CN105358650A - 在地下井中保持层位隔离的方法 - Google Patents

在地下井中保持层位隔离的方法 Download PDF

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CN105358650A
CN105358650A CN201480038071.9A CN201480038071A CN105358650A CN 105358650 A CN105358650 A CN 105358650A CN 201480038071 A CN201480038071 A CN 201480038071A CN 105358650 A CN105358650 A CN 105358650A
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cement
hydrogen sulfide
well
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rubber
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H·比尔泰-卢瓦耶
L·勒尼奥德拉莫特
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Abstract

本发明提供一种用于其中存在硫化氢的井中的水泥，其包含聚合物颗粒。在水泥-基体失效、或者水泥/套管界面之间或水泥/井壁界面之间结合失效的情况下，所述聚合物颗粒在与硫化氢接触时发生膨胀。所述膨胀密封水泥基体中的空隙，或所述膨胀沿着结合界面，从而恢复层位隔离。

Description

在地下井中保持层位隔离的方法
技术领域
本发明涉及用于处理地下岩层的组合物和方法，特别是用于对其中存在硫化氢的井进行固井和完井的组合物和方法。
背景技术
本部分的内容仅提供与本发明相关的背景技术信息，并且可能不构成现有技术。
在构造地下井过程中，在钻井期间和之后，将管状体放入井眼中是常见的。管状体可以包含钻杆、套管、衬管、挠性管或它们的组合。管状体的目的是充当管道，通过所述管道可以输送并收集来自井的期望流体。管状体通常由水泥环固定在井中。水泥环提供机械支撑和被井穿透的区域或层之间的液压隔离。后一作用是重要的，因为这防止了可能导致污染的在区域之间的液压连通。例如，水泥环阻挡来自油或气区域的流体进入地下水面并污染饮用水。此外，为了优化井的生产效率，可以期望例如将产油区与产气区隔离。
水泥环由于具有低渗透性而实现了液压隔离。此外，水泥环与管状体和井眼二者之间的紧密结合对于防止泄漏是必要的。然而，随着时间的推移，水泥环会劣化，变成可渗透的。或者，水泥环与管状体或井眼之间的结合可能会受到影响。劣化和分离(debonding)的主要原因包括与构造运动相关的物理性应力、温度变化、套管内压力变化以及水泥的化学劣化。
一些油田和气田具有其流体含有酸性气体(如二氧化碳和硫化氢)的地层。从层位隔离(zonalisolation)的角度来看，这样的井可能是具有挑战性的。
含有较高量硫化氢的油和气被称为“酸的(sour)”。据估计在美国15％至25％的天然气可能含有硫化氢。在世界范围内，所述百分比可高达30％。硫化氢是一种有毒物质；因此，防止它通过水泥环逸入含水层或到达地面是重要的。另外，硫化氢对钢具有腐蚀性，保持能胜任的(competent)水泥环对于防止在井的寿命期间内套管劣化是必要的。
发明内容
本发明通过描述以下组合物和方法而实现了改进，其中所述组合物甚至在硫化氢环境中也可以形成持久的水泥环，通过所述方法可以制备所述组合物并将其施用在地下井中。
在一个方面中，实施方案涉及用于在具有其中存在硫化氢的井眼的地下井中保持层位隔离的方法。将包含与硫化氢接触时膨胀的材料的水泥浆泵送入井眼。使所述水泥浆凝固和硬化。在水泥-基体或结合失效的情况下，将凝固的水泥暴露于含硫化氢的井眼流体。使所述材料膨胀，从而恢复层位隔离。
在另一个方面中，实施方案涉及对具有其中存在硫化氢的井眼的地下井进行固井的方法。将包含与硫化氢接触时膨胀的材料的水泥浆泵送入井眼。使所述水泥浆凝固和硬化。在水泥-基体或结合失效的情况下，将凝固的水泥暴露于含硫化氢的井眼流体。使所述材料膨胀，从而恢复层位隔离。
在还有一个方面中，实施方案涉及对具有其中存在硫化氢的井眼的地下井进行完井的方法。将包含与硫化氢接触时膨胀的材料的水泥浆泵送入井眼。使所述水泥浆凝固和硬化。在水泥-基体或结合失效的情况下，将凝固的水泥暴露于含硫化氢的井眼流体。使所述材料膨胀，从而恢复层位隔离。
在另外一个方面中，实施方案涉及对具有井眼的地下井进行固井或完井的方法。通过测试、分析或其它方式确定井眼包含硫化氢或将来可能包含硫化氢。将包含与硫化氢接触时膨胀的材料的水泥浆泵送入井眼。使所述水泥浆凝固和硬化。在水泥-基体或结合失效的情况下，将凝固的水泥暴露于含硫化氢的井眼流体。使所述材料膨胀，从而恢复层位隔离。
附图说明
图1示出了聚丙烯颗粒和天然橡胶/苯乙烯-丁二烯颗粒在氮气、纯H2S和含H2S的储层流体的存在下的膨胀行为。
图2是用来执行如实施例2中所述的测试的测试室的剖面图。
图3是放置在测试室中的岩心夹持器的剖面图。
图4是具有凝固水泥的样品的测试室的剖面图，其中通过张力破裂，在样品中制造了平行于岩心轴的裂纹。
图5示出了包含聚丙烯颗粒的有裂纹的水泥岩心减少含H2S的侵入气态储层流体的流量的能力。
具体实施方式
开始时，应该注意的是在任何此类实际实施方案的开发中，必须做出大量执行方式(implementation)-特定性决定以实现开发者的特定目标，例如遵守与系统相关的和与商业相关的约束，这会使一个执行方式与另一个执行方式不同。此外，应该理解的是此类开发努力可能是复杂的且耗时的，但是对于受益于本发明的本领域技术人员而言，这仍然是常规任务。此外，本发明中所使用的/所公开的组合物除了包含所提及的那些以外还可以包含一些其它成分。在发明内容部分和本具体实施方式部分中，除非在上下文中另有说明，否则每个数值都应该如同被术语“约”所修饰那样读取一次(除非已经明确地表达如此修饰)，接着如同未被如此修饰那样再读取一次。此外，在发明内容部分和本具体实施方式部分中，应该理解的是作为可用的或合适的等所列出或描述的浓度范围意欲表示，在所述范围内的任何一个和每一个浓度(包括端点)都被认为是已经被陈述过的。例如，“从1至10的范围”被读作表示沿着约1至约10的连续统(continnum)的每一个可能的数。因此，即使明确确认在所述范围内的具体数据点或者甚至在所述范围内没有明确确认具体数据点，或者提及仅几个具体的点，但是应该理解的是本申请的申请人了解并理解在所述范围内的任何和所有数据点都被认为是已经被具体指定，并且申请人具备整个范围和所述范围内所有点的知识。
在包含硫化氢的环境中形成耐久水泥环的水泥体系将被工业积极接受。申请人已经确定，包含在硫化氢的存在下膨胀的材料的水泥组合物将会应对工业挑战。当结合入水泥组合物中时，所述硫化氢膨胀化合物可以使水泥环闭合可能出现的其自身的空隙和/或裂纹。
申请人已经确定，某些聚合物可以满足对所需的在硫化氢的存在下可膨胀的能力的要求。这类聚合物可包括：天然橡胶，丁腈橡胶，苯乙烯-丁二烯橡胶，包含乙烯和/或丙烯的聚合物或共聚物，丁基(异丁烯-异戊二烯)橡胶，氢化丁腈橡胶，丙烯腈-丁二烯共聚物，或它们的组合。在一些实施方案中，这样的聚合物包括聚丙烯，天然橡胶和苯乙烯-丁二烯橡胶的共混物，或它们的组合。在一些实施方案中，这样的聚合物是聚丙烯。在一些实施方案中，这样的聚合物是天然橡胶和苯乙烯-丁二烯橡胶的共混物。
在一个方面中，实施方案涉及用于在具有其中存在硫化氢的井眼的地下井中保持层位隔离的方法。将包含与硫化氢接触时膨胀的材料的水泥浆泵送入井眼。使所述水泥浆凝固和硬化。在水泥-基体或结合失效的情况下，将凝固的水泥暴露于含硫化氢的井眼流体。使所述材料膨胀，从而恢复层位隔离。
在另一个方面中，实施方案涉及对具有其中存在硫化氢的井眼的地下井进行固井的方法。将包含与硫化氢接触时膨胀的材料的水泥浆泵送入井眼。使所述水泥浆凝固和硬化。在水泥-基体或结合失效的情况下，将凝固的水泥暴露于含硫化氢的井眼流体。使所述材料膨胀，从而恢复层位隔离。
在还有一个方面中，实施方案涉及对具有其中存在硫化氢的井眼的地下井进行完井的方法。将包含与硫化氢接触时膨胀的材料的水泥浆泵送入井眼。使所述水泥浆凝固和硬化。在水泥-基体或结合失效的情况下，将凝固的水泥暴露于含硫化氢的井眼流体。使所述材料膨胀，从而恢复层位隔离。
在另外一个方面中，实施方案涉及对具有井眼的地下井进行固井或完井的方法。通过测试、分析或其它方式确定井眼包含硫化氢或将来可能包含硫化氢。将包含与硫化氢接触时膨胀的材料的水泥浆泵送入井眼。使所述水泥浆凝固和硬化。在水泥-基体或结合失效的情况下，将凝固的水泥暴露于含硫化氢的井眼流体。使所述材料膨胀，从而恢复层位隔离。
对于所有方面，井眼穿透至少一个含有流体的储层，所述储层包含硫化氢浓度高于每升流体约五摩尔的流体。硫化氢可以是超临界的、湿的、干的或者溶解在油或水中的。硫化氢也可以由沥青烃类或重质烃类在热采井中蒸汽的存在下的解离(水热裂解)释放。所述重质原油可含有有机硫化物(R-S-R')、多硫化物(R-Sx-R')、噻吩(thiofene)和硫醇(R-S-H)。因此，本发明可应用于其中采用蒸汽辅助重力泄油(SAGD,steamassistedgravitydrainage)或周期注蒸汽增产法(CSS,cyclicsteamstimulation)的井。对于CSS应用，可膨胀材料可以是熔点比注蒸汽温度高的热固性或热塑性材料。
对于所有方面，材料可以包括：天然橡胶，丁腈橡胶，苯乙烯-丁二烯橡胶，包含乙烯、丙烯或二者都有的聚合物或共聚物，丁基(异丁烯-异戊二烯)橡胶，氢化丁腈橡胶，丙烯腈-丁二烯共聚物，或它们的组合。这样的聚合物可包括：聚丙烯，丁腈橡胶和苯乙烯-丁二烯橡胶的共混物，或它们的组合。在一些实施方案中，这样的聚合物是聚丙烯。在一些实施方案中，这样的聚合物是天然橡胶和苯乙烯-丁二烯橡胶的共混物。材料的浓度可为约5％至50％，按水泥浆中固体的体积计，这也可以被称为“按共混物的体积计(BVOB,byvolumeofblend)”。或者，所述范围可以是约10％至40％BVOB。为了获得最佳性能，材料的粒径分布可以是平均粒径为约10μm至约1000μm。平均粒径也可以是约100μm至900μm。
本领域技术人员可以认识到，本发明的聚合物的用途与它们作为水泥增量剂(即减少水泥的量或减小水泥浆密度)或作为改进水泥柔韧性的材料的用途是不同的。
聚合物的杨氏模量可以为约1至4000MPa，或者所述聚合物的杨氏模量可以为约1至2000MPa。聚合物的泊松比可以大于0.4，或者聚合物的泊松比可以大于0.45。
对于所有方面，水泥可以另外包含一种或多种选自以下的成分：波特兰水泥、铝酸钙水泥、飞灰、高炉矿渣、石灰-二氧化硅共混物、沸石、地质聚合物、索瑞尔水泥(Sorelcement)、化学结合磷酸盐陶瓷、聚合物树脂及它们的混合物。聚合物树脂可包括环氧树脂、呋喃树脂、酚醛树脂及它们的组合。所述组合物应是可泵送的。本领域技术人员会认识到，在固井的情况下，可泵送流体在固井操作期间以及在将所述组合物放置于井中所必要的时间期间流体所暴露的温度下在100s-1的剪切速率下具有低于约1000mPa-s的粘度。而且，管状体可包括一种或多种选自以下的构件：钻杆、套管、衬管和挠性管。此外，井眼可穿透至少一个含有流体的储层，所述储层优选包含硫化氢浓度高于每升约五摩尔的流体。
水泥浆可以进一步包含分散剂、防滤失剂、缓凝剂、促凝剂、发泡剂、气体发生剂、消泡剂、增量剂、加重剂、循环液漏失控制剂、柔性颗粒、自复原添加剂及它们的组合。也可以存在其它化合物，例如煤、石油焦、石墨或天然沥青及它们的混合物。另外，可以将硫化氢可膨胀聚合物连接(couple)至超吸水聚合物，例如聚甲基丙烯酸酯、聚丙烯酰胺和非溶性丙烯酸聚合物。还可以用选自以下颗粒的含水反相乳液中的一种或多种化合物进一步结合(association)：包含甜菜碱基的聚合物、聚2,2,1-二环庚烯(聚降冰片烯)、烷基苯乙烯、交联的取代的乙烯基丙烯酸酯共聚物、硅藻土、硫化橡胶、聚异戊二烯橡胶、乙酸乙烯酯橡胶、氯丁橡胶、丙烯腈丁二烯橡胶、氢化丙烯腈-丁二烯橡胶、乙烯丙烯二烯单体、乙烯丙烯单体橡胶、苯乙烯-丁二烯橡胶、苯乙烯/丙烯/二烯单体、溴化聚(异丁烯-共聚-4-甲基苯乙烯)、丁基橡胶、氯磺化聚乙烯、聚丙烯酸酯橡胶、聚氨酯、硅酮橡胶、溴化丁基橡胶、氯化丁基橡胶、氯化聚乙烯、表氯醇-环氧乙烷共聚物、乙烯丙烯酸酯橡胶、乙烯丙烯二烯三元共聚物橡胶、磺化聚乙烯、氟硅橡胶、含氟弹性体、取代的苯乙烯丙烯酸酯共聚物和二价阳离子化合物，或任何其它颗粒(例如，WO2004/101951中所述的那些，这些颗粒在暴露于液态烃时膨胀，所述国际申请的全部内容通过援引加入的方式纳入本文)。可以与热塑性嵌段聚合物进一步结合，所述聚合物包括例如苯乙烯-异戊二烯-苯乙烯(SIS)、苯乙烯-丁二烯-苯乙烯(SBS)及它们的混合物。
水泥浆可进一步包含在另一种酸性气体的存在下膨胀的材料。所述材料可以是弹性体，包括：含氯氟烃、四氟乙烯-丙烯共聚物、乙烯-丙烯共聚物、异丁烯-异戊二烯橡胶、丁腈橡胶、氢化丁腈橡胶或四氟乙烯-全氟乙烯基甲基醚共聚物，及它们的组合。
本领域技术人员会认识到，这些方法可在初次固井(primarycementing)操作或补固井(remedialcementing)操作过程中实施。初次注水泥操作包括在井的井眼内部或在管状体内部安装管状体。水泥浆的泵送可以传统的方式执行(即泵送水泥浆沿套管向下和沿环形空间向上)，或通过“反向固井(reversecementing)”执行，所述“反向固井”包括泵送水泥浆沿环形空间向下。可应用所公开的水泥浆的补固井技术包括塞固井(plugcementing)和挤固井(squeezecementing)。
实施例
以下实施例用来进一步示例说明本发明。在所公开的实验中，将聚合物颗粒暴露于各种类型的流体。所述流体是氮气、纯H2S和三种储层流体(流体1、2和3)。储层流体组成列于表1中。
表1.颗粒膨胀测试中使用的储层流体的组成
实施例1
将聚合物颗粒放置在压力室内，所述压力室具有一个窗口用以观察材料在所述室内的行为。所述室的供应商是TemcoInc.，位于Houston,TexasUSA。所述室的温度也是可调节。照相机捕捉压力室内的图像，并使用图像分析软件来解释说明所述室内材料的行为。在将聚合物颗粒引入所述室内后，将所述室密封。将各种类型的流体引入到所述室中，并用照相机记录所述颗粒在暴露于60℃(140°F)和34.5MPa(5000psi)下360分钟时的尺寸变化。
对两种类型的颗粒进行测试：聚丙烯(颗粒A)和天然橡胶与苯乙烯-丁二烯橡胶的共混物(颗粒B)。将所述颗粒暴露于四种不同的测试流体：氮气、纯H2S和两种含有H2S的储层流体(流体1和2)。它们的组成列于表1中。在测试条件下，流体1为液体，流体2为气态。
结果示于图1中，其表明这两种颗粒在H2S的存在下均显著膨胀，而在氮气的存在下膨胀最小。
实施例2
以下实施例表明了嵌在水泥基体中的H2S可膨胀颗粒阻止H2S流动通过裂纹或微环隙的能力。
实验是在样品测试室中进行的。如图2中所示，测试室10由不锈钢制成，并且大体上是圆柱形的。圆柱的外直径11是38.1mm，其内直径12是21.2mm，其长度13是180mm。将测试水泥试样制成适合于在所述测试室内。所述测试室位于岩心夹持器20内，如图3中所示。岩心夹持器是基于Hassler套筒的岩心驱替系统，使用直径38.1mm的样品。这种套筒是本领域中公知的。用两个容积泵以32mL/min的总容量将测试流体输送至所述室。用回压调节器在水泥样品的出口面保持恒定的压力。
第一水泥组成是G级水泥+10％BVOB颗粒A+45％BVOB二氧化硅+10％BVOB微粒硅+1％的按共混物的重量计的(BWOB,byweightofblend)氧化镁+2L/吨聚乙二醇消泡剂+1.3％BWOB聚萘磺酸盐分散剂+0.65％BWOC木质素磺酸盐缓凝剂+85L/吨乳胶降滤失剂。加入足够的水以达到1950kg/m3的浆密度。
如图4中所示，制备圆柱体凝固水泥样品40并使其损坏，使得裂纹43沿其纵向轴线延伸。在测试室10中，容纳有在厚金属圆筒41中的水泥样品。由周围套筒42将岩心保持在适当的位置。
将如表1中所述的流体2以8mL/min泵入测试室。所述室的条件是60℃，34.5MPa。结果如图5中所示，表明水泥样品在暴露于流动流体2的约50分钟内自修复。通过所述室的标准化(normalized)流速下降了97％。用如表1中所述的流体3重复所述实验。在所述室条件下，流体3是气态的。请注意，流体3不含有H2S。这一次，通过所述室的标准化流速增加了10％。
第二水泥组成是G级水泥+10％BVOB颗粒B+35％BVOB二氧化硅+10％BVOB微粒硅+1％的按共混物的重量计的(BWOB)氧化镁+6L/吨聚乙二醇消泡剂+0.5％BWOB聚萘磺酸盐分散剂+0.57％BWOC木质素磺酸盐缓凝剂+85L/吨乳胶降滤失剂。加入足够的水以达到1950kg/m3的浆密度。
将流体2以16mL/min泵送通过如上所述的样品。通过所述室的标准化流速下降了82％。用流体3重复所述实验。这一次，通过所述室的标准化流速下降了5％。
结果表明，为提供足够的流量减小，在储层流体中存在H2S对于聚合物颗粒是必要的。
虽然已结合可实施的公开内容描述了各实施方案，但应当理解的是，前述信息不限于所公开的实施方案。在阅读说明书后本领域技术人员可以想到的变型和修改也在本发明的范围内，而本发明的范围由所附的权利要求限定。

Claims (15)

1.在具有其中存在硫化氢的井眼的地下井中保持层位隔离的方法，包括：
(i)泵送水泥浆进入所述井眼，所述水泥浆包含与硫化氢接触时膨胀的材料；
(ii)使所述水泥浆凝固和硬化；
(iii)在水泥-基体或结合失效的情况下，将凝固的水泥暴露于含硫化氢的井眼流体；和
(iv)使所述材料膨胀，从而恢复层位隔离。
2.权利要求1的方法，其中所述材料包括：天然橡胶，丁腈橡胶，苯乙烯-丁二烯橡胶，包含乙烯、丙烯或二者都有的聚合物或共聚物，丁基(异丁烯-异戊二烯)橡胶，氢化丁腈橡胶，丙烯腈-丁二烯共聚物，或它们的组合。
3.权利要求1或2的方法，其中所述材料在所述水泥浆中的浓度是约5％至约50％，按固体共混物的体积计。
4.权利要求1-3中任一项的方法，其中所述材料的平均粒径是约10μm至约1000μm。
5.权利要求1-4中任一项的方法，其中所述硫化氢是超临界的、湿的、干的或者溶解在油或水中的。
6.权利要求1-5中任一项的方法，其中所述井眼穿透至少一个含有流体的储层，所述储层包含硫化氢浓度高于每升约五摩尔的流体。
7.权利要求1-6中任一项的方法，其中所述水泥浆包含一种或多种选自以下的成分：波特兰水泥、铝酸钙水泥、飞灰、高炉矿渣、石灰-二氧化硅共混物、沸石、地质聚合物、索瑞尔水泥、化学结合磷酸盐陶瓷和聚合物树脂。
8.权利要求1-7中任一项的方法，其中管状体包括一种或多种选自以下的构件：钻杆、套管、衬管和挠性管。
9.对具有其中存在硫化氢的井眼的地下井进行固井的方法，包括：
(i)泵送含水的水泥浆进入所述井眼，所述水泥浆包含与硫化氢接触时膨胀的材料；
(ii)使所述水泥浆凝固和硬化；
(iii)在水泥-基体或结合失效的情况下，将凝固的水泥暴露于含硫化氢的井眼流体；和
(iv)使所述材料膨胀，从而恢复层位隔离。
10.权利要求9的方法，其中所述材料包括：天然橡胶，丁腈橡胶，苯乙烯-丁二烯橡胶，包含乙烯、丙烯或二者都有的聚合物或共聚物，丁基(异丁烯-异戊二烯)橡胶，氢化丁腈橡胶，丙烯腈-丁二烯共聚物，或它们的组合。
11.权利要求9或10的方法，其中所述材料在所述水泥浆中的浓度是约5％至约50％，按固体共混物的体积计。
12.权利要求9-11中任一项的方法，其中所述材料的平均粒径是约10μm至约1000μm。
13.权利要求9-12中任一项的方法，其中所述硫化氢是超临界的、湿的、干的或者溶解在油或水中的。
14.权利要求9-13中任一项的方法，其中所述井眼穿透至少一个含有流体的储层，所述储层包含硫化氢浓度高于每升约五摩尔的流体。
15.权利要求9-14中任一项的方法，其中所述水泥包含一种或多种选自以下的成分：波特兰水泥、铝酸钙水泥、飞灰、高炉矿渣、石灰-二氧化硅共混物、沸石、地质聚合物、索瑞尔水泥、化学结合磷酸盐陶瓷和聚合物树脂。
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