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CN1662727A - 处理地下地层的方法 - Google Patents

处理地下地层的方法 Download PDF

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CN1662727A
CN1662727A CN03814098.5A CN03814098A CN1662727A CN 1662727 A CN1662727 A CN 1662727A CN 03814098 A CN03814098 A CN 03814098A CN 1662727 A CN1662727 A CN 1662727A
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杰西·李
埃里克·尼尔森
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Abstract

已经发现可将以松散粉末形式存在的多种固体化学物质添加到地下处理流体中，而延迟释放，此时所述化学物质是以胶囊形式输送的，所述胶囊由包胶的颗粒构成，所述包胶的颗粒是通过在压力下聚集松散粉末以形成压实材料，以及任选地干粉碎所述压实材料，以制备所需尺寸的颗粒而获得的。本发明特别适用于输送用于增产流体的新型破裂剂或用于井筒胶接的添加剂。

Description

处理地下地层的方法
技术领域
本发明涉及处理地下地层(subterranean formation)的领域，以及更具体地涉及通过受控的延迟释放将材料输送进地层的方法。本发明特别适用于包胶破裂剂(encapsulated breaking agent)的制备。
背景技术
长久以来，地下地层的水力压裂就被建立为从井筒(wellbore)中增产(stimulation)油气(hydrocarbon)流体产量的有效方式。在水力压裂中，注入油井增产流体(通常称为压裂液)并使其经过井筒，以及在至少足够在地层中产生裂缝的压力下，挤压(against)由井筒穿透的地下地层的表面。通常，首先注入“前置(pad)液”以产生裂缝，然后以足够将裂缝从井筒延伸更深至地层的压力和速率注入压裂液，压裂液通常带有颗粒支撑剂(granular proppingagent)。如果使用支撑剂，则目的通常是从裂缝的顶端反向至井筒之间产生支撑剂填充区域。在任何情况下，水力引发的裂缝比地层的渗透性强，以及水力引发的裂缝在地层中起到油气流体的通道或管道的作用，以流至井筒，然后流至它们的收集表面。
用作压裂液的流体也可以有多种，但是多数(如果不是大多数)是水性流体，这些水性流体已经通过加入天然或合成聚合物(交联或未交联的)或者粘弹性表面活性剂而增粘(viscosified)或稠化(thickened)。载体流体通常是水或盐水(例如，氯化钠和/或氯化钾的稀水溶液)。
增粘聚合物一般为可溶剂化的(或可水合的)多糖，例如半乳甘露聚糖胶(galactomannan gum)、葡糖聚糖胶(glycomannan gum)或纤维素衍生物。该聚合物的实例包括瓜耳胶(guar)、羟丙基瓜耳胶、羧甲基瓜耳胶、羧甲基羟乙基瓜耳胶、羟乙基纤维素、羧甲基-羟乙基纤维素、羟丙基纤维素、黄原胶、聚丙烯酰胺和其它的合成聚合物。在这些当中，由于商用可获得性和成本性能的原因，瓜耳胶、羟丙基瓜耳胶和羧甲基羟乙基瓜耳胶一般是优选的。
但在多数(如果不是大多数)情况下，增粘聚合物是用合适交联剂交联的。交联聚合物具有更高的粘度并且甚至更有效地将支撑剂运送至压裂的地层中。一般在高pH值的流体中，已经广泛使用硼酸根离子作为瓜耳胶、瓜耳胶衍生物和其它半乳甘露聚糖的交联剂。其它交联剂包括，例如钛交联剂、铬、铁、铝和锆。
粘弹性表面活性剂流体通常是通过在载体流体中混合至合适量的合适表面活性剂，例如阴离子、阳离子、非离子和两性表面活性剂而制备的。粘弹性表面活性剂流体的粘度归因于流体中组分所形成的三维结构，这是因为当粘弹性表面活性剂的浓度显著高于临界浓度时，表面活性剂分子聚集成胶束，该胶束可高度缠结形成表现出弹性的网络结构。
粘弹性表面活性剂溶液通常是通过将某些试剂加入表面活性剂的浓缩溶液中而形成的，所述表面活性剂的浓缩溶液通常由如溴化十六烷基三甲基铵(CTAB)等长链季铵盐组成。在表面活性剂溶液中产生粘弹性的通用试剂是盐，如氯化铝、氯化钾、水杨酸钠和异氰酸钠，和非离子有机分子如氯仿。表面活性剂溶液中电解质含量也是控制其粘弹性的重要因素。
油井处理，例如水力压裂的关键方面是“排液”，例如在处理结束后从裂缝中除去载体流体(即，没有支撑剂的基本流体)。用于促进裂缝排液的技术通常包括尽可能实际地降低压裂液的粘度，以使其容易流回至井筒。
凝胶破裂剂(gel breaker)是增产等中常用的常规聚合物类流体，这是因为与粘弹性表面活性剂类流体不同的是，常规聚合物类流体与油气或水性地层流体接触时不能自发断裂，并且在地层中留下高粘度流体将导致地层的可渗透性降低，并因此导致产量降低。最广泛使用的破裂剂是氧化剂和酶。可将破裂剂溶解或悬浮在处理流体的液体(水性的、非水性的或乳液)相中以及在整个处理中接触聚合物(“内部”添加)，或者在处理后的某个时间接触流体(“外部”添加)。
最常用的外部方法和组合物涉及包胶酶或包胶氧化剂，或涉及包含破胶剂的前冲洗剂或后冲洗剂。破裂可发生在井筒、砾石充填(gravel pack)、滤饼、岩石基体中，裂缝中或者另外添加的或产生的环境中。例如，参见已经转让给Schlumberger Dowell的美国专利4741401(Walles等人的)，在此将其引入作为参考。
地层流体中含有的油气流体通过粘弹性类压裂液而自发破裂，有时候它更适合控制破裂。在2002年1月10日公开的、公开号为20020004464的美国专利申请09/826127(在此将其引入作为参考)中，提出几种类型破裂剂，包括：包胶的盐，例如过硫酸铵、水杨酸钠；无机盐，例如NaPF6(六氟磷酸钠)和KCl(氯化钾)。
包胶材料的释放通常涉及几种机理。这些机理一般涉及胶囊外壳(enclosure)的部分溶解、渗透或化学扩散。然而，由于在不迟于压裂操作结束时发生破裂是合适的，所以当裂缝由于地层压力而闭合时，关键的机理是破裂剂通过外壳或包胶的涂层的破裂而释放。显而易见的是，胶囊越大，在裂缝闭合中被压碎的可能性越大。另一方面，必须将包胶破裂剂泵送至井底，因此通常选择与支撑剂的尺寸类似的破裂剂胶囊尺寸。
最常用的支撑剂是由尺寸在约0.1毫米至约2毫米之间的砂粒制成的，最常用的是尺寸在0.2毫米和0.5毫米之间的砂粒制成的。因此，当研究一种新材料以确定其作为包胶的破裂剂的适应性时，关键的限制是具有在包胶过程中存留的足够强度的颗粒的可获得性。多种固体材料实际上只能以粉末形式存在，该粉末形式是通过具有对应于250目的筛(根据ASTM标准)而获得，或者由主要介于0.03毫米和0.05毫米之间的颗粒构成。
应当进一步强调的是，即使破裂剂释放的预期基本机理不是通过裂缝闭合而引起的压碎，而是，例如通过外壳的溶解或泄漏。在使用可支付的(affordable)技术时，粉末状材料的涂覆通常导致一些颗粒不能被涂覆或不能被完全涂覆。因此，破裂剂过早地与交联聚合物反应，以使在支撑剂被正确置入裂缝之前，流体可能就释放其悬浮特性。对于有效包胶而言，必须涂覆几乎所有颗粒，以防止整个压裂操作失败。
在其它用于在油井服务操作中的流体，例如胶接流体(cementing fluid)中，延迟释放诸如促进剂的一些添加剂也是合适的。尽管粒度对压裂液来说不是至关紧要的，但是能够输送一些包胶形式的添加剂是有益的。
仍然存在改进的油井服务流体的需要，并且以下的发明至少部分满足该需要。
发明概述
已经发现可将以松散粉末(bulk powder)形式存在的多种固体化学物质添加到地下处理流体中，而延迟释放，此时所述化学物质是以胶囊形式输送的，所述胶囊由包胶的颗粒构成，所述包胶的颗粒是通过在压力下聚集松散粉末以形成压实材料(densified material)而获得的，以及任选地干粉碎所述压实材料，以制备所需尺寸的颗粒。
取决于所需的尺寸，压实材料是通过以干法(dry process)用辊筒压制松散粉末形成压实片材(compacted sheet)，然后干粉碎成颗粒而获得的。只要挤压的压实材料大于或等于所需颗粒尺寸，则不是必须在造粒前具有片材，因而，可首先制备例如大于20目的团块(briquette)，然后将其尺寸减小至20/40目，以适合用于大多数油井增产应用。
附图说明
图1是粉末(A)的微观图(比例60倍)，由粘结(binding)材料聚集的(B)和涂布的(C)。
图2是本发明的粉末(A)的微观图(比例60倍)，压实成片材(D)，粒化的(E)和涂布的(F)。
图3是在包胶的聚集物(空心圆)和包胶的颗粒(实心方块)中释放的破裂剂的百分比与时间(单位：分)的点线图。
发明详述
A显示的是只能以粉末形式存在的无机磺酸盐(平均粒度为约250目)。它可以由粘结材料聚集，以产生尺寸范围在20/40目内的颗粒(B)。然而聚集物的形状对包胶来说太没有规则，以及颗粒也太不牢固而不能经受涂布过程。部分聚集物将在涂布过程中存留下来(图C)。然而，即使涂布程度高，释放速率也十分快(图3，实心方块)。
在油井增产的情况下，实质上是通过地层闭合的原因压碎胶囊，涂层材料优选将包胶的颗粒释放至油井处理流体中。在其它的情况下，所述外壳在地下地层中存在的压力和温度条件下降解。当然，两种释放机理和如渗透等其它机理的结合也可发生，并且取决于应用而优选。
相同的材料(A)可加工成压实片材(D)，然后将其粒化成10/40目(E)。这些生成的颗粒牢固且能以合理的涂布程度成功包胶(F)。如图3所示，在没有闭合压力下，空心环，即芯材料(core material)的释放速率几乎是零。
压实片材是通过干辊筒压制而制备的。在该方法中，通常预加工粉末以进行预压实和脱气。然后将粉末装入可施加几公吨压实力的压实辊的辊隙中，以形成片状结构，该结构的厚度约为2毫米。该片可断裂成较小的片，将较小的片装入压碎辊中，以将它们压碎成颗粒。在输送前，优选将该粉末预压实和脱气，例如通过螺旋式进料器进入辊隙区域和密封系统。
多年以来，人们就在肥料和药物产品的制造中知道干法。该干法允许制造极其致密的颗粒，这些颗粒可容易获得相对均匀的涂层。因此，高涂布程度不是必须的，并且涂层厚度可以作为预期的释放时间的函数来调整。
在一些情况中，粘合剂可用来使粉末颗粒更“粘”。
干辊筒压制过程允许可使用多种化学物质，这些化学物质在化学上适合用作油田服务的添加剂，但只能以松散粉末形式存在。因此，现在可获得更多选择的化学物质的受控释放。
这些材料的实例包括凝胶破裂剂，例如聚电解质(阳离子的或阴离子的)、离子交联聚合物、非离子聚合物和氧化剂。其它应用包括井胶接添加剂，例如缓凝剂(retarders)、分散剂、流体损失控制添加剂(fluid-loss controladditive)、促凝剂或增量剂(extender)。
凝胶破裂剂的实例列于下表1中。
表1
聚电解质 阳离子的 聚(2-乙烯基咪唑鎓盐)(poly(2-vinylimidazoliniumsalt)聚(N-乙烯基咪唑鎓盐)聚(1-乙烯基-2-甲基-2-咪唑鎓盐)聚(N-乙烯基哌啶)
阴离子的 聚丙烯酸及其盐聚甲基丙烯酸及其盐聚衣康酸及其盐聚巴豆酸及其盐聚(3-丙烯酰胺基-3-甲基丁酸)及其盐聚(3-甲基丙烯酰胺基-3-甲基丁酸)及其盐聚(萘磺酸)及其盐聚(苯乙烯磺酸)及其盐聚(木质素磺酸)及其盐
离子交联聚合物 聚(4-乙烯基吡啶)
聚(乙烯-共-甲基丙烯酸)及其盐聚(丙烯酸乙酯-共-4-乙烯基吡啶)聚(丙烯酸乙酯-共-N-甲基-4-乙烯基吡啶鎓碘化物(vinylpyridinum iodides))聚(对苯二甲酸乙二酯-共-磺酸锌)聚(苯乙烯-共-甲基丙烯酸)及其盐聚(苯乙烯-共-苯乙烯磺酸盐(sulfonate))聚酰胺-6聚(丙烯酸乙酯)
非离子聚合物 聚环氧乙烷聚环氧丙烷
氧化剂 过氧化钠过氧化钡过氧化氢尿素加合物过氧化镁氯酸钾铬酸钾重铬酸钾碘酸钾硝酸盐亚硝酸钾过硼酸钠氧化物例如氧化铬、氧化镁、氧化锰、氧化钼、氧化铁、氧化钴、氧化钨、氧化锇、氧化铑、氧化铱、氧化钌、氧化镍、氧化锌、氧化锆、氧化钛、氧化硼、氧化铍、氧化钙、氧化钡和氧化铝
在上述所列的材料中，聚(萘磺酸)的盐(分子量为约7000)和聚(苯乙烯磺酸)的盐(分子量为约70000)特别优选用作两性表面活性剂，如甜菜碱表面活性剂的破裂剂。
随着井的胶接，添加剂的延迟释放可导致改善对水泥(cement)浆料性能的控制。例如，水泥缓凝剂的性能可通过延迟它们的释放直到水泥经历过初始水合阶段而得以改进。促进剂的延迟释放可导致改善对固化时间(settime)的控制。类似的效率改进可通过延迟释放流体损失添加剂、分散剂等而得以实现。对胶接来说，包胶的颗粒的粒度不如用于压裂液的包胶的破裂剂的粒度重要。大范围的粒度可以是合适的。例如，适合用于井胶接中的添加剂的实例列于表2中。
表2
缓凝剂/分散剂 木质素磺酸钠
流体损失控制添加剂 羟乙基纤维素羟丙基纤维素黄原胶AA/AMPS共聚物羧甲基羟乙基纤维素磺化聚苯乙烯苯乙烯/马来酸酐的磺化共聚物磺化聚乙烯基甲苯
促进剂 硫酸铝甲酸盐氯化铝硫酸铁
增量剂 膨润土高吸水性聚合物硅镁土(attapulgite)
对于所述添加剂的延迟释放而言，外壳部件是重要元素。该外壳是通过提供基本均匀的涂料或被介于100目至5目之间的包胶的单个颗粒材料的方法涂布的任何合适的涂层。通过改变涂层厚度，可较大程度地改变释放特性。更短的释放时间通过较薄的涂层获得。
两种主要涂布方法，即顶喷和底喷法是以在固体颗粒流体化床的顶部或底部处的喷嘴的位置为特征的。喷嘴喷涂雾化的涂层溶液的流体，同时将颗粒悬浮在流体化空气流中，空气气流携带颗粒经过喷嘴。然后，当在循环流动中颗粒被携带出喷嘴时，颗粒与雾化的涂层材料相互碰撞。设定流态化空气的温度，以在与颗粒碰撞之后不久，蒸发溶液或悬浮液体介质或固化涂层材料。固化的涂层材料将逐渐覆盖颗粒。继续该方法直到各颗粒被均匀地涂布至所需厚度。
1.涂布了的颗粒的性质可通过涂层配方、加工条件、不同涂层材料的层压来调节。材料的选择取决于多种因素，例如所使用材料的物理和化学性质。涂层材料可选自下述范畴之一：水性和有机溶液、分散体和热熔体。非限制性的实例包括丙烯酸(酯)类、卤化碳、聚乙烯醇、Aquacoat水性分散体、烃树脂、聚氯乙烯、Aquateric肠溶衣(enteric coating)、HPC、聚(醋酸乙烯酯苯二甲酸酯)(polyvinylacetate phthalate)、HPMC、聚偏二氯乙烯、HPMCP、蛋白质、Kynar、氟塑料、橡胶(天然或合成的)、酪蛋白酸盐、麦芽糖糊精、紫胶、氯化橡胶、有机硅(silicone)、Coateric涂料、微晶蜡、淀粉、涂敷黄油、乳固体、硬脂、Daran胶乳、糖蜜、蔗糖、糊精、尼龙、表面活性剂、Opadry涂料系统、Surelease涂料系统、肠溶物(enterics)、石蜡、Teflon碳氟化合物、Eudragits聚甲基丙烯酸酯、酚醛塑料、蜡、乙氧化乙烯醇、乙烯醇共聚物、聚交酯、玉米醇溶蛋白、脂肪、聚氨基酸、脂肪酸、聚乙烯明胶、聚乙二醇、甘油酯、聚乙酸乙烯酯、植物胶和聚乙烯吡咯烷酮。

Claims (16)

1.一种处理地下地层的方法，其包括：将含有以松散粉末形式存在的固体添加剂的油井处理流体注入地下地层，其中所述固体添加剂是作为胶囊输送的，所述胶囊由包胶至用于延迟释放所述添加剂的外壳中的颗粒构成，所述颗粒是通过包括在压力下聚集松散粉末以形成压实材料的工艺而获得的。
2.权利要求1所述的方法，其中所述压实材料是通过以干法用辊筒压制松散粉末形成压实片材而获得的。
3.上述任一项权利要求所述的方法，其中所述处理是水力压裂并且颗粒在20/40目的尺寸范围内。
4.上述任一项权利要求所述的方法，其中所述外壳包括涂层材料，以使通过地层闭合的原因压碎所述胶囊，使所述固体添加剂释放至油井处理流体中。
5.上述任一项权利要求所述的方法，其中所述外壳在地下地层中存在的压力和温度条件下至少部分降解。
6.上述任一项权利要求所述的方法，其中所述固体添加剂是选自聚电解质(阳离子的或阴离子的)、离子交联聚合物、非离子聚合物或氧化剂中的凝胶破裂剂。
7.权利要求6所述的方法，其中所述添加剂是选自聚(2-乙烯基咪唑鎓盐)、聚(N-乙烯基咪唑鎓盐)、聚(1-乙烯基-2-甲基-2-咪唑鎓盐)或聚(N-乙烯基哌啶)中的阳离子聚电解质。
8.权利要求6所述的方法，其中所述添加剂是选自聚丙烯酸及其盐、聚甲基丙烯酸及其盐、聚衣康酸及其盐、聚巴豆酸及其盐、聚(3-丙烯酰胺基-3-甲基丁酸)及其盐、聚(3-甲基丙烯酰胺基-3-甲基丁酸)及其盐、聚(萘磺酸)及其盐、聚(木质素磺酸)及其盐或聚(苯乙烯磺酸)及其盐中的阴离子聚电解质。
9.权利要求6所述的方法，其中所述添加剂是选自聚(4-乙烯基吡啶)、聚(乙烯-共-甲基丙烯酸)及其盐、聚(丙烯酸乙酯-共-4-乙烯基吡啶)、聚(丙烯酸乙酯-共-N-甲基-4-乙烯基吡啶鎓碘化物)、聚(对苯二甲酸乙二醇酯-共-磺酸锌)、聚(苯乙烯-共-甲基丙烯酸)及其盐、聚(苯乙烯-共-苯乙烯磺酸酯)、聚酰胺-6或聚(丙烯酸乙酯)中的离子交联聚合物。
10.权利要求6所述的方法，其中所述添加剂是选自聚环氧乙烷和聚环氧丙烷中的非离子聚合物。
11.权利要求6所述的方法，其中所述添加剂是选自过氧化钠、过氧化钡、过氧化氢尿素加合物、过氧化镁、氯酸钾、铬酸钾、重铬酸钾、碘酸钾、硝酸钾、亚硝酸钾、过硼酸钠或聚环氧丙烷中的氧化剂。
12.上述任一项权利要求所述的方法，其中所述固体添加剂是选自分散剂、流体损失控制添加剂、促凝剂或增量剂中的井胶接添加剂。
13.权利要求12所述的方法，其中所述固体添加剂是选自木质素磺酸钠、木质素磺酸钙、聚(萘磺酸盐)、聚(三聚氰胺磺酸盐)或磷酸胺中的分散剂。
14.权利要求12所述的方法，其中所述固体添加剂是选自羟乙基纤维素、羟丙基纤维素、黄原胶、AA/AMPS共聚物、羧甲基羟乙基纤维素、磺化聚苯乙烯、苯乙烯/马来酸酐的磺化共聚物或磺化聚乙烯基甲苯中的流体损失控制添加剂。
15.权利要求12所述的方法，其中所述固体添加剂是选自硫酸铝、甲酸盐和氯化铝中的促进剂。
16.权利要求12所述的方法，其中所述固体添加剂选自膨润土、高吸水性聚合物和硅镁土中的增量剂。
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CA2490077C (en) 2007-12-04
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CA2490077A1 (en) 2003-12-31
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