性物质的混合物或可溶性液体促进剂的或者受其影响的组分(如缓冲剂或增粘剂)，那么可以调节固体酸-前体或固体酸-前体和固体酸-反应性物质的混合物或可溶性液体促进剂的量和性质，或者干扰组分或被干扰组分的量和性质，以补偿它们之间的相互作用。这通过简单的实验室实验很容易确定。 
尽管就生产油和/或气的井描述了本发明的组合物和方法的实施方案，但该组合物和方法还有其它的用途，例如它们可以用于注入井(如用于提高回收或者用于储存或处理)和其它流体如二氧化碳或水的生产井中。 
实施例1.在油田处理中，乳酸没有甲酸、乙酸和柠檬酸常用。进行试验以确定乳酸在82℃下对方解石的溶解能力。图1示出了用试剂纯的乳酸溶解的方解石的ppm浓度(通过ICP-AES以Ca++测定)与水中酸的重量百分 比的关系。乳酸溶解方解石的能力与乙酸或甲酸相似，但比柠檬酸高得多。这些试验表明从乳酸酯聚合物中产生的乳酸对碳酸钙的溶解是有效的。 
实施例2.进行实验(表1)评估PLA的水解速率并比较在加入或未加入方解石时PLA的水解速率。PLA是购自Cargill Dow，Minnetonka，MN，USA的NATUREWORKSTM PLA Polylactide Resin 4042D，D-乳酸和L-乳酸的聚合混合物。使用的材料是直径为约4mm的珠子。方解石是试剂纯的粉末。在使用时，将45.04克PLA和20克方解石加入到500ml的蒸馏水中。显示的时间为100％水解时的时间。 
表1 
  组成 121℃ 135℃ 149℃
  PLA 在大于2小时内溶解 在大于2小时内溶解 在小于2小时内溶 解
  PLA+方解石 在大于2小时30分钟   内溶解 在大于2小时30分钟   内溶解 在小于45分钟内 溶解
  方解石 不溶解 不溶解 不溶解
在另一实验中，发现双轴拉伸的PLA薄膜的样品在149℃下几乎和NATUREWORKSTM PLA Polylactide Resin 4042D一样易于溶解在蒸馏水中，该双轴拉伸的PLA薄膜为购自Cargill Dow，Minnetonka，MN，USA的NATUREWORKSTM BOPLA Biaxially Oriented Polylactide acid Film MLF100。这些结果表明这些固体酸-前体以适用于酸压裂中酸源的合适速率水解和溶解，并且它们溶解方解石。此外，在这些条件下不溶于水的方解石加速了PLA的水解速率。 
实施例3.进行实验以证明可溶性液体促进剂的功效。将45.04克NATUREWORKSTM PLA Polylactide Resin 4042D添加至500毫升蒸馏水中。如果完全水解，这将有1摩尔乳酸。改变促进剂的量，添加浓度为约0.1摩尔至约1摩尔。然后，在90℃下搅拌该混合物。数小时后，没有观察到完全水解。发现氢氧化钠的反应性近似于二乙酸丙二醇酯；这两者比氢氧化 钾的反应性强，而氢氧化钾的反应性又比氢氧化铵的反应性强。一旦开始PLA溶解，其速率没有受到所添加组分的浓度的影响。 

Claims (17)

1.一种酸压裂被井筒穿透的地下地层的方法，包括：
a)在足以压裂地层的压力下，向地层中注入包括浓度为约0.05至约0.6kg/L固体酸-前体颗粒的流体，和b)将至少一部分的所述固体酸-前体水解，其中该固体酸-前体与选自下列的固体酸-反应性物质混合：氢氧化镁、碳酸镁、碳酸钙镁、碳酸钙、氢氧化铝、草酸钙、磷酸钙、偏磷酸铝、多磷酸钠锌钾玻璃和多磷酸钠钙镁玻璃。
2.权利要求1的方法，其中固体酸-前体选自丙交酯、乙交酯、聚乳酸、聚乙醇酸、聚乳酸和聚乙醇酸的共聚物、乙醇酸和其它含有羟基、羧酸或羟基羧酸的部分的共聚物、乳酸和其它含有羟基、羧酸或羟基羧酸的部分的共聚物，及其混合物。
3.权利要求2的方法，其中固体酸-前体是聚乳酸。
4.权利要求1的方法，其中固体酸-前体颗粒与固体酸-反应性物质颗粒物理混合。
5.权利要求1的方法，其中固体酸-前体与固体酸-反应性物质在相同的颗粒中。
6.权利要求5的方法，其中固体酸-反应性物质被固体酸-前体包裹。
7.权利要求6的方法，其中包裹固体酸-反应性物质的固体酸-前体涂覆有水解-延迟材料。
8.一种酸压裂被井筒穿透的地下地层的方法，包括：
a)在足以压裂地层的压力下，向地层中注入包括浓度为约0.05至约0.6kg/L固体酸-前体颗粒的流体，和b)将至少一部分的所述固体酸-前体水解，其中该固体酸-前体涂覆有水解-延迟材料。
9.上述权利要求8的方法，其中所述固体酸-前体选自丙交酯、乙交酯、聚乳酸、聚乙醇酸、聚乳酸和聚乙醇酸的共聚物、乙醇酸和其它含有羟基、羧酸或羟基羧酸的部分的共聚物、乳酸和其它含有羟基、羧酸或羟基羧酸的部分的共聚物，及其混合物。
10.权利要求9的方法，其中所述固体酸-前体是聚乳酸。
11.一种酸压裂被井筒穿透的地下地层的方法，包括：
a)在足以压裂地层的压力下，向地层中注入包括浓度为约0.05至约0.6kg/L固体酸-前体颗粒的流体，和b)将至少一部分的所述固体酸-前体水解，其中所述流体还包括加速固体酸-前体水解的水溶性试剂，所述试剂选自酯、二酯、酐、内酯、碱金属醇盐、碳酸盐、碳酸氢盐、醇、碱金属氢氧化物、氢氧化铵、酰胺、胺、烷醇胺，及其混合物。
12.权利要求11的方法，其中所述试剂选自氢氧化钠、氢氧化钾、氢氧化铵和二乙酸丙二醇酯。
13.权利要求11的方法，其中所述固体酸-前体选自丙交酯、乙交酯、聚乳酸、聚乙醇酸、聚乳酸和聚乙醇酸的共聚物、乙醇酸和其它含有羟基、羧酸或羟基羧酸的部分的共聚物、乳酸和其它含有羟基、羧酸或羟基羧酸的部分的共聚物，及其混合物。
14.权利要求13的方法，其中所述固体酸-前体是聚乳酸。
15.一种酸压裂被井筒穿透的地下地层的方法，包括：
a)在足以压裂地层的压力下，向地层中注入包括浓度为约0.05至约0.6kg/L固体酸-前体颗粒的流体，和b)将至少一部分的所述固体酸-前体水解，其中所述流体还包含选自下列的酸：盐酸、氢氟酸、氟化氢铵、甲酸、乙酸、乳酸、乙醇酸、氨基多羧酸、多氨基多羧酸，它们的盐和混合物。
16.权利要求15的方法，其中所述固体酸-前体选自丙交酯、乙交酯、聚乳酸、聚乙醇酸、聚乳酸和聚乙醇酸的共聚物、乙醇酸和其它含有羟基、羧酸或羟基羧酸的部分的共聚物、乳酸和其它含有羟基、羧酸或羟基羧酸的部分的共聚物，及其混合物。
17.权利要求16的方法，其中所述固体酸-前体是聚乳酸。
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