CN107207956A - 水力压裂组合物、其制造和使用方法 - Google Patents
水力压裂组合物、其制造和使用方法 Download PDFInfo
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- CN107207956A CN107207956A CN201580066463.0A CN201580066463A CN107207956A CN 107207956 A CN107207956 A CN 107207956A CN 201580066463 A CN201580066463 A CN 201580066463A CN 107207956 A CN107207956 A CN 107207956A
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- acid
- fracturing composition
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- polymer
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Abstract
本发明提供了一种水力压裂组合物,所述水力压裂组合物包含:呈膨胀状态的超吸附性聚合物;安置在所述超吸附性聚合物中的多个支撑剂颗粒;井处理剂;和用于使所述超吸附性聚合物膨胀至所述膨胀状态的流体。本发明提供了一种用井处理剂对井进行处理的方法,所述方法包括将包含所述井处理剂的水力压裂组合物安置在井中。所述井处理剂可以是阻垢剂、示踪剂、pH值缓冲剂或其组合。
Description
对相关申请的交叉引用
本申请要求2014年12月15日提交的美国申请号14/570003的权益,所述美国申请以全文引用的方式并入本文中。
技术领域
水力压裂能提高来自地下地层的例如油和气等理想流体的流量,并且涉及以足以在地下地层或区域中施加应力且伴随在地下地层或区域中产生裂缝的速率和压力将压裂流体放置到地下地层或区域中。一些压裂流体含有增粘剂或胶凝剂,例如在放置在地层中之前或之后不久便会破裂的多糖。
除了产生裂缝以外,所述压裂流体还将支撑剂输送到裂缝中。所述支撑剂应该在水压释放后使所述裂缝保持张开。此外,所述支撑剂建立了传导性通道,在这些通道中理想流体流动至钻孔。由于所述支撑剂能提供比周围岩石要高的传导性,因此所述裂缝在烃类产生中具有更大的潜力。然而,一些压裂流体在裂缝闭合之前便破裂,而且所述支撑剂与所述压裂流体分离并沉降在裂缝的底部。在这种情况下,所述支撑剂沉降并集中在裂缝底部,并且因此损害裂缝的几何结构和井生产力。
因此,非常需要能提供相对较高的渗透性并且能提高来自断裂地层的烃类产量的组合物和方法。
概述
在一个实施方案中,利用一种水力压裂组合物克服了上述和其他缺陷,所述水力压裂组合物包含:超吸附性聚合物,所述超吸附性聚合物呈膨胀状态并且被构造为响应于破裂条件而破裂;多个支撑剂颗粒,所述多个支撑剂颗粒被安置在所述超吸附性聚合物中,随后响应于使所述超吸附性聚合物破裂而从所述超吸附性聚合物释放所述多个支撑剂颗粒;井处理剂,所述井处理剂包括阻垢剂、示踪剂、缓冲剂或其组合;和流体,所述流体用于使所述超吸附性聚合物膨胀至所述膨胀状态。
在一个实施方案中,提供了一种在裂缝中安置多个支撑剂颗粒的方法,所述方法包括:在井下环境中安置水力压裂组合物,所述水力压裂组合物包含:超吸附性聚合物,所述超吸附性聚合物呈膨胀状态并且被构造为响应于破裂条件而破裂,以便由使所述超吸附性聚合物破裂而形成分解聚合物;多个支撑剂颗粒,所述多个支撑剂颗粒被安置在所述超吸附性聚合物中,随后响应于使所述超吸附性聚合物破裂而从所述超吸附性聚合物释放所述多个支撑剂颗粒;井处理剂,所述井处理剂包括阻垢剂、示踪剂、缓冲剂或其组合;和流体,所述流体用于使所述超吸附性聚合物膨胀至所述膨胀状态;在井下环境中形成裂缝;将所述水力压裂组合物安置在所述裂缝中;在形成所述裂缝之后,使所述超吸附性聚合物破裂;以及从所述超吸附性聚合物释放所述多个支撑剂颗粒,以将所述多个支撑剂颗粒安置在所述裂缝中。
附图简述
以下描述无论如何都不应该被视为具限制性。参考附图,相同元件带相同编号:
图1示出了根据一个实施方案的安置在呈膨胀状态的超吸附性聚合物中的支撑剂颗粒;
图2示出了根据一个实施方案的安置在呈膨胀状态的超吸附性聚合物中的支撑剂颗粒;
图3示出了呈未膨胀状态的超吸附性聚合物;
图4示出了分解聚合物和支撑剂颗粒;
图5示出了在破裂条件之前的安置在裂缝中的水力压裂组合物;
图6示出了图5的水力压裂组合物对破裂条件的反应;
图7示出了在裂缝闭合之前的安置在裂缝中的流体和支撑剂颗粒;
图8示出了在裂缝闭合之前沉降的支撑剂颗粒对裂缝尺寸的影响;
图9示出了安置在瓜尔胶或超吸附性聚合物中的支撑剂颗粒在180℉下随时间变化的函数;
图10示出了在180℉下向瓜尔胶或超吸附性聚合物中加入破裂剂;
图11示出了在注入水力压裂组合物期间的裂缝单元;
图12示出了在向安置在裂缝单元中的水力压裂组合物中注入水之后的裂缝单元;
图13示出了单独SPP流体和与线性凝胶体系组合的SPP流体的粘度差异;
图14A和图14B,统称为图14,示出了SPP和线性凝胶对泡沫压裂流体的泡沫品质的影响;
图15示出了交替注入包含SPP、支撑剂颗粒、用于使SPP膨胀的流体的含支撑剂流体与包含水和润滑剂的无支撑剂流体之后的裂缝单元;以及
图16示出了交替注入包含SPP流体的无支撑剂流体与包含水、润滑剂和支撑剂颗粒的含支撑剂流体之后的裂缝单元。
图17示出了流体pH值对超吸附性聚合物的粘度的影响。
详细描述
本文中以举例而不是限制的方式呈现了一个或多个实施方案的详细描述。
已经发现,本文中所描述的水力压裂组合物能在地层中产生裂缝,并且在不改变裂缝的几何结构的情况下将支撑剂颗粒输送到裂缝中,从而优化通过裂缝的烃传输和回收。支撑剂颗粒保持悬浮在水力压裂组合物中而不沉降到裂缝底部,由此提高了井的产量。
如图1中所示,水力压裂组合物10包括超吸附性聚合物12(例如,多个超吸附性聚合物颗粒12)、安置在超吸附性聚合物12中的多个支撑剂颗粒18和使超吸附性聚合物12膨胀至膨胀状态的流体(未示出)。在膨胀状态下,超吸附性聚合物12被构造为响应于破裂条件而破裂,并且由使超吸附性聚合物12破裂而形成分解聚合物。在超吸附性聚合物12破裂后,多个支撑剂颗粒18从超吸附性聚合物12释放。
超吸附性聚合物12包括多个聚合物链13,在超吸附性聚合物12的聚合物链13之间具有内部交联14。在一个实施方案中,所述支撑剂颗粒18被包括在相邻超吸附性聚合物颗粒12之间的空间22中。在一些实施方案中,支撑剂颗粒18被安置在空间22中,并且受到超吸附性聚合物颗粒12的颗粒内交联26限制。设想流体围绕超吸附性聚合物12的外部24、其内部空间22、在颗粒12内部或其组合。
超吸附性聚合物12是交联、中和或部分中和的聚合物,其能够吸收大量水性液体,诸如水、盐水、酸或碱,从而膨胀并且形成凝胶或粘性材料,并且在一定压力或温度下保留所吸收的流体。超吸附性聚合物具有内部交联、表面交联或其组合。超吸附性聚合物颗粒是超吸附性聚合物或超吸附性聚合物组合物的颗粒。首字母缩略词SAP可以用于代替超吸附性聚合物、超吸附性聚合物组合物和本文中的颗粒或纤维(等)。
SAP具有亲水性网状结构,所述亲水性网状结构可保留相对于SAP重量来说大量的水性液体。在一个实施方案中,本文中的SAP是当与水性流体接触时与水反应或吸收水并且膨胀的多种有机聚合物。此类SAP的非限制性实例是多糖材料(例如,在干燥状态下吸收并保留重量等于或大于其自身重量的水)、聚丙烯酸2-羟基乙酯、聚丙烯酸烷基酯、聚丙烯酰胺、聚甲基丙烯酰胺、聚乙烯吡咯烷酮和聚乙酸乙烯酯。在一个实施方案中,SAP是丙烯酰胺与例如马来酸酐、乙酸乙烯酯、环氧乙烷、乙二醇、丙烯腈或其组合的共聚物。SAP是例如由丙烯酰胺(AM)或丙烯酸和其盐产生。
在一个实施方案中,所述SAP是由非离子、阴离子、阳离子单体或其组合聚合而来。形成SAP的聚合反应可以通过自由基聚合、溶液聚合、凝胶聚合、乳液聚合、分散液聚合或悬浮液聚合来进行。此外,聚合反应可以在水相中、反相乳液中或反相悬浮液中进行。
用于制造SAP的非离子单体的实例包括非离子单体,诸如丙烯酰胺、甲基丙烯酰胺、N,N-二(C1-C8烷基)丙烯酰胺(诸如N,N-二甲基丙烯酰胺)、乙烯醇、乙酸乙烯酯、烯丙醇、甲基丙烯酸羟基乙酯、丙烯腈和其衍生物。此类衍生物包括例如丙烯酰胺衍生物,具体来说被烷基取代的丙烯酰胺或者丙烯酰胺或甲基丙烯酰胺的被氨基烷基取代的衍生物,并且更具体来说丙烯酰胺、甲基丙烯酰胺、N-甲基丙烯酰胺、N-甲基甲基丙烯酰胺、N,N-二甲基丙烯酰胺、N-乙基丙烯酰胺、N,N-二乙基丙烯酰胺、N-环己基丙烯酰胺、N-苯甲基丙烯酰胺、N,N-二甲基氨基丙基丙烯酰胺、N,N-二甲基氨基乙基丙烯酰胺、N-叔丁基丙烯酰胺、N-乙烯基甲酰胺、N-乙烯基乙酰胺、丙烯腈、甲基丙烯腈或其组合。
用于制造SAP的阴离子单体的实例包括含有酸性基团,包括羧酸基团、磺酸基团、膦酸基团、其盐、其衍生物或其组合的烯属不饱和阴离子单体。在一个实施方案中,所述阴离子单体是丙烯酸、甲基丙烯酸、乙基丙烯酸、马来酸、马来酸酐、富马酸、衣康酸、α-氯丙烯酸、β-氰基丙烯酸、β-甲基丙烯酸(巴豆酸)、α-苯基丙烯酸、β-丙烯酰氧基丙酸、山梨酸、α-氯山梨酸、2'-甲基异巴豆酸、肉桂酸、对氯肉桂酸、β-硬脂酸、柠康酸、中康酸、戊烯二酸、乌头酸、2-丙烯酰胺基-2-甲基丙烷磺酸、烯丙基磺酸、乙烯基磺酸、烯丙基膦酸、乙烯基膦酸或其组合。
用于制造SAP的阳离子单体的实例包括丙烯酸N,N-二-C1-C8烷基氨基-C1-C8烷基酯(例如,丙烯酸N,N-二甲基氨基乙酯)、甲基丙烯酸N,N-二-C1-C8烷基氨基-C1-C8烷基酯(例如,甲基丙烯酸N,N-二甲基氨基乙酯),包括季化形式(例如甲基氯季化形式)、二烯丙基二甲基氯化铵、N,N-二-C1-C8烷基氨基-C1-C8烷基丙烯酰胺和其季化形式,诸如丙烯酰胺基丙基三甲基氯化铵。
在一个实施方案中,SAP是含有阳离子取代基和阴离子取代基二者的两性SAP。阳离子取代基和阴离子取代基以不同的化学计量比例存在,包括1:1,或一个取代基与另一个取代基相比以更大的化学计算量存在。代表性两性SAP包括非离子单体、阴离子单体和阳离子单体的三元共聚物。
在一个实施方案中,所述SAP包括瓜尔胶和角叉菜胶。合适的材料包括日本专利申请号P2003-154262A中公开的那些,所述日本专利申请的内容以全文引用的方式并入本文中。
根据一个实施方案,SAP中使用的瓜尔胶包括天然瓜尔胶以及酶处理过的瓜尔胶;后者是通过用半乳糖苷酶、甘露糖苷酶或另一种酶处理天然瓜尔胶而获得。瓜尔胶还可以是通过用化学物质处理天然瓜耳胶以引入羧基、羟基烷基、硫酸酯基、磷酸酯基等而制备的半乳甘露聚糖衍生物。另外,在一个实施方案中,包括除瓜耳和角叉菜胶以外的天然多糖。示例性天然多糖包括淀粉、纤维素、黄原胶、琼脂、果胶、海藻酸、黄蓍胶、普兰兰、结冷胶、罗望子籽胶、卡兰、阿拉伯树胶、葡甘露聚糖、甲壳素、壳聚糖、透明质酸等。
角叉菜胶是离子线性多糖,其包括可以单独硫酸化或未硫酸化的重复半乳糖单元。具体的角叉菜胶类型包括κ、ι、λ等。在一些实施方案中,使用诸多角叉菜胶类型的混合物。在一个具体实施方案中,使用能形成凝胶的角叉菜胶或角叉菜胶样材料。除天然角叉菜胶以外,合适的角叉菜胶包括天然角叉菜胶或衍生化角叉菜胶的酶处理物质,例如通过处理天然角叉菜胶(例如,用化学物质)以引入官能团(例如羧基、羟基烷基、硫酸酯基、磷酸酯基等)而制备的那些。
SAP在SAP的聚合物链中包括多个交联。根据一个实施方案,所述交联是共价的,并且是由利用交联剂使SAP交联而产生。在一个实施方案中,所述交联剂是烯属不饱和单体,其含有例如两个烯属不饱和位点(即,两个烯属不饱和双键)、一个烯属不饱和双键和一个对SAP的聚合物链的官能团(例如,酰胺基团)具有反应性的官能团或若干个对SAP的聚合物链的官能团具有反应性的官能团。在一个实施方案中,选择SAP中的交联度以控制SAP的膨胀量(即,流体吸收或体积膨胀)。
示例性交联剂包括二胺的二丙烯酰胺或甲基丙烯酰胺,诸如哌嗪二丙烯酰胺;二、三、四羟基化合物的丙烯酸酯或甲基丙烯酸酯酯,包括乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、乙氧基化三羟甲基三丙烯酸酯、乙氧基化季戊四醇四丙烯酸酯等;由偶氮基团分开的二乙烯基或二烯丙基化合物,诸如2,2'-偶氮二(异丁酸)二烯丙基酰胺或者二官能酸或三官能酸的乙烯基或烯丙基酯。额外交联剂包括水溶性二丙烯酸酯,诸如聚(乙二醇)二丙烯酸酯(例如PEG 200二丙烯酸酯)或PEG 400二丙烯酸酯;和多元醇的多官能乙烯基衍生物,诸如乙氧基化(9-20)三羟甲基三丙烯酸酯。交联剂的其他实例包括脂肪族不饱和酰胺,诸如亚甲基双丙烯酰胺或亚乙基双丙烯酰胺;多元醇或烷氧基化多元醇与烯属不饱和酸的脂肪族酯,诸如丁二醇、乙二醇、聚二醇、三羟甲基丙烷的二(甲基)丙烯酸酯或三(甲基)丙烯酸酯;三羟甲基丙烷(其被用诸如环氧乙烷等环氧烷加以烷氧基化(诸如乙氧基化))的二丙烯酸酯和三丙烯酸酯;甘油或季戊四醇的丙烯酸酯和甲基丙烯酸酯;用例如环氧乙烷加以乙氧基化的甘油和季戊四醇的丙烯酸酯和甲基丙烯酸酯;烯丙基化合物(诸如(甲基)丙烯酸烯丙酯、与例如环氧乙烷、氰尿酸三烯丙酯、异氰脲酸三烯丙酯、马来酸二烯丙酯、聚烯丙基酯、四烯丙氧基乙烷、三烯丙基胺、四烯丙基乙二胺、二醇、多元醇、羟基烯丙基或丙烯酸酯化合物反应的烷氧基化(甲基)丙烯酸烯丙酯和磷酸或亚磷酸烯丙酯);或能够交联的单体,诸如不饱和酰胺(诸如甲基丙烯酰胺或丙烯酰胺)的N-羟甲基化合物,以及由其衍生的醚。还可以使用交联剂的组合。
在一个实施方案中,SAP是包括发生在SAP内部以外的表面交联的颗粒(或纤维或其他形式)。表面交联例如由向SAP颗粒中加入表面交联剂并且进行热处理而引起。表面交联使SAP在其表面附近的交联密度相对于SAP内部的交联密度有所增加。一些表面交联剂具有对SAP的一组聚合物链具有反应性的官能团,例如酸或酰胺基团。表面交联剂是前述交联剂之一,并且包括诸如醇、胺、醛或羧酸酯基团等官能团。在一个实施方案中,表面交联剂具有多个不同的官能团,诸如多元醇、聚胺、聚氨基醇和碳酸亚烷基酯。可以使用乙二醇、二乙二醇、三乙二醇、聚乙二醇、甘油、聚甘油、丙二醇、二乙醇胺、三乙醇胺、聚丙二醇、环氧乙烷与环氧丙烷的嵌段共聚物、脱水山梨糖醇脂肪酸酯、乙氧基化脱水山梨糖醇脂肪酸酯、三羟甲基丙烷、乙氧基化三羟甲基丙烷、季戊四醇、乙氧基化季戊四醇、聚乙烯醇、山梨糖醇、碳酸亚乙酯和碳酸亚丙酯。表面交联剂还给SAP提供了以下化学性质:SAP的聚合物链在表面交联之前不具有和控制SAP的化学性质,例如SAP对诸如矿物质(例如硅酸盐)等其他材料或诸如石油化合物(例如烃类、沥青质等)等其他化学物质的疏水性、亲水性或粘附性。其他交联剂包括硼酸盐、钛酸盐、锆酸盐、铝酸盐、铬酸盐或其组合。硼交联剂包括例如硼酸、四硼酸钠、包封硼酸盐等。在一些实施方案中,使用硼酸盐交联剂与缓冲剂和pH值控制剂,诸如氢氧化钠、氧化镁、倍半碳酸钠和碳酸钠;胺(诸如羟基烷基胺、苯胺、吡啶、嘧啶、喹啉、吡咯烷和羧酸盐,诸如乙酸盐和草酸盐);延迟剂,诸如山梨糖醇、醛、葡糖酸钠等。在某些实施方案中,使用锆交联剂,例如乳酸锆(例如乳酸钠锆)、三乙醇胺、2,2'-亚氨基二乙醇或其组合。用于交联的钛酸盐包括例如乳酸盐和三乙醇胺等。
在一个实施方案中,SAP包括包含丙烯酸酯、丙烯酰胺、乙烯基吡咯烷酮、乙烯基酯(例如乙酸乙烯酯)、乙烯醇、其衍生物或其组合的重复单元。根据一个实施方案,SAP是具有聚乙二醇二丙烯酸酯交联的聚丙烯酰胺。在一些实施方案中,SAP是聚丙烯酸,其中交联是乙烯基酯寡聚物。在一个实施方案中,SAP是可购自Sigma Aldrich的聚(丙烯酸)部分钠盐接枝聚(乙二醇)。此外,SAP可以呈多种形式,包括颗粒(例如粉末)、纤维、股链、编织物等或其组合。SAP的尺寸是10μm至100,000μm,具体来说是50μm至10,000μm,并且更具体来说是50μm至1,000μm。如本文中所使用,“尺寸”是指最大线性尺寸,例如球形颗粒的直径。SAP颗粒是任何形状,包括球形、角形和多面体形。根据一个实施方案,SAP是在SAP的聚合物链之间具有孔隙或空间,从而允许流体或支撑剂颗粒进入其中的颗粒。水力压裂组合物包括多个SAP颗粒(或诸如纤维或编织物等其他形式),它们聚结在一起并且形成一块SAP,在本文中也称为超吸附性聚合物(SAP)。此外,虽然图1将SAP显示为多个超吸附性聚合物颗粒12,但是在一些实施方案中,SAP是如图2中所示的多个超吸附性聚合物纤维12。一些实施方案设想了不同形式的SAP的组合。
具有交联的SAP可用作流体或支撑剂颗粒的载体。在压裂操作(例如水力压裂)中,在SAP响应于破裂条件而破裂时,被安置在SAP中的支撑剂颗粒保留在裂缝中并且当用于形成裂缝的压力被释放时使裂缝保持张开。支撑剂颗粒具有1μm至2000μm,具体来说10μm至1000μm,并且更具体来说10μm至500μm的尺寸。此外,支撑剂颗粒具有任何形状,包括球形、角形和多面体形,并且是单分散的或多分散的,具有单峰或多峰,例如双峰平均粒度分布。
在一个实施方案中,由于SAP和支撑剂颗粒的相对尺寸之故,支撑剂颗粒被安置在相邻的SAP颗粒(图1物品)12或纤维(图2物品12)之间,例如在由此类相邻SAP颗粒或纤维之间的空隙或空间22形成的孔隙或通道中,或者被安置在膨胀状态的SAP中的个别SAP颗粒或纤维内。
支撑剂颗粒包括陶瓷、砂、矿物、坚果壳、砾石、玻璃、树脂颗粒、聚合物颗粒或其组合。在一个实施方案中,取决于水力压裂组合物的具体应用来选择支撑剂颗粒。陶瓷的实例包括基于氧化物的陶瓷、基于氮化物的陶瓷、基于碳化物的陶瓷、基于硼化物的陶瓷、基于硅化物的陶瓷或其组合。在一个实施方案中,基于氧化物的陶瓷是二氧化硅(SiO2)、二氧化钛(TiO2)、氧化铝、氧化硼、氧化钾、氧化锆、氧化镁、氧化钙、氧化锂、氧化磷和/或氧化钛或其组合。基于氧化物的陶瓷、基于氮化物的陶瓷、基于碳化物的陶瓷、基于硼化物的陶瓷或基于硅化物的陶瓷含有非金属(例如氧、氮、硼、碳或硅等)、金属(例如铝、铅、铋等)、过渡金属(例如铌、钨、钛、锆、铪、钇等)、碱金属(例如锂、钾等)、碱土金属(例如钙、镁、锶等)、稀土(例如镧、铈等)或卤素(例如氟、氯等)。示例性陶瓷包括氧化锆、稳定氧化锆、莫来石、氧化锆增韧氧化铝、尖晶石、硅酸铝(例如莫来石、堇青石)、钙钛矿、碳化硅、氮化硅、碳化钛、氮化钛、碳化铝、氮化铝、碳化锆、氮化锆、碳化铁、氮氧化铝、氮氧化硅铝、钛酸铝、碳化钨、氮化钨、滑石等或其组合。
适用于支撑剂颗粒的砂的实例包括但不限于亚利桑那砂、威斯康星砂、獾州砂、布雷迪砂和渥太华砂。在一个实施方案中,将由诸如铝矾土等矿物制成的支撑剂颗粒烧结以获得硬质材料。在一个实施方案中,铝矾土或烧结铝矾土具有相对较高的渗透性,诸如美国专利号4,713,203中公开的铝矾土材料,该美国专利的内容以全文引用的方式并入本文中。
天然存在的支撑剂颗粒包括坚果壳,诸如核桃、椰子、美洲山核桃、杏仁、象牙果、巴西坚果等;诸如李子、橄榄、桃、樱桃、杏等水果的种壳;诸如玉米(例如玉米穗或玉米粒)等其他植物的种壳;木材,诸如来自橡树、山核桃、胡桃、杨树、桃花心木等的那些。此类材料是通过粉碎、研磨、切割、切屑等形成的颗粒。
在一个实施方案中,支撑剂颗粒涂布有例如树脂。也就是说,个别支撑剂颗粒具有施加给其的涂层。以这种方式,如果支撑剂颗粒在例如压裂期间或随后在足以由其产生细颗粒的压力下被压缩,那么细颗粒保持固结在涂层内,所以它们不会被释放到地层中。设想了细颗粒能减少烃类(或其他流体)通过裂缝或裂缝中的孔隙进行的传导,并且通过涂布支撑剂颗粒加以避免。用于支撑剂颗粒的涂层包括例如热固性或热塑性树脂的固化、部分固化或未固化涂层。举例来说,使支撑剂颗粒上的涂层固化发生在将支撑剂颗粒安置在SAP中之前或之后或者在将水力压裂组合物安置在井下之前或之后。
在一个实施方案中,所述涂层是有机化合物,包括环氧树脂、酚醛树脂、聚氨酯、聚碳化二亚胺、聚酰胺、聚酰胺酰亚胺、呋喃树脂或其组合。酚醛树脂是例如通过苯酚、双酚或其衍生物与甲醛的反应获得的酚醛树脂。示例性热塑性树脂包括聚乙烯、丙烯腈-丁二烯苯乙烯、聚苯乙烯、聚氯乙烯、含氟塑料、聚硫化物、聚丙烯、苯乙烯丙烯腈、尼龙和苯醚。示例性热固性树脂包括环氧树脂、酚醛树脂(真热固性树脂,诸如甲阶酚醛树脂,或由硬化剂致使热固化的热塑性树脂)、聚酯树脂、聚氨酯、环氧改性酚醛树脂和其衍生物。
在一个实施方案中,用于涂层的固化剂是含氮化合物,诸如胺和其衍生物;含氧化合物,诸如羧酸封端的聚酯、酸酐、酚醛树脂、氨基甲醛树脂、苯酚、双酚A和甲酚酚醛清漆树脂、酚类封端的环氧树脂;含硫化合物,诸如多硫化物、多硫醇;和催化性固化剂,诸如叔胺、路易斯酸、路易斯碱;或其组合。
在一个实施方案中,支撑剂颗粒包括交联涂层。交联涂层典型地为支撑剂颗粒提供压碎强度或抗性,并且即使在高压和高温条件下也能防止支撑剂颗粒聚集。在一些实施方案中,支撑剂颗粒具有可固化涂层,从而在地表下,例如在井下或在裂缝中固化。可固化涂层在地表下储层中的高压和高温条件下固化。因此,具有可固化涂层的支撑剂颗粒被用于高压和高温条件。
根据一个实施方案,通过在容器(例如反应器)中进行混合而将涂层安置在支撑剂颗粒上。将个别组分,例如支撑剂颗粒和树脂材料(例如,用于形成例如环氧树脂或聚酰胺涂层的反应性单体)组合在容器中以形成反应混合物,并且搅动以混合组分。此外,在与形成涂层相称的温度或压力下加热反应混合物。在另一个实施方案中,通过喷涂,诸如通过使支撑剂颗粒与涂层材料的喷雾接触而将涂层安置在颗粒上。加热涂布过的支撑剂颗粒以诱导涂层交联。
在一些实施方案中,除了支撑剂颗粒和SAP以外,水力压裂组合物还包括破裂剂。所述破裂剂接触SAP以使SAP破裂。在一个实施方案中,所述破裂剂接触SAP并且使SAP的聚合物链骨架中的键、交联剂中的键、交联剂与SAP的聚合物链之间的键或其组合破裂。也就是说,使SAP破裂包括使SAP崩解、分解或离解,诸如通过使SAP骨架中的键破裂、使SAP链中的交联破裂、改变超吸附性聚合物的几何构象或其组合。以这种方式,水力压裂组合物的粘度降低。在一些实施方案中,破裂剂使SAP破裂以形成分解聚合物,诸如与SAP相比具有更低分子量的多个片段。在使SAP破裂之后,多个支撑剂颗粒得以从SAP中释放出来。
根据一个实施方案,破裂剂包括氧化剂,诸如过氧化物、过硫酸盐、过磷酸盐、过硼酸盐、过碳酸盐、过硅酸盐、卤素的含氧酸、卤素的氧阴离子、过酸、其衍生物或其组合。
在一个实施方案中,破裂剂是过硫酸盐,诸如过硫酸钠、过硫酸铵、过硫酸钾、过氧单硫酸(卡罗酸)钾或其组合。破裂剂是例如卤素的含氧酸或氧阴离子,例如次氯酸、次氯酸盐、亚氯酸和亚氯酸盐、氯酸和氯酸盐、高氯酸和高氯酸盐、其衍生物或其组合。
在一个实施方案中,过氧化物破裂剂在其分子结构中具有氧-氧单键。过氧化物破裂剂是过氧化氢或另一种用于提供过氧化物或过氧化氢以使SAP破裂的材料。可以使用金属过氧化物,诸如过氧化钠、过氧化钙、过氧化锌、过氧化镁或其他过氧化物,诸如超氧化物、有机过氧化物等。
另外,在一个实施方案中,过氧化物破裂剂是一种稳定过氧化物破裂剂,其中过氧化氢在与例如水性流体(诸如水)接触之前被另一种化合物或分子结合、抑制等,使得其在被水性流体接触时形成或释放过氧化氢。示例性稳定过氧化物破裂剂包括过氧化氢与另一个分子的加合物,并且包括过氧化脲或过氧化尿素(C(=O)(NH2)2·H2O2)、过碳酸盐(例如过碳酸钠(2Na2CO3·3H2O2)、过碳酸钾、过碳酸铵等)等。稳定过氧化物破裂剂还包括在水中经历水解以释放过氧化氢的化合物,例如过硼酸钠。在一个实施方案中,还使用经适当表面活性剂稳定过的过氧化氢作为稳定过氧化物破裂剂。
根据一个实施方案,破裂剂是过酸,例如过乙酸、过苯甲酸、其衍生物或其组合。另外,使用多种过氧羧酸作为过酸破裂剂。过氧羧酸包括酯过氧羧酸、烷基酯过氧羧酸、磺基过氧羧酸或其组合。过氧羧酸(或过羧酸)是具有通式R(CO3H)n的酸。在一个实施方案中,R基团是饱和或不饱和的,以及被取代或未被取代的。如本文中所描述,R是烷基、烯基、芳基烷基、芳基烯基、环烷基、环烯基、芳香族、杂环或酯基团或其组合(例如烷基酯基团),其中n是1、2或3。示例性酯基包括脂肪族酯基团,诸如R1OC(O)R2,其中R1和R2独立地是上文针对R所描述的基团(例如,烷基),使得R1和R2独立地是例如小碳链烷基,诸如C1-C5烷基。
本领域技术人员应了解,过氧羧酸可能不如羧酸那样稳定,并且其稳定性可能随着分子量的增加而增加。过酸的热分解通过例如自由基和非自由途径、通过光分解或自由基诱导的分解,或者通过金属离子或络合物的作用来进行。在一个实施方案中,过羧酸过酸是通过过氧化氢与羧酸的直接酸催化平衡作用、通过醛的自氧化或由酰氯和氢化物或羧酸酐与氢或过氧化钠来制备。
示例性过氧羧酸包括过氧甲酸、过氧乙酸、过氧丙酸、过氧丁酸、过氧戊酸、过氧己酸、过氧庚酸、过氧辛酸、过氧壬酸、过氧癸酸、过氧十一烷酸、过氧十二烷酸、过氧乳酸、过氧柠檬酸、过氧马来酸、过氧抗坏血酸、过氧羟基乙酸(过氧乙醇酸)、过氧草酸、过氧丙二酸、过氧丁二酸、过氧戊二酸、过氧己二酸、过氧庚二酸、过氧辛二酸、过氧癸二酸等。
在一个实施方案中,过酸包括若干种过氧羧酸的组合。根据一个实施方案,组合物包括C2-C4过氧羧酸、C8-C12过氧羧酸、酯过氧羧酸、烷基酯过氧羧酸,或者具有至多12个碳原子并且更具体来说2至12个碳原子的单过氧羧酸或二过氧羧酸。在一个实施方案中,过氧羧酸包括过氧乙酸(POAA)(即,具有式CH3COOOH的过乙酸)或过氧辛酸(POOA)(即,具有例如正过氧辛酸的化学式的过辛酸:CH3(CH2)6COOOH)。
在一个实施方案中,过酸是酯过氧羧酸。如本文中所使用,酯过氧羧酸是指具有下式的分子:
其中R1和R2独立地是有机基团(例如直链或环状、芳香族或饱和烷基)或被取代的有机基团(例如,具有杂原子或有机基团)。在一个实施方案中,酯过氧羧酸是通过使用用于制造过氧羧酸的方法,诸如组合相应的酯羧酸与氧化剂(例如过氧化氢)来制造。
示例性烷基酯过氧羧酸包括单甲基单过氧戊二酸、单甲基单过氧己二酸、单甲基单过氧草酸、单甲基单过氧丙二酸、单甲基单过氧丁二酸、单甲基单过氧庚二酸、单甲基单过氧辛二酸和单甲基单过氧癸二酸;单乙基单过氧草酸、单乙基单过氧丙二酸、单乙基单过氧丁二酸、单乙基单过氧戊二酸、单乙基单过氧己二酸、单乙基单过氧庚二酸、单乙基单过氧辛二酸和单乙基单过氧癸二酸;单丙基单过氧草酸、单丙基单过氧丙二酸、单丙基单过氧丁二酸、单丙基单过氧戊二酸、单丙基单过氧己二酸、单丙基单过氧庚二酸、单丙基单过氧辛二酸、单丙基单过氧癸二酸,其中丙基是正丙基或异丙基;单丁基单过氧草酸、单丁基单过氧丙二酸、单丁基单过氧丁二酸、单丁基单过氧戊二酸、单丁基单过氧己二酸、单丁基单过氧庚二酸、单丁基单过氧辛二酸、单丁基单过氧癸二酸,其中丁基是正丁基、异丁基或叔丁基;等等。
在一些实施方案中,过酸破裂剂是磺基过氧羧酸。磺基过氧羧酸,也被称为磺化过酸,包括过氧羧酸形式的磺化羧酸。在一些实施方案中,磺化过酸是中链磺化过酸,即,包括与碳连接的磺酸酯基团的过酸,所述碳是来自过羧酸链的碳骨架中的过羧酸基团的碳的至少一个碳(例如,至少三个位置),其中所述至少一个碳不在末端位置。如本文中所使用,术语“末端位置”是指过羧酸碳骨架链上距过羧酸基团最远的碳。因此,在一个实施方案中,磺基过氧羧酸具有下式:
其中R3是氢或者被取代或未被取代的烷基;R4是被取代或未被取代的烷基;X是氢、阳离子基团或成酯部分;或者其盐或酯。
在一些实施方案中,R3是被取代或未被取代的Cm烷基;X是氢、阳离子基团或成酯部分;R4是被取代或未被取代的Cn烷基;m=1至10;n=1至10;并且m+n小于18;或者其盐、酯或组合。在一些实施方案中,R3是氢。在其他实施方案中,R3是被取代或未被取代的烷基。在一些实施方案中,R3是被取代或未被取代的烷基,不包括环烷基。在一些实施方案中,R3是被取代的烷基。在一些实施方案中,R3是未被取代的C1-C9烷基。在一些实施方案中,R3是未被取代的C7或C8烷基。在其他实施方案中,R3是被取代的C8-C10烷基。在一些实施方案中,R3是被取代的C8-C10烷基,并且被至少1个或至少2个羟基取代。在再其他实施方案中,R3是被取代的C1-C9烷基。在一些实施方案中,R3 1是被取代的C1-C9被取代的烷基,并且被-SO3H基团取代。在其他实施方案中,R3是C9-C10被取代的烷基。在一些实施方案中,R3是被取代的C9-C10烷基,其中碳骨架上的至少两个碳形成杂环基团。在一些实施方案中,所述杂环基团是环氧基团。
在一个实施方案中,R4是被取代的C1-C10烷基。在一些实施方案中,R4是被取代的C8-C10烷基。在一些实施方案中,R4是未被取代的C6-C9烷基。在其他实施方案中,R4是被至少一个羟基取代的C8-C10烷基。在一些实施方案中,R4是被至少两个羟基取代的C10烷基。在其他实施方案中,R4是被至少一个-SO3H基团取代的C8烷基。在一些实施方案中,R4是被取代的C9基团,其中碳骨架上的至少两个碳形成杂环基团。在一些实施方案中,所述杂环基团是环氧基团。在一些实施方案中,R4是C8-C9被取代或未被取代的烷基,并且R4是C7-C8被取代或未被取代的烷基。
根据一个实施方案,在水力压裂组合物中,破裂剂被包封在包封材料中以防止破裂剂与SAP接触。包封材料被构造为响应于破裂条件而释放破裂剂。所述破裂剂是固体或液体。作为固体,所述破裂剂是例如结晶或颗粒状材料。在一个实施方案中,所述固体被包封或设有涂层以延迟其释放或与SAP接触。包封材料与以上关于支撑剂颗粒指出的涂层材料相同或不同。将包封材料安置在破裂剂上的方法与将涂层安置在支撑剂颗粒上相同或不同。在一个实施方案中,将液体破裂剂溶解在水溶液或另一种合适的溶剂中。
在一个实施方案中,所述包封材料是以可控方式,例如以受控速率或浓度释放破裂剂的聚合物。此类材料是在一段时间内降解以释放破裂剂的聚合物,并且是取决于所期望的释放速率而选择。包封材料聚合物的聚合物的降解例如通过水解、溶剂分解、熔融等而发生。在一个实施方案中,包封材料的聚合物是乙醇酸酯与乳酸酯的均聚物或共聚物、聚碳酸酯、聚酸酐、聚原酸酯、聚磷腈或其组合。
根据一个实施方案,包封破裂剂是包封过氧化氢、包封金属过氧化物(例如过氧化钠、过氧化钙、过氧化锌等)或本文中的任何过酸或其他破裂剂。
在水力压裂组合物中,包括流体以接触SAP并且使SAP膨胀至膨胀状态。流体是水性流体,包括水、盐水、诸如无机酸或有机酸等酸或碱。盐水是例如海水、产出水、完井盐水或其组合。盐水的性质可以取决于盐水的特性和组分。作为一个实例,海水除了典型的含卤离子的盐以外还含有许多成分,诸如硫酸盐、溴和痕量金属。在一些实施方案中,产出水是从生产储层(例如,烃储层)中提取或从地表产出的水。产出水也称为储层盐水,并且含有诸如钡、锶和重金属等组分。除了天然存在的盐水(海水和产出水)以外,通过加入不同的盐,诸如KCl、NaCl、ZnCl2、MgCl2或CaCl2以增加盐水的密度,例如10.6磅每加仑CaCl2盐水而由淡水合成的完井盐水。完井盐水典型地提供优化的静水压力以抵抗井下储层压力。在一个实施方案中,以上盐水经过改性以包括额外的盐。在一个实施方案中,盐水中包括的额外的盐是NaCl、KCl、NaBr、MgCl2、CaCl2、CaBr2、ZnBr2、NH4Cl、甲酸钠,甲酸铯等。盐是以流体的重量计以约0.5重量%(wt%)至约50wt%,具体来说约1wt%至约40wt%,更具体来说约1wt%至约25wt%的量存在于盐水中。
根据一个实施方案,所述流体是无机酸,其包括盐酸、硝酸、磷酸、硫酸、硼酸、氢氟酸、氢溴酸、过氯酸或其组合。在一些实施方案中,所述流体是有机酸,其包括羧酸、磺酸或其组合。示例性羧酸包括甲酸、乙酸、氯乙酸、二氯乙酸、三氯乙酸、三氟乙酸、丙酸、丁酸、草酸、苯甲酸、邻苯二甲酸(包括邻位、间位和对位异构体)等。示例性磺酸包括烷基磺酸或芳基磺酸。烷基磺酸包括例如甲磺酸。芳基磺酸包括例如苯磺酸或甲苯磺酸。在一个实施方案中,烷基可以是支链或非支链的,而且含有1至约20个碳原子并且是被取代或未被取代的。在一个实施方案中,芳基是被烷基取代的,即,是烷基芳基,或通过亚烷基与磺酸部分连接(即,芳基烷基)。在一个实施方案中,芳基被杂原子取代。芳基具有3个碳原子至20个碳原子,并且包括例如多环结构。
在一个实施方案中,水力压裂组合物还包括用于流量保证、性能提高和流体稳定性的井处理剂。合适的井处理剂包括可以解决由结垢、盐形成、石蜡沉积、沥青质沉积、发泡剂沉积、乳化、气体水合物形成、腐蚀、发泡剂、氧清除剂、H2S清除剂、杀生物剂、表面活性剂或其组合导致的不良影响的那些。具体的井处理剂包括阻垢剂、示踪剂、pH值缓冲剂或其组合。
井处理剂可以呈液体或固体形式照原样或者呈盐或其他络合物的形式使用。井处理剂可以涂布、包封、合并至粘合剂中、吸附至基质上或吸附至基质中。合适的涂层包括以上所描述的供与支撑剂一起使用的热塑性、热固性和交联涂层。合适的包封剂包括以上所描述的供与破裂剂一起使用的那些。与涂层或包封剂相同的可用热塑性、热固性和交联材料还适合用作粘合剂或用于吸附井处理剂的基质。用于吸附井处理材料的基质是多孔的,优选微孔的,并且可以是有机的(例如,开孔聚合物泡沫,诸如聚氨酯泡沫)或无机的(例如沸石、金属硅酸盐和铝磷酸盐)。
阻垢剂可以用于控制或预防井中结垢以及其他功能。阻垢剂可以是含羧酸、磺酸或膦酸的化合物、含羧酸、磺酸或膦酸的聚合物或其组合,例如氨基三亚甲基膦酸、1-羟基亚乙基-1,1-二膦酸、2-膦酰基丁烷-1,2,4-三甲酸、2-羟乙基-氨基-双(亚甲基膦酸)、乙二胺四(亚甲基膦酸)、四亚甲基二胺四(亚甲基膦酸)、六亚甲基二胺四(亚甲基膦酸)、2-羟基膦酰基乙酸、二亚乙基三胺五(亚甲基膦酸)、双(六亚甲基三胺五(亚甲基膦酸))、聚氨基聚醚亚甲基膦酸酯或其盐、膦酸基聚羧酸盐、聚丙烯酸、聚马来酸、丙烯酸共聚物、磺酸酯化聚丙烯酸酯共聚物、聚乙烯磺酸酯、羧甲基菊粉、聚天冬氨酸盐或其组合。
阻垢剂是以能有效抑制水垢达到所期望的程度的量存在于水力压裂组合物中,该量可以是例如约0.001wt%至约10wt%或约0.01wt%至约10wt%或约0.01wt%至约5wt%,优选约0.1wt%至约2wt%,各量是以组合物的总重量计。
可以使用示踪剂以便稍后检测或推断关于井、钻孔或钻井地层的信息。在钻井期间使用的示踪剂可以是泥浆示踪剂和滤液示踪剂。示踪剂可以是油溶性或水溶性的。示踪剂的实例包括氟化苯甲酸、全氟化烃、醇、酮、有机酸、卤代化合物或其组合。
示例性全氟化烃是全氟化C1-C18烃,例如四氟甲烷、四氟乙烷、四氟丙烷等。
醇的实例包括C1-C24单官能和多官能醇,诸如甲醇、乙醇、乙二醇、丙醇、丙二醇、丁醇、戊醇、季戊四醇、己醇、辛醇、癸醇、十二烷醇等。优选的醇是C10-C24单官能醇。
示例性酮是C1-C18酮和二酮,诸如丙酮、环丙酮、甲基乙基酮、环己酮、乙酰丙酮、二苯甲酮等。
示例性有机酸包括C1-C18单羧酸、二羧酸和三羧酸。有机酸的实例是乙酸、丙酸、丁酸、草酸、丙二酸、丁二酸、戊二酸、己二酸、癸二酸、柠檬酸等。
卤代化合物可以是单氯化、二氯化、三氯化和四氯化C1-C12烃类。实例包括二氯甲烷、三氯甲烷、四氯化碳、三氯乙烯、四氯乙烯、六氯环己烷、苄基氯、亚苄基氯、三氯甲苯等。
示踪剂是以能有效追踪所期望的流体或组合物的量存在于水力压裂组合物中,该量可以是例如约0.001wt%至约10wt%或约0.001wt%至约5wt%或约0.01wt%至约5wt%,优选约0.01wt%至约1wt%,各量是以组合物的总重量计。
缓冲剂可以是用于在加入另一种酸或碱之后维持溶液的pH值在选定值附近的弱酸或弱碱。缓冲剂的功能是防止当将酸或碱加入溶液时pH值发生快速变化。对于酸区中的缓冲剂,通过向缓冲剂中加入诸如HCl等强酸而将pH值调节至所期望的值。对于碱性缓冲剂,加入诸如NaOH等强碱。替代地,可以由酸与其共轭碱的组合(例如混合物)制造缓冲剂组合。举例来说,乙酸盐缓冲剂可以由乙酸与乙酸钠的混合物制造。类似地,碱性缓冲剂可以由碱与其共轭酸的混合物制造。pH值缓冲剂与pH值调节剂的不同之处在于,缓冲剂在地下井的井下温度下维持流体的pH值在所期望的范围内,例如约6至约9的pH值,优选约6.5至约8.5的pH值,最优选约7至约8的pH值。缓冲剂的实例包括碱金属和碱土金属碳酸盐、碳酸氢盐、乙酸盐、柠檬酸盐、葡糖酸盐、磷酸盐、硼酸盐或酒石酸盐,例如碳酸钠和碳酸钾、CaCO3、倍半碳酸钠和倍半碳酸钾;碱土金属氧化物,诸如MgO和CaO;有机聚电解质;或其组合。
缓冲剂是以能有效缓冲组合物的量存在于水力压裂组合物中,该量可以是例如约0.005wt%至约10wt%或约0.01wt%至约10wt%或约0.01wt%至约5wt%或约0.1wt%至约2wt%,各量是以组合物的总重量计。
缓冲剂可以任选地与缓慢释放破裂剂(例如缓慢释放酸)组合使用。酸可以是乙二醛、固体酸、包封酸、涂布酸或其组合。乙二醛是可以缓慢释放酸的二醛。酸的缓慢释放可以克服缓冲剂,并且导致流体pH值逐渐降低,直到达到适合于使SAP破裂的选定pH值为止。
当使用时,上述井处理剂可以在完井时通过井下注入点连续注入,或可以进行周期性挤压处理以便将添加剂放在储层基质中,以供随后与产出流体混合。
在一些实施方案中,除了SAP以外,水力压裂组合物还包括粘性聚合物。所述粘性聚合物包括瓜尔胶、由甘露糖和半乳糖组成的高分子量多糖、黄原胶、瓜尔胶或淀粉或瓜尔胶衍生物,诸如羟丙基瓜尔胶(HPG)、羧甲基瓜尔胶(CMG)和羧甲基羟丙基瓜尔胶(CMHPG)、半乳甘露聚糖胶、葡甘露聚糖胶、瓜尔胶、衍生化瓜尔胶、纤维素衍生物或其组合。还使用纤维素衍生物,诸如羟乙基纤维素(HEC)、羧甲基纤维素(CMC)、羟丙基纤维素(HPC)和羧甲基羟乙基纤维素(CMHEC);羟丙基淀粉;或木质素磺酸盐。
根据一个实施方案,粘性聚合物包括包含丙烯酸酯、丙烯酰胺、乙烯基吡咯烷酮、乙烯基酯(例如乙酸乙烯酯)、乙烯醇、2-丙烯酰胺-2-甲基丙磺酸、其衍生物或其组合的重复单元。在一些实施方案中,粘性聚合物是聚丙烯酸。
在一个示例性实施方案中,粘性聚合物包含线性聚合物,诸如聚丙烯酰胺、瓜尔胶、瓜尔胶衍生物、甘油、多糖(诸如纤维素和淀粉)或其组合。不希望受理论束缚,认为水力压裂组合物中存在粘性聚合物能增加粘度,从而增加组合物的支撑剂悬浮能力。粘性聚合物的存在还有助于减小摩擦压力。当水力压裂组合物是泡沫流体时,粘性聚合物通过改善泡沫品质和泡沫半衰期而进一步稳定泡沫流体。
粘性聚合物由于与水力压裂组合物流体(或另一种流体,诸如水、盐水或其他井下流体)接触而形成粘性凝胶。当粘性聚合物包含甘油、诸如线性聚丙烯酰胺、瓜尔胶、瓜尔胶衍生物等线性聚合物、诸如纤维素和淀粉等多糖或其组合时,所形成的粘性凝胶可以称为线性凝胶。在一些实施方案中,使用流体的组合,第一流体使SAP膨胀并且第二流体使粘胶聚合物胶凝。不希望受理论束缚,认为粘性聚合物由于长聚合物链缠结而具有增加的粘度。粘性聚合物的缠结聚合物链产生网状结构,从而产生复杂的粘度特性。在一个实施方案中,粘性聚合物是含有无规排列或呈嵌段形式的两种或更多种不同的单体的共聚物。此外,通过使粘胶聚合物的聚合物链交联来增加粘性聚合物的粘度。粘性聚合物的交联剂包括硼酸盐、钛酸盐、锆酸盐、铝酸盐、铬酸盐或其组合。硼交联的粘胶聚合物包括例如与硼酸、四硼酸钠或包封硼酸盐交联的瓜尔胶和取代瓜尔胶;硼酸盐交联剂可以与缓冲剂和pH值控制剂(诸如氢氧化钠、氧化镁、倍半碳酸钠和碳酸钠)、胺(诸如羟烷基胺、苯胺、吡啶、嘧啶、喹啉和吡咯烷)和羧酸盐(诸如乙酸盐和草酸盐)和与延迟剂(诸如山梨糖醇、醛和葡糖酸钠)一起使用。锆交联的粘胶聚合物包括例如由乳酸锆(例如乳酸钠锆)、三乙醇胺、2,2'-亚氨基二乙醇或其组合交联的那些。用于交联的钛酸盐包括例如乳酸盐和三乙醇胺等。
在一个实施方案中,水力压裂组合物包括SAP,例如具有以下项的SAP:交联聚合物颗粒,诸如聚丙烯酸、聚丙烯酰胺、多糖或其组合;多个支撑剂颗粒;用于使SAP膨胀的流体;和粘胶聚合物。一旦SAP与流体合并,它就会在维持其形状的同时膨胀。粘性聚合物是在流体中发生水合而且粘度由水合线性聚合物的缠结程度决定的线性聚合物。设想缠结的线性聚合物可以原位交联以形成交联的凝胶。因此,水力压裂组合物具有有益的流变性质,包括可调的粘度和破裂性质。
水力压裂组合物还可以包含表面活性剂。可用的表面活性剂包括具有至多22个碳原子的脂肪酸,诸如硬脂酸以及其酯和聚酯;聚(烷二醇),诸如聚(环氧乙烷)、聚(环氧丙烷),以及嵌段和无规聚(环氧乙烷-环氧丙烷)共聚物,诸如由BASF以商品名PLURONIC销售的那些。其他表面活性剂包括聚硅氧烷,诸如聚(二甲基硅氧烷)的均聚物或共聚物,包括具有官能化端基的那些,等等。其他有用的表面活性剂包括具有聚合物分散剂的那些,所述聚合物分散剂具有聚(烷二醇)侧链、脂肪酸或氟化基团,诸如接枝到聚合物骨架的全氟化C1-4磺酸。聚合物骨架包括基于聚酯、聚(甲基)丙烯酸酯、聚苯乙烯、聚(苯乙烯-(甲基)丙烯酸酯)、聚碳酸酯、聚酰胺、聚酰亚胺、聚氨酯、聚乙烯醇或包含这些聚合物骨架中的至少一种的共聚物的那些。另外,表面活性剂是阴离子、阳离子、两性离子或非离子的。
示例性阳离子表面活性剂包括但不限于烷基伯胺、仲胺和叔胺、烷醇酰胺、季铵盐、烷基化咪唑鎓和吡啶鎓盐。阳离子表面活性剂的额外实例包括伯至叔烷基胺盐,诸如例如单硬脂基氯化铵、二硬脂基氯化铵、三硬脂基氯化铵;季烷基铵盐,诸如例如单硬脂基三甲基氯化铵、二硬脂基二甲基氯化铵、硬脂基二甲基苄基氯化铵、单硬脂基-双(聚乙氧基)甲基氯化铵;烷基吡啶鎓盐,诸如例如氯化N-十六烷基吡啶鎓、氯化N-十八烷基吡啶鎓;N,N-二烷基吗啉鎓盐;脂肪酸酰胺盐,诸如例如聚乙烯聚胺;等等。
例示性阴离子表面活性剂包括烷基硫酸盐、烷基磺酸盐、脂肪酸、磺基琥珀酸盐和磷酸盐。阴离子表面活性剂的实例包括具有羧基的阴离子表面活性剂,诸如烷基羧酸钠盐、烷基羧酸钾盐、烷基羧酸铵盐、烷基苯羧酸钠盐、烷基苯羧酸钾盐、烷基苯羧酸铵盐、聚氧化烯烷基醚羧酸钠盐、聚氧化烯烷基醚羧酸钾盐、聚氧化烯烷基醚羧酸铵盐、N-酰基肌氨酸钠盐、N-酰基肌氨酸钾盐、N-酰基肌氨酸铵盐、N-酰基谷氨酸钠盐、N-酰基谷氨酸钾盐、N-酰基谷氨酸铵盐;具有磺酸基的阴离子表面活性剂;具有膦酸的阴离子表面活性剂;等等。
在一个实施方案中,非离子表面活性剂是例如乙氧基化脂肪醇、聚乙氧基化烷基苯酚、脂肪酸酯、甘油酯、二醇酯、聚醚、烷基多糖苷、胺氧化物或其组合。示例性非离子表面活性剂包括脂肪醇(例如鲸蜡醇、硬脂醇、鲸蜡硬脂醇、油醇等);聚氧乙二醇烷基醚(例如八乙二醇单十二烷基醚、五乙二醇单十二烷基醚等);聚氧丙二醇烷基醚(例如,四丙二醇单壬基醚);葡萄糖苷烷基醚(例如癸基葡糖苷、月桂基葡糖苷、辛基葡糖苷);聚氧乙二醇辛基苯酚醚(例如Triton X-100(乙氧基化辛基苯酚));聚氧乙二醇烷基苯酚醚(例如壬苯酚醚-9);甘油烷基酯(例如月桂酸甘油酯);聚氧乙二醇脱水山梨糖醇烷基酯(例如聚山梨糖醇酯,诸如脱水山梨糖醇单月桂酸酯、脱水山梨糖醇单棕榈酸酯、脱水山梨糖醇单硬脂酸酯、脱水山梨糖醇三硬脂酸酯、脱水山梨糖醇单油酸酯等);脱水山梨糖醇烷基酯(例如,聚氧乙烯脱水山梨糖醇单月桂酸酯、聚氧乙烯脱水山梨糖醇单棕榈酸酯、聚氧乙烯脱水山梨糖醇单硬脂酸酯、聚氧乙烯脱水山梨糖醇单油酸酯等);椰油酰胺乙醇胺(例如椰油酰胺单乙醇胺、椰油酰胺二乙醇胺等);胺氧化物(例如,十二烷基二甲基胺氧化物、十四烷基二甲基胺氧化物、十六烷基二甲基胺氧化物、十八烷基胺氧化物等);聚乙二醇与聚丙二醇的嵌段共聚物(例如,可以商品名Pluronics购自BASF的泊洛沙姆);聚乙氧基化胺(例如聚乙氧基化牛脂胺);聚氧乙烯烷基醚,诸如聚氧乙烯硬脂基醚;聚氧乙烯亚烷基醚,诸如聚氧乙烯油基醚;聚氧化烯烷基苯基醚,诸如聚氧乙烯壬基苯基醚;聚氧烷二醇,诸如聚氧丙二醇、聚氧乙二醇;聚氧乙烯单烷基化物,诸如聚氧乙烯单硬脂酸酯;双聚氧乙烯烷基胺,诸如双聚氧乙烯硬脂胺;双聚氧乙烯烷基酰胺,诸如双聚氧乙烯硬脂酰胺;烷基胺氧化物,诸如N,N-二甲基烷基胺氧化物;等等。
两性离子表面活性剂(其在同一分子上包括阳离子和阴离子官能团)包括例如甜菜碱,诸如羧酸烷基铵(例如[(CH3)3N+-CH(R)COO-]或磺酸盐(磺基甜菜碱),诸如[RN+(CH3)2(CH2)3SO3 -],其中R是烷基)。实例包括正十二烷基-N-苯甲基-N-甲基甘氨酸[C12H25N+(CH2C6H5)(CH3)CH2COO-]、N-烯丙基N-苯甲基N-甲基牛磺酸[CnH2n+1N+(CH2C6H5)(CH3)CH2CH2SO3 -]。
在一个实施方案中,表面活性剂是粘弹性表面活性剂。所述表面活性剂是粘弹性的,这是因为与即使在高浓度下也能形成粘度略高于水的牛顿溶液的许多表面活性剂不同,它能够在较低浓度下形成粘弹性流体。这种特有的流变特性主要是由于流体中所存在的表面活性剂聚集体的类型。在低粘度流体中,表面活性剂分子聚集在球形胶束中,而在粘弹性流体中,存在可以描述为蠕虫状、线状或棒状胶束的长胶束并且缠结。
本发明的粘弹性表面活性剂通常是离子型的。它可能是阳离子、阴离子或两性离子,取决于其头部基团的电荷。当表面活性剂是阳离子型时,它与负抗衡离子缔合,所述负抗衡离子可以是无机阴离子,诸如硫酸根、硝酸根、过氯酸根或卤离子,诸如Cl、Br;或芳香族有机阴离子,诸如水杨酸根、萘磺酸根、对氯和间氯苯甲酸根、3,5-二氯苯甲酸根和3,4-二氯苯甲酸根和2,4-二氯苯甲酸根、叔丁基苯酚酸根和乙基苯酚酸根、2,6-二氯苯酚酸根和2,5-二氯苯酚酸根、2,4,5-三氯苯酚酸根、2,3,5,6-四氯苯酚酸根、对甲基苯酚酸根、间氯苯酚酸根、3,5,6-三氯吡啶酸根、4-氨基-3,5,6-三氯吡啶酸根、2,4-二氯苯氧基乙酸根。当表面活性剂是阴离子型时,它与正抗衡离子缔合,例如Na+或K+。当它是两性离子型时,它与负抗衡离子和正抗衡离子二者缔合,例如Cl和Na+或K+。美国专利号7,081,439和7,279,446中已经描述了其他粘弹性表面活性剂。
水力压裂组合物可以是液体或泡沫。液体包括基于表面活性剂的流体、线性凝胶流体或交联的凝胶流体。基于表面活性剂的流体可以指包含粘弹性表面活性剂的水力压裂组合物。线性凝胶流体可以指包含线性凝胶的水力压裂组合物。类似地,交联的凝胶流体是指包含交联的凝胶的水力压裂组合物。
泡沫流体是气体和液体的稳定混合物。它一般以其泡沫品质,即,气体体积与泡沫体积的比率来描述。泡沫半衰期是评估泡沫流体的稳定性的另一个重要参数。泡沫流体的半衰期是用于产生泡沫的液体的一半在大气条件下从泡沫中突破而出所需的时间。泡沫体系主要用于压裂低压或水敏感性地层。
水溶性聚合物,诸如瓜尔胶、由甘露糖和半乳糖组成的高分子量多糖或诸如羟丙基瓜尔胶(HPG)、羧甲基羟丙基瓜尔胶(CMHPG)等瓜尔胶衍生物,可以用于制备泡沫流体的液相。可以使用基于硼、钛、锆或铝络合物的交联剂来提高聚合物的有效分子量,并且使其更适合用于高温井。
使用粘弹性表面活性剂可以获得泡沫流体的无聚合物液相。这些流体通常是通过在水溶液中以适当的量混合合适的表面活性剂,诸如阴离子、阳离子、非离子和两性离子表面活性剂来制备。粘弹性表面活性剂流体的粘度归因于由流体中的组分形成的三维结构。当粘弹性流体中的表面活性剂的浓度显著超过临界浓度时,并且在大部分情况下在存在电解质时,表面活性剂分子聚集成诸如胶束等物质,其可以相互作用以形成表现出粘度和弹性特性的网状结构以进一步稳定发泡体系。同时,表面活性剂还起着发泡剂的作用,从而产生气体在粘性液体中的稳定分散液。
在一个实施方案中,水力压裂组合物中包括不同的额外添加剂。示例性额外添加剂包括润滑剂、非乳化剂、粘土稳定剂、杀生物剂、酸、腐蚀抑制剂、pH值调节剂或其组合。
在一个实施方案中,所述额外添加剂中的非乳化剂是以上表面活性剂的组合或表面活性剂与短链醇或多元醇(诸如月桂基硫酸酯)与异丙醇或乙二醇的组合。非乳化剂能防止水力压裂组合物中形成乳液。
在一个实施方案中,所述额外添加剂是润滑剂,诸如聚丙烯酰胺、石油馏出物、加氢处理轻质石油馏出物、短链醇(例如甲醇)或多元醇(例如乙二醇或甘油)。此类润滑剂使摩擦力减至最小并且包括例如聚合物,诸如聚丙烯酰胺、聚甲基丙烯酸异丁酯、聚甲基丙烯酸甲酯或聚异丁烯,以及水溶性润滑剂,诸如瓜耳胶、瓜尔胶衍生物、聚丙烯酰胺和聚环氧乙烷。在一个实施方案中,润滑剂包括瓜尔胶、瓜尔胶衍生物、甘油、聚丙烯酰胺、多糖(诸如纤维素和淀粉)或其组合。
所述额外添加剂中的粘土稳定剂能防止井下的粘土在与水力压裂组合物接触时或在所施加的压裂压力下膨胀。在一个实施方案中,粘土稳定剂包括季胺、盐水(例如,KCl盐水)、氯化胆碱、四甲基氯化铵等。
根据一个实施方案,所述额外添加剂是pH值调节剂,其调节水力压裂组合物的pH值。pH值调节剂是有机或无机碱、有机或无机酸或缓冲剂,其是酸与共轭碱的任何适当的组合。示例性无机碱包括由MOH表示的那些,其中M是周期表中第1族或第2族的金属、过渡金属或者第13族、第14族或第15族的金属或准金属;碳酸盐;碳酸氢盐;或其组合。示例性无机酸包括HCl、HBr、氟硼酸、硫酸、硝酸、乙酸、甲酸、甲磺酸、丙酸、氯乙酸或二氯乙酸、柠檬酸、乙醇酸、乳酸或其组合。在一个实施方案中,选择pH值调节剂以避免赋予水力压裂组合物以有利的特征。在一个实施方案中,选择pH值调节剂以避免破坏含有水力压裂组合物的地表设备或者避免破坏井孔或地下地层。
在一个实施方案中,水力压裂组合物的额外添加剂是防止微生物(例如细菌)注入井下的杀生物剂。杀生物剂能杀死、消除或减少水力压裂组合物(诸如水)中的细菌(例如,当使用河水作为流体时)。以这种方式,防止将活细菌引入地层,从而减少例如酸性气体的产生。
根据一个实施方案,所述杀生物剂不干扰水力压裂组合物的其他组分,并且不具有健康风险。在一个实施方案中,所述杀生物剂是醛,诸如戊二醛。杀生物剂的实例包括非氧化性和氧化性杀生物剂。示例性氧化性杀生物剂包括次氯酸盐漂白剂(例如次氯酸钙和次氯酸锂)、过乙酸、单过硫酸钾、过氧单硫酸钾、溴氯二甲基乙内酰脲、二氯乙基甲基乙内酰脲、氯异氰脲酸酯、三氯异氰尿酸、二氯异氰尿酸、氯化乙内酰脲等。额外氧化性杀生物剂包括例如溴产物,诸如稳定次溴酸钠、活化溴化钠或溴化乙内酰脲。其他氧化性杀生物剂包括二氧化氯、臭氧、无机过硫酸盐(诸如过硫酸铵)或过氧化物(诸如过氧化氢和有机过氧化物)。
示例性非氧化性杀生物剂包括二溴硝基丙酰胺、硫代氰基甲基硫代苯并噻唑、二硫代氨基甲酸甲酯、四氢二甲基硫杂二硫酮、三丁基氧化锡、溴硝基丙二醇、溴硝基苯乙烯、二硫代氰基甲烷、氯甲基异噻唑啉酮、甲基异噻唑啉酮、苯并异噻唑啉酮、十二烷基胍盐酸盐、聚六亚甲基双胍、四(羟甲基)硫酸磷、戊二醛、烷基二甲基苯甲基氯化铵、二癸基二甲基氯化铵、聚[氧乙烯-(二甲基亚氨基)乙烯(二甲基亚氨基)二氯乙烷]、癸基硫代乙胺、叔丁基吖嗪等。额外非氧化性杀生物剂是季铵盐、醛和季鏻盐。在一个实施方案中,季化杀生物剂具有脂肪烷基和三个甲基,但是在鏻盐中,甲基例如被羟甲基取代而基本上不影响杀生物活性。在一个实施方案中,它们还被芳基取代。实例包括甲醛、乙二醛、糠醛、丙烯醛、甲基丙烯醛、丙醛、乙醛、巴豆醛、吡啶鎓杀生物剂、苯扎氯铵、神经酰胺、十六烷基三甲基氯化铵、苄索氯铵、氯化十六烷基吡啶、安索氯芬铵、醋酸地喹铵、地喹氯铵、溴化度米芬、醋酸劳利铵、氯化苄乙氧铵、氯化十四烷基-γ-甲吡啶、奥酚氯铵(ortaphonium chloride)、曲比氯铵、烷基二甲基苯甲基氯化铵、椰油基二胺、棉隆、1-(3-氯烯丙基)-氯-3,5,7-三氮杂-1-氮阳离子金刚烷或其组合。
在一个实施方案中,如上文关于支撑剂颗粒或破裂剂所讨论对杀生物剂进行包封或涂布。在一个实施方案中,使用任何合适的包封材料,通过任何合适的包封方法对杀生物剂进行包封或涂布。包封材料是不会与杀生物剂发生不利相互作用或化学反应从而破坏其效用的任何材料。在一个实施方案中,在选定的时间从涂层中释放杀生物剂。
在水力压裂组合物中,支撑剂颗粒是以在地层沉降期间当支撑剂从SAP中释放时能有效地使裂缝保持张开而不改变裂缝的几何结构的量存在。在一个具体实施方案中,支撑剂颗粒是以组合物的总体积计以0.1磅/加仑(lb/gal)至20磅/加仑、具体来说0.25磅/加仑至16磅/加仑并且更具体来说0.25磅/加仑至12磅/加仑的质量浓度存在。在一个实施方案中,SAP是以组合物的总体积计以1磅SAP每一千加仑流体(ppt)至200ppt、具体来说5ppt至100ppt并且更具体来说15ppt至50ppt的质量浓度存在。在水力压裂组合物中,支撑剂颗粒的量与SAP的量的任何比率都是适用的,只要使支撑剂颗粒悬浮在由SAP形成的凝胶中就行。
在一个实施方案中,破裂剂是以组合物的总体积计以0ppt至20ppt、具体来说0ppt至15ppt并且更具体来说0ppt至10ppt的质量浓度存在于水力压裂组合物中。在一些实施方案中,杀生物剂是以10百万分率(ppm)至2000ppm,具体来说50ppm至1500ppm,并且更具体来说50ppm至1000ppm的量存在。粘胶聚合物(如果存在)的量是以总水力压裂组合物体积计0.25加仑粘胶聚合物每1000加仑流体(gpt)至10gpt,具体来说是0.5gpt至8gpt,并且更具体来说是0.5gpt至4gpt。
水力压裂组合物可以用多种方式制造。根据一个实施方案,制造水力压裂组合物的方法包括使超吸附性聚合物与流体接触以使超吸附性聚合物膨胀至膨胀状态,和将多个支撑剂颗粒安置在超吸附性聚合物中以制造水力压裂组合物。如图3中所示,SAP(例如,颗粒12或纤维50)呈具有内部交联14的未膨胀状态20,并且在与流体(未示出)接触之前具有直径D2。如图1和图2中所指示,一旦与流体接触后,SAP(12或50)便随着流体被吸收至SAP(12或50)中而膨胀至直径D1(其中D1大于D2)。另外,在SAP纤维50或具有长轴的SAP的情况下,在由于吸收流体而膨胀后,SAP 50的长度可以延长。应当注意,交联14限制了SAP 12的体积膨胀和最终尺寸。在膨胀状态下(图1或图2),支撑剂颗粒18被安置在SAP(12或50)中。图1、图2和图3中所示的SAP(12或50)表示SAP 12的单个颗粒、纤维等或多个此类物品以及组成SAP(12或50)的聚合物链的聚集体。
可以在安置SAP(12或50)和支撑剂颗粒18之前或之后将添加剂,包括阻垢剂、示踪剂、缓冲剂或其组合加入到流体中。任选地,将添加剂加入到SAP和支撑剂颗粒中。根据一个实施方案,在安置SAP(12或50)和支撑剂颗粒18之前或之后将破裂剂加入到流体中。任选地,将破裂剂加入到SAP和支撑剂颗粒中。
在一个实施方案中,在诸如混合器、掺合器等容器中实现合并水力压裂组合物的组分。在一些实施方案中,水力压裂组合物在不加混合的情况下注入,例如它被“飞速”注入。对组分进行混合、搅动、搅拌等。在一个实施方案中,在水力压裂组合物正被安置在井下时将组分合并。
本文中的水力压裂组合物具有诸多有利的性质,包括在延长的时间段内或者在升高的温度或压力下使支撑剂颗粒悬浮在SAP中。支撑剂颗粒保持悬浮在SAP中的时长、温度或压力是由组成SAP的聚合物链以及交联剂化合物、交联度、支撑剂颗粒的存在量、SAP的浓度和流体的特性决定。
因此,水力压裂组合物包括高度交联SAP、轻度交联SAP或其组合。在水力压裂组合物中,SAP被构造为响应于破裂条件而破裂并且释放支撑剂颗粒。破裂条件包括温度、pH值、破裂剂与SAP之间的接触、SAP呈膨胀状态与使超吸附性聚合物破裂之间的时间流逝。在一个实施方案中,在大于或等于150℉的温度下,在从SAP中释放之前,支撑剂颗粒被安置在SAP中的时间是大于或等于48小时,具体来说是大于或等于36小时,更具体来说是大于或等于24小时,甚至更具体来说是大于或等于18小时,并且又更具体来说是大于或等于20分钟,优选10分钟至18小时。
在一个实施方案中,用于使SAP破裂的pH值是能有效地使SAP中的键、交联剂中的键、SAP与交联剂之间的键或其组合破裂的pH值。同样,在一个实施方案中,pH值导致SAP颗粒之间发生离解,从而从其中释放支撑剂颗粒。在一个实施方案中,pH值是酸性或碱性的,使得SAP中的聚合物链的离子基团被中和,由此影响SAP中存在的流体的量并且引起SAP收缩和支撑剂颗粒迫出。根据一个实施方案,pH值是1至12,具体来说是3至12,并且更具体来说是5至11.5。
在一个实施方案中,即使不存在破裂剂,SAP也会由于破裂条件而破裂。因此,在一个实施方案中,SAP在不与破裂剂接触的情况下便在某一温度、pH值、时间流逝等下发生破裂。
在一个实施方案中,SAP在膨胀状态下的粘度是1厘泊(cP)至1000cP,并且具体来说是1cP至300cP,如针对低于100cP粘度利用Ofite M900流变仪或针对超过100cP粘度利用Grace M5500流变仪在180℉的温度下所测得。
水力压裂组合物可用于例如在裂缝中输送和安置支撑剂颗粒而不使SAP破裂,直到安置支撑剂颗粒之后,从而防止支撑剂颗粒沉降并且因此增加总断裂表面积。根据一个实施方案,水力压裂组合物被用于形成裂缝。在一个实施方案中,在裂缝中安置多个支撑剂颗粒的方法包括将水力压裂组合物安置在井下环境中。所述水力压裂组合物包括SAP,所述SAP呈膨胀状态并且被构造为响应于破裂条件而破裂,从而由超吸附性聚合物形成分解聚合物。水力压裂组合物还包括多个支撑剂颗粒,所述多个支撑剂颗粒被安置在所述SAP中,随后响应于使所述SAP破裂而从所述SAP释放所述多个支撑剂颗粒;添加剂,所述添加剂包含阻垢剂、示踪剂、缓冲剂或其组合;和流体,所述流体使所述SAP膨胀至膨胀状态。在这种方法中,在井下环境中形成裂缝是通过以下方式实现:由所述水力压裂组合物对井下环境施加液压力;将所述水力压裂组合物安置在裂缝中;在形成裂缝之后使超吸附性聚合物破裂;和从超吸附性聚合物释放所述多个支撑剂颗粒,从而将所述多个支撑剂颗粒安置在裂缝中。以这种方式,支撑剂颗粒不会沉降至裂缝底部。所述井下环境是例如储层温度、地层水、地层岩石、砂等,其在此类岩石、砂等中含有例如不同尺寸的孔隙或纹理。
如图4中所示,在破裂条件出现之后,SAP呈破裂状态30,使得SAP与从SAP中释放的支撑剂颗粒18形成例如分解聚合物32。虽然分解聚合物32被显示为分开的片段(例如,聚合物、寡聚物、单体、分子、原子等,其带电或呈电中性),但是在一个实施方案中,所述分解聚合物是通过使所有或一些交联破裂而由SAP形成,因此SAP的聚合物链保持完整。设想SAP中的构象变化会从SAP中释放支撑剂颗粒并且确保良好传导性。
在一个实施方案中,交联或SAP因某些条件(诸如热或pH值)而被降解。降解通过使交联剂中的键或交联剂与SAP的聚合物链之间的键破裂来降低SAP中的交联度。一般来说,降低SAP的交联度会增加被SAP吸收的流体的量,或增加由于流体吸收所致的SAP体积增加。在一个实施方案中,上述条件使交联中的键裂解,而基本上不会使SAP的聚合物骨架降解。在一些实施方案中,这些条件还使SAP的聚合物骨架降解。
除了将水力压裂组合物安置在井下环境中以便水力压裂地层以外,该方法还包括安置其他要素,诸如水、井下流体(例如盐水或其他上述流体)、粘胶聚合物或其组合。因此,在一个实施方案中,该方法还包括将水、粘胶聚合物或其组合安置在井下环境中和利用水力压裂组合物、水、粘胶聚合物或其组合物来形成裂缝。加入顺序可以变化,并且注入每一者的时间相同或不同。根据一个实施方案,为了水力压裂地层,将无支撑剂流体和含支撑剂流体以交替的顺序注入到地下地层中。可以首先注入无支撑剂流体,然后注入含支撑剂流体。替代地,首先注入含支撑剂流体,然后注入无支撑剂流体。
在一个示例性实施方案中,所述无支撑剂流体包含水性载体,所述水性载体包含水、盐水、酸或碱和润滑剂。所述润滑剂可以包含聚丙烯酰胺、瓜尔胶、瓜尔胶衍生物、甘油、多糖(诸如纤维素和淀粉)或其组合。当润滑剂包含聚丙烯酰胺,例如MaxPerm 20A时,MaxPerm20A是以0.25至15加仑每一千加仑无支撑剂流体的量存在。当润滑剂包含瓜尔胶时,润滑剂是以1至50磅每一千加仑无支撑剂流体的量存在。含支撑剂流体包含SPP、安置在SPP中的多个支撑剂颗粒、使SPP膨胀至膨胀状态的流体和任选的包含瓜尔胶、瓜尔胶衍生物、聚丙烯酰胺、甘油、多糖或其组合的线性凝胶或粘性聚合物。含支撑剂流体可以是本文中公开的水力压裂组合物。通过使用该方法,在支撑剂堆内产生高传导性通道。效果在图15中加以说明。
在另一个示例性实施方案中,无支撑剂流体包含SPP、使SPP膨胀的流体和任选的包含瓜尔胶、瓜尔胶衍生物、聚丙烯酰胺、甘油、多糖或其组合的粘性聚合物。对于无支撑剂流体,通常在一千加仑无支撑剂流体中制备20至60磅SPP。含支撑剂流体包含水性载体,所述水性载体包含水、盐水、酸或碱、支撑剂和润滑剂。所述润滑剂可以包含聚丙烯酰胺、瓜尔胶、瓜尔胶衍生物、甘油、多糖或其组合。当润滑剂包含聚丙烯酰胺,例如MaxPerm 20A时,MaxPerm 20A是以0.25至15加仑每一千加仑无支撑剂流体的量存在。当润滑剂包含瓜尔胶时,聚合物是以1至50磅每一千加仑含支撑剂流体的量存在。通过这种方法可以实现异质支撑剂分布。有益效果在图16中加以说明。
在一个实施方案中,水(或盐水)和粘性聚合物的初始注入是例如各15分钟,但是在一些实施方案中,注入时长是不同的。水力压裂组合物的注入时间与水或粘胶聚合物相同或不同,例如持续2小时。设想注入时间可以变化并且是基于地层条件和水力压裂组合物、其他流体(例如,盐水)、粘胶聚合物等的性质加以选择。
水力压裂组合物的益处在于,支撑剂颗粒保持安置在SAP中,直到破裂条件引起SAP破裂。如图5中所示,安置在套管102中的管状物104穿过地层100,但是在一些实施方案中,只存在套管102或只存在管状物104。水力压裂组合物120通过管状物104中的孔口(未示出)从管状物104的内部转移,从而接触地层100。水力压裂组合物120(其与图1或图2的类似或相同)使地层100断裂以产生裂缝106。支撑剂颗粒18被安置在SAP 12中,直到出现破裂条件,此时SAP 12破裂以形成分解聚合物122并且释放支撑剂颗粒18,如图6中所示。这里,在裂缝106闭合之前,SAP 12没有破裂,支撑剂颗粒18也没有从SAP 12中释放。因此,在裂缝106闭合之前,支撑剂颗粒18没有沉降到裂缝106底部,所以裂缝106的几何结构不会因SAP12破裂而受到负面影响。也就是说,在裂缝106闭合之前,它具有高度H1。闭合之后,裂缝具有高度H2。在裂缝开始闭合之后,SAP 12破裂,并且形成分解聚合物122。由于支撑剂颗粒18高度悬浮在SAP 12中,所以裂缝106的高度H2相对于原始闭合前高度H1没有显著变化,使得高度H2(闭合后)与原始高度H1(闭合前)的大小几乎相同。
在SAP 12破裂过程中,地层压力原位挤压支撑剂颗粒,通过已破裂流体泄出而免于沉降至裂缝底部。以这种方式,水力压裂组合物在裂缝中实现了增强的支撑剂颗粒输送和垂直分布。因此,相对于支撑剂颗粒18的不完全或不完美安置,烃类或其他流体通过裂缝106从地层100传导至管状物104(或在管状物104与套管102之间的空间)中有所增加,如图7和图8中所示。因此,水力压裂组合物120输送并且安置支撑剂颗粒18,以确保支撑剂颗粒18维持裂缝106以与初始形成的裂缝106相同或基本上相同的几何结构张开,并且因此提供断裂程度更甚于支撑剂颗粒沉降至裂缝底部时的表面区域,如图7和图8中所示。以这种方式,当使用本文中的水力压裂组合物时,出现了在地层与钻孔之间传输烃类和其他流体的高传导途径。
关于图7和图8,当在不利于SAP使支撑剂颗粒130悬浮的情况下使用不含本文中的水力压裂组合物的某些压裂体系,诸如悬浮在流体132中的支撑剂颗粒130时,支撑剂颗粒130从流体132中沉降并且在裂缝106闭合之前聚集在裂缝106底部(图7)。虽然裂缝106在闭合之前具有原始高度H2(图7),但是所述高度H2在闭合之后降至降低的高度H4,因为支撑剂颗粒130在裂缝106闭合之前沉降到裂缝106底部。
通过以下非限制性实施例进一步说明本文中的水力压裂组合物和方法。
将超吸附性聚合物(SAP)(QX-A1051;Nippon Shokubai)以40千分率(ppt)(w/v)的浓度与自来水混合。测定混合物的pH值是约7。使用缓冲液BF-10L(得自Baker Hughes)将pH值调节至大于7,并且使用得自Baker Hughes的缓冲液BF-9L将pH值调节至小于7。在20℃和大气压下,使用Chandler M5550仪器,根据API RP 39标准来记录混合物在不同的pH值下的粘度。图17是显示这一实施例中pH值对粘度的影响的图。如图17中所示,在约7至约8的流体pH值下记录到最大粘度。
本文中公开的所有范围都包括端点,并且所述端点可以独立地彼此组合。所述范围是连续的,并且因此含有在所述范围中的每个值和其子集。除非另有陈述或对上下文不适用,否则所有百分比在表达数量时都是重量百分比。如本文中所使用,“组合”包括掺合物、混合物、合金、反应产物等等。此外,如本文中所使用,“组合”是指包含所指出的成分、组分、化合物或要素中的至少一种任选地与未指出的一种或多种类似成分、组分、化合物或要素的组合。除非本文中另外指明或者与上下文明显矛盾,否则在描述本发明的上下文中(尤其是在以下权利要求书的上下文中)使用术语“一个/种”和“所述”以及类似指代语应当被视为涵盖单数和复数二者。“或”意指“和/或”。连词“或”用于连接列出的对象或替代物,并且不是反义连词;相反,所述要素可以单独使用,或者可以在适当的情况下组合在一起。
应当进一步指出,术语“第一”、“第二”、“主要”、“次要”等在本文中不表示任何顺序、数量或重要性,而是用于区分一个要素与另一个要素。结合数量使用的修饰语“约”包括所述值,并且具有上下文所规定的含义(例如,其包括与具体数量的测量相关的误差度)。所有参考文献都以引用的方式并入本文中。
虽然已经示出并且描述了一个或多个实施方案,但是可以在不脱离本发明的精神和范围的情况下对其进行修改和替换。因此,应了解,已经通过说明而不是限制的方式描述了本发明。本文中的实施方案可以独立地加以使用或者可以加以组合。
Claims (15)
1.一种水力压裂组合物,所述水力压裂组合物包含:
超吸附性聚合物,所述超吸附性聚合物呈膨胀状态并且被构造为响应于破裂条件而破裂;
多个支撑剂颗粒,所述多个支撑剂颗粒被安置在所述超吸附性聚合物中,随后响应于使所述超吸附性聚合物破裂而从所述超吸附性聚合物释放所述多个支撑剂颗粒;
井处理剂,所述井处理剂包括阻垢剂、示踪剂、pH值缓冲剂或其组合;和
流体,所述流体用于使所述超吸附性聚合物膨胀至所述膨胀状态。
2.如权利要求1所述的水力压裂组合物,其中所述超吸附性聚合物包含来源于丙烯酸酯、丙烯酰胺、乙烯基吡咯烷酮、乙酸乙烯酯、乙烯醇、糖、2-丙烯酰胺-2-甲基丙磺酸、其衍生物或其组合的重复单元;并且其中所述超吸附性聚合物包含多个交联。
3.如权利要求1至2中任一项或多项所述的水力压裂组合物,所述水力压裂组合物包含以所述水力压裂组合物的总重量计约0.001重量%至约5重量%的所述阻垢剂。
4.如权利要求1至3中任一项或多项所述的水力压裂组合物,其中所述阻垢剂包括含羧酸、磺酸或膦酸的化合物、含羧酸、磺酸或膦酸基团的聚合物,或其组合。
5.如权利要求1至4中任一项或多项所述的水力压裂组合物,其中所述阻垢剂包括氨基三亚甲基膦酸、1-羟基亚乙基-1,1-二膦酸、2-膦酰基丁烷-1,2,4-三甲酸、2-羟乙基-氨基-双(亚甲基膦酸)、乙二胺四(亚甲基膦酸)、四亚甲基二胺四(亚甲基膦酸)、六亚甲基二胺四(亚甲基膦酸)、2-羟基膦酰基乙酸、二亚乙基三胺五(亚甲基膦酸)、双(六亚甲基三胺五(亚甲基膦酸)、聚氨基聚醚亚甲基膦酸酯或其盐、膦基聚羧酸盐、聚丙烯酸、聚马来酸、丙烯酸共聚物、磺酸酯聚丙烯酸酯共聚物、聚乙烯磺酸酯、羧甲基菊粉、聚天冬氨酸盐或其组合。
6.如权利要求1至5中任一项或多项所述的水力压裂组合物,所述水力压裂组合物包含以所述水力压裂组合物的总重量计约0.001重量%至约10重量%的所述示踪剂。
7.如权利要求1至6中任一项或多项所述的水力压裂组合物,其中所述示踪剂包括氟化苯甲酸、全氟化烃、醇、酮、有机酸、卤代化合物或其组合。
8.如权利要求1至7中任一项或多项所述的水力压裂组合物,其中所述示踪剂被包封、涂布、合并至粘合剂中、吸附至基质上或吸附至基质中。
9.如权利要求1至8中任一项或多项所述的水力压裂组合物,所述水力压裂组合物包含以所述水力压裂组合物的总重量计约0.01重量%至约10重量%的所述pH值缓冲剂。
10.如权利要求1至9中任一项或多项所述的水力压裂组合物,其中所述pH值缓冲剂将所述水力压裂组合物的pH值维持为约6至约9。
11.如权利要求1至10中任一项或多项所述的水力压裂组合物,其中所述pH值缓冲剂是碱金属或碱土金属碳酸盐、柠檬酸盐、葡萄糖酸盐、磷酸盐或酒石酸盐、碱土金属氧化物、有机聚电解质或其组合。
12.如权利要求1至11中任一项或多项所述的水力压裂组合物,其中所述水力压裂组合物包含所述pH值缓冲剂,而且还包含缓释酸,其中所述缓释酸包括乙二醛、包封酸、涂布酸或其组合。
13.如权利要求1至12中任一项或多项所述的水力压裂组合物,所述水力压裂组合物还包含破裂剂,其中所述破裂剂包括过氧化物、过硫酸盐、过酸或其组合。
14.一种在裂缝中安置多个支撑剂颗粒的方法,所述方法包括:
在井下环境中的裂缝中安置水力压裂组合物,所述水力压裂组合物包含:
超吸附性聚合物,所述超吸附性聚合物呈膨胀状态并且被构造为响应于破裂条件而破裂,以便由所述超吸附性聚合物形成分解聚合物;
多个支撑剂颗粒,所述多个支撑剂颗粒被安置在所述超吸附性聚合物中,随后响应于使所述超吸附性聚合物破裂而从所述超吸附性聚合物释放所述多个支撑剂颗粒;
井处理剂,所述井处理剂包括阻垢剂、示踪剂、pH值缓冲剂或其组合;和
流体,所述流体用于使所述超吸附性聚合物膨胀至所述膨胀状态;以及
在安置在所述裂缝中之后,使所述超吸附性聚合物破裂;以及
从所述超吸附性聚合物释放所述多个支撑剂颗粒,以将所述多个支撑剂颗粒安置在所述裂缝中。
15.如权利要求14所述的方法,所述方法还包括与不含所述井处理剂的组合物相比,减少由结垢、盐形成、石蜡沉积、沥青质沉积、发泡剂沉积、乳化、气体水合物形成、腐蚀、发泡剂、氧清除剂、H2S清除剂、杀生物剂、表面活性剂或其组合导致的不良影响。
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CN107956470A (zh) * | 2017-11-15 | 2018-04-24 | 北京捷贝通石油技术有限公司 | 一种气基痕量化学示踪剂及利用其测量气井各段产气贡献量的方法 |
CN107989600A (zh) * | 2017-12-13 | 2018-05-04 | 北京捷贝通石油技术有限公司 | 一种水基痕量化学示踪剂及用于测量注水井井间连通性的方法 |
CN107989600B (zh) * | 2017-12-13 | 2023-09-12 | 捷贝通石油技术集团股份有限公司 | 一种水基痕量化学示踪剂及用于测量注水井井间连通性的方法 |
CN108919379A (zh) * | 2018-05-08 | 2018-11-30 | 中国石油天然气股份有限公司 | 氟化类气体示踪剂及其应用与监测示踪方法 |
CN108708707A (zh) * | 2018-05-25 | 2018-10-26 | 中国石油大学(华东) | 一种磁性支撑剂的丘陵式铺置方法及应用 |
CN110835523A (zh) * | 2018-08-17 | 2020-02-25 | 中国石油化工股份有限公司 | 一种用于稠油冷采的乳化降粘剂及其制备方法 |
CN110835523B (zh) * | 2018-08-17 | 2022-02-15 | 中国石油化工股份有限公司 | 一种用于稠油冷采的乳化降粘剂及其制备方法 |
CN113631682A (zh) * | 2018-11-02 | 2021-11-09 | 罗地亚经营管理公司 | 用于在增产处理期间进行蜡抑制的聚合物分散体 |
CN113631682B (zh) * | 2018-11-02 | 2024-01-26 | 能源解决方案(美国)有限责任公司 | 用于在增产处理期间进行蜡抑制的聚合物分散体 |
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CN110566190B (zh) * | 2019-09-29 | 2021-02-19 | 西南石油大学 | 高颗粒浓度实验条件下的缝内支撑剂运动轨迹追踪方法 |
CN110669481A (zh) * | 2019-10-22 | 2020-01-10 | 石家庄华莱鼎盛科技有限公司 | 钻井液用抗盐降滤失剂改性树胶树脂 |
CN110724515B (zh) * | 2019-10-29 | 2020-06-23 | 成都一桶石油科技有限公司 | 一种压裂支撑剂用空气悬浮剂及其施工方法 |
CN110724515A (zh) * | 2019-10-29 | 2020-01-24 | 成都一桶石油科技有限公司 | 一种压裂支撑剂用空气悬浮剂及其施工方法 |
CN111335863B (zh) * | 2020-04-10 | 2021-03-12 | 西南石油大学 | 一种常规和胶囊型可溶支撑剂交替注入的通道压裂方法 |
CN111335863A (zh) * | 2020-04-10 | 2020-06-26 | 西南石油大学 | 一种常规和胶囊型可溶支撑剂交替注入的通道压裂方法 |
CN113653486A (zh) * | 2021-09-03 | 2021-11-16 | 捷贝通石油技术集团股份有限公司 | 一种缓释型长效示踪剂及其制备方法 |
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AU2015362929B2 (en) | 2018-02-01 |
NZ733169A (en) | 2018-05-25 |
MX2017007128A (es) | 2017-08-18 |
RU2679778C2 (ru) | 2019-02-12 |
RU2017122066A (ru) | 2019-01-17 |
CA2970488A1 (en) | 2016-06-23 |
EP3234060A4 (en) | 2018-06-13 |
AU2015362929A1 (en) | 2017-07-13 |
EP3234060A1 (en) | 2017-10-25 |
NO20171068A1 (en) | 2017-06-29 |
RU2017122066A3 (zh) | 2019-01-17 |
CA2970488C (en) | 2020-07-07 |
BR112017011956A2 (pt) | 2017-12-26 |
WO2016100048A1 (en) | 2016-06-23 |
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