CN88100379A - 处理地层的方法 - Google Patents

处理地层的方法 Download PDF

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CN88100379A
CN88100379A CN88100379.4A CN88100379A CN88100379A CN 88100379 A CN88100379 A CN 88100379A CN 88100379 A CN88100379 A CN 88100379A CN 88100379 A CN88100379 A CN 88100379A
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capsule
disrupting agent
closure casing
fluid
fracturing fluid
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CN1018011B (zh
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维尔海姆·E·瓦利斯
多纳德·L·托姆金森
特里沃尔·D·维利亚姆森
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Dow Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/70—Compositions for forming crevices or fractures characterised by their form or by the form of their components, e.g. foams
    • C09K8/706—Encapsulated breakers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/66—Compositions based on water or polar solvents
    • C09K8/68—Compositions based on water or polar solvents containing organic compounds
    • C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/92—Compositions for stimulating production by acting on the underground formation characterised by their form or by the form of their components, e.g. encapsulated material
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH DRILLING; MINING
    • E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/25—Methods for stimulating production
    • E21B43/26—Methods for stimulating production by forming crevices or fractures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S507/00—Earth boring, well treating, and oil field chemistry
    • Y10S507/902—Controlled release agent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S507/00—Earth boring, well treating, and oil field chemistry
    • Y10S507/921—Specified breaker component for emulsion or gel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S507/00—Earth boring, well treating, and oil field chemistry
    • Y10S507/922—Fracture fluid

Abstract

用一种含有由封闭壳体包封的破坏剂的可控释放封壳破坏压裂液。封闭壳体对于地层中的至少一种液体或对于随封壳一同注入的液体具有可渗透性，因此当封壳充分暴露于液体中，封壳的破坏可以延迟到预定的时间，尔后向地层释放破坏剂。破坏剂的释放时间是可以控制的，使全部破坏剂都引入地层。

Description

本发明涉及一种用可控制的释放封壳向压裂液提供破坏剂来进行压裂地层用的水基压裂液的破胶的方法，以及一种包含此种可控制的释放封壳的水基压裂液。
在钻井及后来从地层中采出诸如原油和天然气之类的流体的过程中，为了提高钻井操作的效率、为了增加从地层中采出流体的产量和/或终止或封掉一口非生产井，在井眼和/或地层中加入了各种物质。一般，这些处理剂都是在它们呈活性状态的情况下在地面加入，然后流入井筒或经过井筒进入地层。
例如，常常用一种处理剂来压裂一个地层，这种处理剂在技术上一般称做压裂液（一种液体如水，盐水等等），以便促进地层流体的采出。在压裂地层的过程中，压裂液以足够高的速度和压力注入地层以在地层中产生一条或多条裂缝和将地层中原已存在的裂缝加以扩张或延伸。这种流体可以含有一种支撑剂，例如砂或烧铝土，该支撑剂沉积在地层的裂缝中以保持地层裂缝张开。这种压裂流体也可以含有一种可以和地层中的酸溶性成分起反应的酸，通过反应造就和扩展流体从地层中流出的通道。
到目前为止，在水力压裂和酸化压裂中一般使用的压裂液是：高粘度凝胶水基压裂液，高粘度水/油乳化液，或气/水分散体泡沫。这些高粘度的流体具有必要的穿透能力以使压裂作业取得最大的效果，并且能使支撑剂（如果使用支撑剂的话）悬浮而不至于过多沉降。此外，与低粘度流体相比，高粘度流体能够使裂缝张开得更宽。
在高粘度水溶液或乳化液被泵入地层中并且形成了裂缝之后，一般要求将凝胶体或乳化液转化为低粘度流体，从而使该流体能从地层中反排出来，并且使所需要的物质如原油或天然气能经过裂缝流入井筒。压裂液的这种粘度的降低通常称作“破胶”或“破乳”。通常，破胶或破乳是通过在所要求的时间向地层中加入降粘剂（一般叫作“破坏剂”）来实现的。不幸的是，上述技术常常不能达到足够高的破胶或破乳（也就是压裂液的粘度降低得不够），或者出现压裂液的过早的破坏。压裂液的过早破坏使其粘度在所要求的压裂作业终止之前便下降了，因而降低了作业的总效果。
人们曾建议过一种控制和/或延缓降粘剂或“破坏剂”的活性的方法，该方法是向地层中注入破坏剂的颗粒或小球，做成颗粒或小球的方法是将破坏剂与能水合的胶凝剂的和胶降解物质混合，然后将混合物成粒或成球。例如，可参阅，美国专利第4，202，795号。当这些颗粒或小球暴露于含水流体时，据称该胶凝剂就水合并在每一个小球的周围形成保护凝胶，这样就能防止破坏剂进入含水流体中，直到此保护凝胶被凝胶降解物质破坏为止。因此，至今人们声称破坏剂是可以有控制地向含水流体释放的。然而，业已发现制备这种小球所需的能水合的胶凝剂的量相当大，且该量要小心地加以控制。此外，释放小球所需的时间可能变化很大。
另一种延迟释放破坏剂的方法是由美国专利第4，506，734号介绍的，该方法是把降粘化学剂引入水力压裂液中，该化学剂是封在空心或多孔的可压碎的小珠中的。据称，当压裂液在地层中流过或向地层滤失时或者当反排压裂液时由于地层裂缝的闭合可使小珠压碎从而释放出小珠内的降粘剂。不幸的是，由地层闭合造成的应力会影响压碎的小珠的百分比，使很大百分比的小珠可能仍未被压碎，尤其当地层裂缝以低速闭合时更是如此。除此之外，大量的小珠可能会在所处理地层的某一个地区被压碎而在其它的区域中压碎的小珠则少得多。因此效能会不一致。
虽然上述方法看来似乎提供了向地层延迟释放破坏剂的方法，但人们仍要求能提供另一种在工业上更为实用的、能收到相同的或更好的效果的方法。
因此，本发明的一个方面是一种使水基压裂液破坏的方法包括向地层注入可控制释放封壳，每一个封壳都含有一封闭的壳体将水基压裂液的破坏剂封闭在其中;封闭壳体足以被存在于地层中的流体或随可控制释放封壳一同注入地层的流体中一种流体渗透，这样当封壳暴露于流体中达足够长时间后壳体能够释放出破坏剂。
使用本发明的上述方法，大大改善了压裂液的破胶或破乳。特别是，不论其释放机理如何，所有的或基本上所有的可控制释放封壳都将在某一时间向地层释放其所含的破坏剂。因此，虽然设想到由于地层的闭合而在封壳上产生的应力可能（而且通常如此）使破坏剂释放，但释放破坏剂不需要地层闭合来压碎封壳。此外，即使这种压碎释放是主要释放机制，那些未被压碎的封壳仍然会向地层释放破坏剂。因此，本发明就完成了一种使用较少材料而收到更为一致的效果的方法。
除此之外，破坏剂的释放比较容易控制。具体地说，设计封壳时可以使活性物质（例如破坏剂）的释放延迟到所要求的时间范围。延迟时间可以少至，例如，数小时，或长至数天或数周，然后封壳的破坏剂就会在所要求的时间比较迅速地向地层释放破坏剂。此外，使用本发明的方法可以在地面向井筒中加入封壳物质，使其流到地层中所要求的位置，在所要求的时间或在到达所要求位置之后将破坏剂释放到压裂液中。一旦到达所要求的位置和/或达到了给定时间，封壳的破坏剂即可释放。
另一方面，本发明是一种含有载液，一种稠化聚合物和可控制释放封壳的水基压裂液;每个封壳含有一包封着稠化聚合物的破坏剂的封闭壳体，封闭壳体可被载液或存在于地层中的流体渗透，因而当封闭壳体暴露于载液中达到预定的时间，封闭壳体就能够破裂，从而将破坏剂释放到压裂液中。
此处所用术语“可渗透的”是指当可控制封壳分散在压裂液中时，在混合温度和压力下（即混合水及其它流体的温度和压力），在混合和输送压裂液所需的时间内，不会释放出并不需要的数量的破坏剂，但是在所处理的地层的压力和温度下却能释放出有效量的破坏剂足以降低增稠了的压裂液的粘度。一般，压裂液是水基流体，为了提供所要求的性能，可控制的释放封壳在接触到10℃至30℃温度和标准压力的头0.5小时内，将释放出少于10%（重量）的破坏剂;较好的是少于5%，最好少于1%;而当暴露于10℃至200℃温度及标准压力下时在48小时内至少释放出50%（重量），较好的是60%（重量）的破坏剂，这样，可控制释放封壳就能够在正常的贮存期包住破坏剂，并最好是一直保持到把封壳送入地层和当封壳内部的压力由于流体渗入封壳而上升到足够高的程度而使封闭壳体破裂时为止。作为在此使用的术语，一种基本上不可渗透的封闭壳体是指在前面所述时间之内不会释放出所封放的破坏剂的壳体。
封闭壳体可采用任何可渗透的材料，它可以是任何由于自身特性而具有渗透性和/或由于有缝隙，裂纹，可溶性添加剂等而具有渗透性。封闭壳至少可被存在于所处理的地层中的或随封壳一起注入地层的压裂液本身中的一种流体（一般为水或盐水）所渗透。这种封闭壳体能够在地层温度下由于封壳内部的压力超过了周围环境的压力而释放出破坏剂。一般，封闭壳体最好是用可被地下环境中的流体或与封壳一同注入地层的流体渗透的材料制备。这样流体穿透封闭壳体壁进入封壳使封壳内部的压力增加。
最有利的封闭壳体材料的选择取决于多种因素。这些因素包括：封闭壳体材料的物理和化学性能;封壳所处的作业条件（包括温度）;所采用的破坏剂及其与封壳材料的相容性，以及所要求的时间和释放机理。例如，由于地层闭合造成的应力值以及在封壳不受外应力作用的情况下所要求的注入封壳后释放时间都应在为一定的用途选择最合适的封闭壳体时加以考虑。
封闭壳体一般是一种非水溶性的、透水的材料。封闭壳体的渗透性，以及厚度和弹性（在较小程度上）决定了封壳周围的环境水（即雨水、水、河水等等）透入封壳的速率，流体透入后是封闭壳体的破裂和破坏剂的释放。可用作封闭壳体的材料的透水率的范围很宽。例如，如果采用较厚的涂层，可用纤维素材料（如乙酸纤维素和乙酸丁酸纤维素都具有较高的透水率）作封闭壳体。然而，一般在本发明的实施中，对封闭壳体材料的透水率的要求是当材料涂复（薄膜）厚度为25微米时在38℃下每24小时在每100厘米2面积上水蒸汽透过率（“WVTR”）一般小于3克，最好小于0.775克水（克/100厘米2/24小时）。虽然也可以选用WVTR较高的材料，但这样一般就需要较厚的涂层，这是不实用的。25微米厚的涂层的WVTR值宜小于约1.25，更理想的是约小于0.775g/100cm2/24小时（在38℃下）。虽然具有起码可测的WVTR值的封闭壳体是可选用的，但对于给定的适当环境来说，一般作壳体的材料的WVTR值在涂层厚度为25μm时在38℃下以大于0.0015g/100cm2/24小时为有利，封闭壳体宜用25微米厚的涂层的WVTR值大于约0.003的材料制成，最好是用WVTR值大于约0.0077[g/100cm2/24小时]的材料制成。
具有所要求的透水率的代表性材料包括各种聚合物，包括烯属不饱和单体的均聚物和共聚物，这些烯属不饱和单体例如有乙烯，丙烯，异丁烯，氯乙烯，1，1-二氯乙烯，苯乙烯，乙基纤维素和具有类似性能的纤维素材料和乙酸乙酯。此外，烃类石腊;环氧乙烷聚合物，环氧丙烷聚合物或它们的组合物;环氧化物;及聚碳酸酯也可以用作封闭壳体的材料。在这些材料中，较理想的是聚乙烯，聚丙烯，聚异丁烯，聚乙酸乙烯酯，氯乙烯与1，1-二氯乙烯的共聚物，苯乙烯与丁二烯的共聚物，1，1-二氯乙烯与一种例如甲基丙烯酸酯的不饱和羧酸酯的共聚物，乙烯与一种不饱和羧酸和/或其盐（例如丙烯酸或其钠盐）的共聚物，乙烯与乙酸乙烯酯的共聚物。
本发明所采用的破坏剂可以是任何一种在要求将破坏剂释放到压裂液之前不会与封闭壳体材料产生不利的作用或与壳体材料起化学反应从而破坏封闭壳体整体性的固体或液体材料。典型的例子有：酶（例如纤维素酶），氧化剂，呈离子化状态的过渡金属的盐，例如离子化状态的铁（例如，Fe Cl3），离子化银（Ag NO3）或离子化状态的铜（Cu SO4）;酸，如无机酸（如HCl）或某种有机酸（如乙酸）或两种及两种以上破坏剂的混合物。这些元素可以在被多孔粘土或其它多孔物质吸收后包封使用。
在本发明的方法中，纯粹由于液体透入封壳而在封闭壳体内部产生的压力将会破坏封闭壳体的完整性。在某些情况下，当破坏剂起反应或与进入封壳的流体发生相互作用而产生气体时便增加了封壳内压使封壳的破裂速度加快。例如，当破坏剂与流体反应产生气体时，随着反应的进行产生的气体使封壳的内压增加，从而使封壳膨胀直至其破裂。由于这一原因，在含水环境中，本发明的方法常与一种氧化剂一起使用，该氧化剂是一种有用的降粘剂或破坏剂。许多这类氧化剂都能与透入封壳的水起反应而生成气体。在这些氧化剂中，较好的有：过硫酸铵，过硫酸钠或过硫酸钾;过氧化钠;亚氯酸钠;次氯酸钠，次氯酸锂或次氯酸钙;漂白粉，过磷酸钾;过硼酸钠;单过羟苯二甲酸镁六水合物;以及很多有机氯的衍生物，例如，N，N′-二氯二甲乙内酰脲和N-氯氰尿酸和/或它们的盐。最好降粘剂是过硫酸铵或过硫酸钠，次氯酸锂或二氯异氰尿酸的钠盐。
破坏剂用封闭壳体涂膜，构成具有所要求的形状、大小和壁厚的可控释放封壳。在这里最有利于使用的可控封壳的形状、大小和组分取决于诸如具体的压裂处理，支撑剂（如果采用的话），具体的可控封壳，需要提供给流体的具体破坏剂的量，要求的释放机理，和要求的释放时间等多种因素。虽然包含有10克之多的破坏剂的封壳易于用注射模塑技术或用含有对于形成封闭壳体有用的材料的漆涂复活性物质来进行制造，但一般封壳还是制成含5毫微克至1克的破坏剂，最好含有0.05至500毫克的破坏剂。一般在这样量的范围内，可控释放封壳的平均颗粒大小将为0.01至5毫米，更好的是从0.05至2毫米。在任何给定的作业中，也可以用两种或两种以上不同颗粒大小的封壳。
可控释放封壳也可以制成使封闭壳体包裹着一种或一种以上液体或固体活性物质。例如，封壳可以制成具有一个由封闭壳体封包的液态或固态破坏剂核的单核颗粒，也可以作成具有多屋壳壁的单核，或者做成多核封壳，在这种多核封壳中每一个核都由可渗透的封壳材料封包但是互相团聚或附着在一起形成单一的颗粒。在这些不同的颗粒形态中，最有利的是由单屋可渗透封闭壳体材料封包的中间有液态或固态破坏剂的单核封壳。封壳基本上可以是任何形状的，包括球形，立方体形或不规则形状，其中以基本上呈球形的珠（如在流化床上加工的）为好。
在破坏剂进行涂膜之前，如果可能最好将固体破坏剂按其颗粒尺寸分离，以便除去细屑和/或块。这样，以后制备的封壳便含有近于相同量的破坏剂，使从封壳中释放破坏剂的时间更为准确，即，颗粒趋向于在一个较窄的时间范围内释放破坏剂。另一种方法是在涂膜之后进行颗粒大小的分类，但这样做不是很好。
本技术领域所熟知的很多技术中的任何一种都可以用来进行可控释放封壳的制造，本发明参考了那些技术。在众多的可用方法中，以使用流化床工艺制造可控释放封壳最为有利。在流化床方法中，破坏剂颗粒被喷涂上在由高速空气流或其它气体流中悬浮的适当的可渗透材料。这种流化床工艺在Knack    H.的“微粒封壳技术，应用与问题”[J，Soc.Cos.Chem.，21，85-98（Feb.4，1970）]一文以及美国专利No3，237，596和3，382，093中有所描述。虽然用来制备可控释放封壳的流化床方法用于涂复在操作温度下为固态的破坏剂最为有利，这种技术也可以用于涂复液态物质，特别是当需要涂复的液体在流化之前或在流化过程中可以冻结或者能被诸如多孔过火粘土之类的多孔颗粒吸附情况下更是如此。其它涂复技术，例如相分离，凝聚和声悬浮技术也可以用于制备可控释放封壳，但一般较差。涂复作业最好是在能防止单个颗粒的互相粘接和使未完全涂复的颗粒减少到最低程度的条件下进行。制备可控释放封壳后，封壳可进行进一步处理，例如热处理，以改变涂层的性能。
在可控释放封壳的制备过程中，可渗透的材料的涂复厚度要足以在作业温度下使破坏剂延迟释放使其达到所要求的时间。此外，在本发明的实施中有用的可控释放封壳宜具有足够的强度和延性，以防止封壳在加工过程中破裂，该加工过程包括通过作业中常用地面泵和混合设备并防止封壳在引入地层过程中破坏。一般，透水的封闭壳体的涂复厚度为0.5至100微米。更为有利的涂复厚度为5至60微米。
采用的加入可控释放封壳的方法及加入的量取决于多种因素，它们包括：具体的最终用途和所要求的封闭壳体的破坏时间。例如，用于压裂液的降粘时，含有降粘剂的可控释放封壳可以随压裂液一起进入地层（在某些情况下，也可以在加压裂液之前或之后加入）。一般最好是先加入压裂液而后加入含有降粘剂的可控释放封壳。
一般可控释放封壳是在地面上加入井筒在含水载液中分散，然后送到地层中所要求的位置。这里所用的术语“地层”包括地层和穿透地层的井筒。术语“含水载液”指的是水（包括碱性或酸性水溶液），盐水，和水与一种或一种以上能与水相混溶的液体[例如一种低级链烷醇，（如乙醇或丙醇）低级酮（如丙酮或甲乙酮）等等]的混合物。携带可控释放封壳的含水载液可以是一般含有0.001至2重量百分数（最好为0.01至1）可空释放封壳的压裂液（上述重量百分数均按所用的含水载体的重量计算）。
随压裂液一起加入可控释放封壳一般是有利的。压裂液及其组分在现有技术中是熟知的，本发明予以引述。基本上所有的压裂液都含有一种载液（通常是含水载液）和一种稠化聚合物。此外，压裂液一般也含有一种或一种以上添加剂，例如表面活性剂，盐如氯化钾，消泡剂，杀菌剂和聚合稠化剂的交联剂。
在本发明的实施中，当由于流体迁移进入封壳造成的内压与环境压力之差足够高时可以使封壳破坏释放出破坏剂。然而，在本发明的一般实践中，使破坏剂释放并不仅仅由于这一机理，这一释放机理并不是唯一的，甚至不是主要的使破坏剂释放到地层中的机理。例如，主要的释放机理可以是由于地层闭合引起的应力。由于内压升高造成封闭壳体的破坏（以及以后使破坏剂释放到地层中）仅对于那些未被应力破坏的封壳起作用。
本发明的方法还可以用来向地层放置两种或两种以上不同的封壳破坏剂材料，或者一种或一种以上封壳破坏剂与一第二种处理剂的混合物。例如，含有单一的破坏剂的可控释放封壳可以与含有不同或相同型的破坏剂（或，不同的处理剂）的可控释放封壳混合，然后送入井筒及地层。另一种方法是，将两种或两种以上破坏剂或至少一种破坏剂与至少一种处理剂混合成为单一的可控释放封壳。另一种方法是将可控释放封壳与其它对地层流体或随封壳一同注入的流体基本上是不可渗透的封壳一起使用，这种基本不渗透的封壳含有与可控释放封壳所含的相同或不同的处理剂。在这种方法中，不同的封壳可以作为混合物加入井筒和/或地层或先后加入。
在本发明的方法中，破坏剂的过早释放会由于封闭壳体的不完全涂复和在混合或向地层输送的步骤中封闭壳体发生无意的或不可防止的破坏等原因而发生。在很多情况下，过早释放破坏剂会对作业产生不利影响。因此，常常随可控释放封壳一起加入如硫代硫酸钠，或其它还原剂一类物质以抵销氧化剂的作用以消除这种意外释放的物质对作业的不利影响，这样做是有利的。
下面给出的实施例仅作为本发明的说明，不应认为是对本发明的范围的限制。所有百分数及份数（另有说明外）均指重量百分数和重量份。
实施例1
将直径约为1毫米的大约400克过硫酸铵晶体（破坏剂）在Uni-Glatt 流化床上用沃斯特柱（Wurster Column）进行流化。然后用约含15%固体的聚合物胶乳（封闭壳体）喷涂晶体。封闭壳体聚合物是一种由大约90摩尔百分数的1，1-二氯乙烯和大约10摩尔百分数的丙烯酸甲酯衍生的共聚物。涂复作业中采用的喷嘴调至水平位置，所用空气压力为3巴（300千帕）并有废气过滤放气系统时间为5秒间隔为45秒。进口温度为60℃，给料速度约为每分钟15亳升。喷涂时间约为10秒。封壳（涂复过的破坏剂晶体）的壁厚为20至50微米，涂层平均厚度为30微米。
在室温下，将10克封壳放入1000克水中。由于涂复的不规则和并非所有的破坏剂晶体都完全用封闭壳体封住，开始接触水之后的大约5小时内大约有20%（重量）的过硫酸盐破坏剂被释放出来。原来包封在封壳中的过硫酸盐只有不到10%是在后来的45小时内释放的，这就表明封闭壳体能有效地保住过硫酸盐破坏剂直到要求释放时为止。
当把10克封壳放入日100克温度保持在65℃的水中时，在头5小时内也释放约20%（重量）的过硫酸盐破坏剂。但以后一直到开始接触后的大约20小时内没有明显量的晶体释放。在此之后，封壳开始大暴裂，并在封壳开始接触水后的三十小时之内封壳中的90%（重量）左右的晶体得以释放进入水中，这就表明，释放可以延迟到所要求的时间，此后活性成分可以在短时间内基本上完全释放。
当把10克封壳放入81℃水中时，在5小时之内封壳所包裹的全部过硫酸盐晶体完全释放。
在封壳释放破坏剂晶体的过程中，通过用50倍显微镜观察，注意到由氧化剂与水的作用产生的气泡使涂膜从被封的材料上隆起。
通过变化涂膜厚度可使封壳的释放特性几乎无限制地变化。例如，当直径约为2毫米的次氯酸锂晶体用上述方法在一定的条件下使其涂膜厚度约为50微米时，室温下在水中它们的爆裂释放时间将为4.75小时（从开始与水接触之时算起）。
当直径约为1毫米的六水单过羟邻二甲酸镁晶体用同样的聚合物和相似的涂膜技术，在使其膜厚只有16.5微米的条件下进行涂复后，其爆裂释放时间仅约9分钟。这样较短的释放时间是由于晶体的涂层厚度大大减少了。与此相似，直径为1.5mm的用聚合物胶乳涂复后厚度为7.9微米的过硼酸钠晶体的平均释放时间约为35分钟。
实施例2
将约1800克过硫酸铵晶体过筛，取其通过20目筛网（美国标准，841微米）但不能通过40目筛（美国标准420微米）之间的颗粒，用沃斯特（Wurster）方法在UniGlatt流化床流化。用固体含量约为12.5%聚合物胶乳喷涂晶体。聚合物是一种由约92摩尔百分数1，1-二氯乙烯、约5摩尔百分数的丙烯酸甲酯与约3摩尔数的丙烯腈衍生的共聚物。聚合物溶液在大约为2巴（200kpa）的压力下粉化，并以每分钟10亳升的速率喷涂了共240秒。入口温度为43℃。这样制成的封壳的平均涂膜厚度约为30微米。
将如此制得的17克封壳放入温度为65℃的80克水中。在接触水后的头2小时内，封壳内的过硫酸盐晶体释放了不到2%。从开始与水接触之时算起的4小时后，封壳释放出13%（重量）的晶体，6小时后释放出40%（重量）的晶体，8小时后释放出47%（重量）的晶体。
实施例3
按照实施例2的程序，将1500克过硫酸铵晶体在UniGlatt流化床上用沃斯特方法（Wurster）进行喷膜，所用的聚合物胶乳含约12%的与实施例2相同的聚合物胶乳和0.3%防粘剂以使封壳能自由流动。
当将封壳放入65℃的水中后，封壳释放过硫酸铵的速率大约与实施例2所述的封壳相同。
将足够量的含有过硫酸铵的封壳，在搅拌下加入装在粘度计杯中的50亳升的1%羟基丙基瓜尔胶水溶液中，以生成封壳在溶液中的2%分散液（1号样品）。然后，使粘度计杯静置（即，不再搅拌分散液）约30分钟，然后测定其粘度。尔后，同氮气将粘度计杯加压到2700千帕并以170秒-1的速度剪切此溶液，以5.5℃/分的速率加温至65℃保持4小时，并在此4小时内每隔30分钟测定粘度一次。然后再使分散液静置44小时，其间每隔4小时测一次粘度。作为时间函数的原溶液粘度保持百分比由下表给出，（时间从含有过硫酸铵的封壳与溶液开始接触之时起算）：
开始接触后的时间    粘度保持率
（小时）    （%）
0.5    99
1.0    97.5
1.5    96
2.0    95
2.5    94
3.0    92
3.5    90
4.0    89
8.0    66.5
12.0    47
16.0    42
20.0    40
24.0    37
28.0    35
32.0    32.5
36.0    30
40.0    25.5
44.0    24
上表中数据清楚地表明，溶液的粘度在4小时内基本上得到了保持。在4至12小时之间粘度急剧下降。表明在开始接触溶液之后的4至8小时之间大多数封壳保持了过硫酸铵，从那一时刻开始过硫酸铵破坏剂就被放到溶液中而且溶液的粘度开始被破坏。12小时后，粘度保持相对稳定，粘度只降低很少。这又表明，在最初接触溶液之后的12至16小时之间封壳仅释放出少量过硫酸铵。这样，可对溶液的破坏进行有效的控制。
用基本相同的方法进行了重复试验，但过硫酸铵是直接加入稠化溶液中的。在65℃下，溶液的粘度在0.5小时内下降到原来粘度的20%以下。因此，当向稠化溶液直接加入破坏剂时，粘度的破坏过于急剧，这是不符合要求的。当不向稠化溶液加入破坏剂时，44小时之后溶液的粘度仍为其原来粘度的80%以上。这样长时间之后的高粘度也是不符合要求的。

Claims (24)

1、一种破坏水基压裂液的方法，该方法包括向地层注入包含封闭壳体的可控释放封壳，在该封闭壳体内包封了水基压裂液的破坏剂；封闭壳体至少对于存在于地层中的或随可控释放封壳一起注入的一种液体来说是可渗透的，因而此封闭壳体可保住大部分包封的破坏剂，直到在液体中暴露到达到预定的时间后才释放破坏剂。
2、权利要求1的方法，其中所述的可控释放封壳是作为一种在含水载液中的分散体注入地层的，此载液含有0.001～2%（重量）（按载液的重量计算）的可控释放封壳。
3、权利要求1的方法，其中所述的可控释放封壳与具有不能被地层流体或随封壳一同注入的流体渗透的壳体材料的封壳混合后注入或先后分开注入，并且这种不可渗透的封壳中包含与可控封壳所包含的相同或不同的破坏剂。
4、权利要求1的方法，其中所述的封闭壳体是用一种具有25微米厚度和在38℃时水蒸汽穿透率小于3g/100cm2/24小时但大于0.0015g/100cm2/24小时的膜状材料制成。
5、权利要求4的方法，其中所述的材料的水蒸汽穿透率在38℃时大约小于0.775g/100cm2/24小时，大约大于0.0077g/100cm2/24小时。
6、权利要求1的方法，其中所述的封闭壳体的材料系选自乙烯、丙烯、异丁烯、氯乙烯，1，1-二氯乙烯的均聚物或共聚物以及它们的混合物。
7、权利要求6的方法，其中所述的封闭壳体材料系选自聚乙烯、聚丙烯、聚异丁烯，氯乙烯与1，1-二氯乙烯的共聚物，1，1-二氯乙烯与一种不饱和羧酸酯的共聚物，乙烯与不饱和羧酸的共聚物，以及它们的混合物。
8、权利要求1的方法，其中所述的封闭壳体系选自环氧化物、聚碳酸酯、环氧乙烷或环氧丙烷的聚合物、乙基纤维素，以及它们的混合物。
9、权利要求1的方法，其中所述的破坏剂是一种能与穿透封闭壳体进入封壳的流体产生反应并生成气体的材料。
10、权利要求1的方法，其中所述的破坏剂系选自酶、氧化剂、离子化了的过渡金属盐、酸，以及它们的混合物。
11、权利要求10的方法，其中所述的氧化剂系选自铵、钠或钾的过硫化物;过氧化钠;亚氯酸钠;钠、锂、或钙的次氯酸盐;漂白粉;过磷酸钾;过硼酸钠;单过羟苯二甲酸镁六水合物;N，N′-二氯二甲基乙内酰脲，以及它们的混合物。
12、权利要求1的方法，其中所述的封闭壳体的壁厚为0.5至60微米。
13、权利要求1的方法，其中所述的可控释放封壳的平均颗粒大小为0.1至2毫米且封闭壳体是由涂膜制成其壁厚为5至40微米。
14、权利要求1的方法，其中所述的可控释放封壳包含多层封闭壳壁。
15、权利要求1的方法，其中所述的可控释放封壳包含每一个核都被可渗透的封闭壳体包裹的多核封壳，但是其中的多核是互相团聚或附着成一个单一的颗粒。
16、一种压裂地层的压裂液，该压裂液含有一种含水载液、一种稠化聚合物和可控释放封壳，每个封壳包括一封闭壳体，该壳体含有稠化聚合物的破坏剂，其中封闭壳体对于载液或至少一种地层液体来说是可渗透的，所述的封壳能在暴露于液体中之后和向载液释放破坏剂之前的予定时间中保持大部分破坏剂处于包封状态。
17、权利要求16的压裂液，该压裂液包含一种选自表面活性剂、盐、消泡剂、杀菌剂和聚合物增粘剂的交联剂的添加剂。
18、权利要求16的压裂液，其中所述的压裂液含有载液重量的0.001～2%的可控释放封壳。
19、权利要求16的压裂液，其中所述的封闭壳体是用厚度为25微米和在38℃时水蒸汽穿透率小于1g/300cm2/24小时但大于0.01g/645cm2/24小时的涂料制备。
20、权利要求16的压裂液，其中所述的破坏剂系选自酶、氧化剂、离子化的过渡金属盐及其混合物。
21、权利要求20的方法，其中所述的氧化剂系选自铵、钠或钾的过硫酸盐;过氧化钠;亚氯酸钠;钠、锂或钙的次氯酸盐;漂白粉;过磷酸钾;过硼酸钠;单过羟苯二甲酸镁六水合物;N，N′-二氯二甲基乙内酰脲，以及它们的混合物。
22、权利要求16的压裂液，其中所述的破坏剂的封闭壳体的涂复厚度为0.5至60微米。
23、权利要求22的压裂液，其中所述的可控释放封壳的平均颗粒大小为0.1～2毫米，封闭壳体是一种涂膜，其厚度为5至40微米。
24、权利要求16的压裂液，其中所述的可控释放封壳包括多层封闭壳壁。
CN88100379.4A 1987-01-16 1988-01-16 处理地层用的水基压裂液及其破胶方法 Expired CN1018011B (zh)

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