CN107429561A - 处理含烃地层的压裂流体和方法 - Google Patents
处理含烃地层的压裂流体和方法 Download PDFInfo
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- CN107429561A CN107429561A CN201680016010.1A CN201680016010A CN107429561A CN 107429561 A CN107429561 A CN 107429561A CN 201680016010 A CN201680016010 A CN 201680016010A CN 107429561 A CN107429561 A CN 107429561A
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- Prior art keywords
- super absorbent
- absorbent polymer
- polymer
- fracturing composition
- fracturing
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- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
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- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
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- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical class OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
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- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- RZKYDQNMAUSEDZ-UHFFFAOYSA-N prop-2-enylphosphonic acid Chemical compound OP(O)(=O)CC=C RZKYDQNMAUSEDZ-UHFFFAOYSA-N 0.000 description 1
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- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium erythorbate Chemical compound [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
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- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
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- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
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- 150000003624 transition metals Chemical class 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- ZBZHVBPVQIHFJN-UHFFFAOYSA-N trimethylalumane Chemical compound C[Al](C)C.C[Al](C)C ZBZHVBPVQIHFJN-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
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- 229910052727 yttrium Inorganic materials 0.000 description 1
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- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK 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
- E21B43/267—Methods for stimulating production by forming crevices or fractures reinforcing fractures by propping
-
- 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
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
-
- 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
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/06—Clay-free compositions
- C09K8/12—Clay-free compositions containing synthetic organic macromolecular compounds or their precursors
-
- 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
- C09K8/02—Well-drilling compositions
- C09K8/32—Non-aqueous well-drilling compositions, e.g. oil-based
- C09K8/34—Organic liquids
-
- 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
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
-
- 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
- C09K8/56—Compositions for consolidating loose sand or the like around wells without excessively decreasing the permeability thereof
- C09K8/57—Compositions based on water or polar solvents
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Abstract
压裂被井穿过的地下地层的方法包括:形成压裂组合物,所述压裂组合物包含载体流体;以及超吸收性聚合物组分,所述超吸收性聚合物组分包含以下中的一种或多种:支撑剂与呈未水合形式的第一超吸收性聚合物的第一复合物,所述第一超吸收性聚合物至少部分嵌入所述支撑剂的空隙区域中;涂布的超吸收性聚合物;具有三维网络的超吸收性材料;或第二超吸收性聚合物与缓释破碎剂的第二复合物;以及将所述水力压裂组合物泵送至所述地下地层中以形成或扩大裂缝。
Description
相关申请的交叉引用
本申请要求2015年3月30日提交的美国专利申请号62/140,105的权益,该申请以引用的方式整体并入本文中。
背景
本公开涉及处理含烃地层的压裂流体和方法,特别是含有超吸收性聚合物的压裂流体以及其在压裂应用中的用途。
水力压裂是一种用于与大面积的地下地层形成高传导性连通的刺激过程。该过程增加地层内的有效井筒区域,使得可加快夹带油或气的生产。该方法的效率通常是用由刺激处理产生的接触的表面积的总量来度量。
在水力压裂期间,在超过目标储集岩的断裂压力的压力下泵送压裂流体,以形成或扩大被井筒穿过的地下地层内的裂缝。在断裂开始后,将后续阶段的含有化学试剂以及支撑剂的流体泵送至所形成的裂缝中。在泵送期间裂缝通常继续生长,并且支撑剂以用以将裂缝撑开的可渗透填充物的形式保留在裂缝中。在处理完成后,裂缝闭拢至支撑剂上。支撑剂使所形成的裂缝保持打开,从而为烃类和/或其他地层流体流入井筒提供高度传导性通路。
可将压裂流体破碎至极小的粘度并且允许其在生产之前流回。对实际问题来说破碎的时间设定可为重要的。往往必须在初始粘度和破碎之后的最终粘度之间达到微妙的平衡。如果压裂流体破碎得太早,那么支撑剂会在完成压裂处理之前从压裂流体分离并且沉降至裂缝的底部。在这种情况下,裂缝的几何形状和井产能会被削弱。
尽管本领域中有所有的进步,但仍需要替代的组合物和方法来压裂含烃地层。如果此类组合物和方法具有改善的支撑剂运输能力,那么将是一个优点。如果可提供组合物和方法来控制破碎压裂流体的时间设定,那么将是另一个优点。
简述
在一个实施方案中,压裂被井穿过的地下地层的方法包括:形成压裂组合物,所述压裂组合物包含载体流体;以及超吸收性聚合物组分,所述超吸收性聚合物组分包含以下中的一种或多种:支撑剂与呈未水合形式的第一超吸收性聚合物的第一复合物,第一超吸收性聚合物至少部分嵌入支撑剂的空隙区域中;涂布的超吸收性聚合物;具有三维网络的超吸收性材料;或第二超吸收性聚合物与缓释破碎剂的第二复合物;以及将水力压裂组合物泵送至地下地层中以形成或扩大裂缝。
在另一实施方案中,压裂被井穿过的地下地层的方法包括:形成压裂组合物,所述压裂组合物包含载体流体;支撑剂;每一千加仑的压裂组合物约10磅至约100磅的超吸收性聚合物;以及每一千加仑的压裂组合物约1磅至约30磅或4至20磅的粘度改性剂,粘度改性剂包括以下中的一种或多种:尤坦胶(diutan);淀粉-丙烯腈接枝聚合物水解产物;磺化聚苯乙烯;聚乙烯醇;聚乙烯吡略烷酮;或聚丙烯腈;以及将水力压裂组合物泵送至地下地层中以形成或扩大裂缝。
在另一实施方案中,压裂被井穿过的地下地层的方法包括:形成压裂组合物,所述压裂组合物包含载体流体;支撑剂;约30磅至约80磅的聚合物,所述聚合物包括以下中的一种或多种:魔芋葡甘露聚糖;淀粉-丙烯腈接枝聚合物水解产物;羧甲基纤维素;交联聚丙烯酸酯;磺化聚苯乙烯;水解聚丙烯酰胺;聚乙烯醇;聚乙酸乙烯酯;聚氧化乙烯;聚乙烯吡略烷酮;或聚丙烯腈。
在另一实施方案中,压裂被井穿过的地下地层的方法包括形成压裂组合物,所述压裂组合物包含载体流体、线性瓜尔胶、以在压裂操作期间有效减少流体损失的量存在的超吸收性聚合物、任选存在的针对线性瓜尔胶的交联剂;以及将水力压裂组合物泵送至地下地层中以形成或扩大裂缝。
压裂被井穿过的地下地层的方法包括:形成压裂组合物,所述压裂组合物包含载体流体、支撑剂、超吸收性聚合物、在大于约250°F的温度下在不存在任何活化剂的情况下有效破碎超吸收性聚合物的破碎剂、包含封装于封装剂内的活化剂的封装的活化剂,活化剂有效活化破碎剂,使得破碎剂或其衍生物在小于约200°F的温度下破碎超吸收性物质;将水力压裂组合物泵送至地下地层中以形成或扩大裂缝;允许活化剂从封装剂中扩散出来;以及破碎超吸收性聚合物。
压裂被井穿过的地下地层的方法包括:将第一压裂组合物注入地下地层,所述第一压裂组合物包含第一载体流体、支撑剂、超吸收性聚合物以及破碎剂和针对破碎剂的活化剂中的一种;将第二压裂组合物注入地下地层,第二压裂组合物包含第二载体流体以及第一压裂组合物中未包括的破碎剂或活化剂;并且在注射第二压裂组合物之后在小于约200°F的温度下破碎超吸收性聚合物。
压裂被井穿过的地下地层的方法包括:将第一压裂组合物注入地下地层,所述第一压裂组合物包含第一载体流体、支撑剂以及超吸收性聚合物,第一压裂组合物不含针对超吸收性聚合物的破碎剂;将第二压裂组合物注入地下地层,第二压裂组合物包含第二载体流体和在小于约200°F的温度下有效破碎超吸收性聚合物的破碎剂;以及在注射第二压裂组合物之后破碎超吸收性聚合R物。
详述
目前,该领域中使用的约三分之一的压裂流体是基于线性瓜尔胶的。这些基于线性瓜尔胶的流体通常含有10至40ppt的标准瓜尔胶聚合物。这些流体的相关流体粘度在5cP至30cP范围内。已发现在压裂应用中可使用含有超吸收性聚合物的组合物来代替基于线性瓜尔胶的流体。超吸收性聚合物在仅使用常规聚合物加载量的一部分时即允许产生相等或更大粘度的压裂流体。基于线性瓜尔胶的流体对地层相对具破碎性,因为它们在破碎后重新得到的传导性低。相反,超吸收性聚合物在破碎后已显示出高的重新得到的传导性。
如本文中所讨论,超吸收性聚合物为一种聚合物,所述聚合物能够在膨胀和形成凝胶或粘性材料的情况下吸收大量的水性液体,诸如水、盐水、酸或碱,并且将所吸收的流体保持在某一压力或温度下。可在压裂组合物中使用超吸收性聚合物来将支撑剂粒子运输至裂缝。发明人已发现各种方法来提高超吸收性聚合物运输支撑剂的效率。
在一个实施方案中,已发现可将呈未水合形式的超吸收性聚合物放置于支撑剂内或至少部分嵌入支撑剂的空隙区域中。将超吸收性聚合物放置于支撑剂中允许聚合物膨胀,从而与支撑剂组合降低压裂流体内所得粒子的有效密度。除了聚合物粒子在膨胀时将起到运输的作用,通过拖曳,支撑剂随着超吸收性聚合物一起被运送至裂缝更深处。影响支撑剂的沉降速率的能力就可以得到解决。
复合物可包括在此公开的超吸收性聚合物中的任一种,除了超吸收性聚合物呈未水合形式。用于制备复合物的支撑剂具有空的间隙或孔隙。多孔支撑剂包括具有固有和/或诱导的孔隙的任何天然存在的或制造的或改造的多孔陶瓷颗粒材料。可使用的支撑剂的类型包括中空棒状支撑剂,以及其中发现空隙或在支撑剂表面上有意地形成间隙的那些。空隙区域内的支撑剂包括可从Baker Hughes Inc.商购获得的LitePropTM材料系列内的那些。
可商购获得的仪器ACCUPYC 1330自动气体比重计(Micromeritics,Norcross,Ga.)使用氦气作为惰性气体,并且可使用制造商建议的程序来测定颗粒的内部孔隙率。用于制备复合物的支撑剂的内部孔隙率通常为约5至约40体积%或约10至约35体积%或约15至约25体积%。在一个实施方案中,复合物中的支撑剂具有小于约2.4的表观比重。
用于复合物中的非天然多孔颗粒材料的实例包括但不限于多孔陶瓷粒子,诸如可作为ECONOPROP从Carbo Ceramics Inc.获得的那些粒子,以及美国专利号5,188,175中所描述的那些烧制高岭石质材料。如本专利中所描述,此类粒子可包括从氧化铝含量在约25%与40%之间且二氧化硅含量在约50%与65%之间的原材料(诸如高岭土)得到的固体球状团粒或粒子。可采用淀粉粘合剂。此类粒子的特征可为具有约1.39至约2.41的二氧化硅与氧化铝含量比,以及约2.20与约2.60之间或约2.20与约2.70之间的ASG。
还应了解,可从原材料选择性地制造多孔陶瓷粒子,诸如美国专利号5,188,175;美国专利号4,427,068;以及美国专利号4,522,731中所描述的那些,诸如通过在初始材料制造过程中包括所选的处理步骤以产生具有所要的孔隙度、渗透性、表观密度或ASG特征以及其组合的材料。举例来说,可在约1235°F或约1300°F的相对低的温度下烧制此类原材料以实现所要晶体结构和更高度多孔并且更轻的结构。在此类粒子的一个示例性实施方案中,可选择来自Carbo Ceramics Inc.的约20/40筛孔尺寸多孔材料烧制高岭石粒子来用于复合物中。这些粒子具有以下内部特征:体积表观密度约1.16、内部孔隙率约59.3%。
如本文所用,术语“嵌入”应进一步指通过例如真空和/或压力浸渍部分或完全用超吸收性聚合物浸渍。举例来说,可将多孔支撑剂浸没在呈未水合形式的超吸收性聚合物中并且然后暴露于压力和/或真空以至少部分渗透或浸渍支撑剂。超吸收性聚合物渗透多孔支撑剂的程度为以体积计不到约1%渗透至以体积计不到约25%渗透。
可通过使用任何合适的湿法或干法用超吸收性聚合物处理多孔支撑剂来制备复合物。多孔支撑剂的孔隙率特征允许通过毛细管作用使未水合的超吸收性聚合物至少部分被拉入多孔支撑剂的多孔基质中。举例来说,可使用真空将一种或多种超吸收性聚合物至少部分拉入多孔颗粒材料的多孔基质中,和/或可在压力下迫使其至少部分进入多孔基质。在另一实施方案中,混合超吸收性聚合物的薄片并且按压在支撑剂粒子上,使得超吸收性聚合物至少部分渗透支撑剂粒子的空的空隙,从而将支撑剂粒子锁定至超吸收性聚合物薄片。
对复合物中的超吸收性聚合物和支撑剂的相对量以及压裂组合物中的复合物的相对量加以选择,使得支撑剂以按组合物的总体积计0.10磅/加仑(lb/gal)至20lb/gal、具体地说0.25lb/gal至16lb/gal并且更具体地说0.25lb/gal至12lb/gal的质量浓度存在,并且超吸收性聚合物以按组合物的总体积计10磅SAP/一千加仑流体(ppt)至200ppt、具体地说20ppt至100ppt并且更具体地说30ppt至80ppt的质量浓度存在。在一个实施方案中,超吸收性聚合物与支撑剂的复合物以每一千加仑的压裂组合物约10磅至约200磅、约20磅至约100磅或约30磅至约80磅的复合物的量存在。
在另一实施方案中,还已发现可通过包括具有三维网络的超吸收性材料来改善水力压裂组合物的支撑剂悬浮能力。如本文所用,三维网络是指包含具有负电荷的超吸收性聚合物以及键合至具有负电荷的所述超吸收性聚合物的阳离子或非离子聚合物的网络。不希望受理论的束缚,据信三维网络是通过带负电荷的超吸收性聚合物与阳离子或非离子聚合物之间的诸如范德华力等力形成。进一步不希望受理论的束缚,据信一旦通过低剂量阳离子或非离子聚合物的聚合物链将超吸收性聚合物球体(弱)连接至三维网络中,即大大提高支撑剂悬浮和运送能力。具有负电荷的示例性超吸收性聚合物包括本文中所公开的阴离子聚合物。特别提及丙烯酸和丙烯酸钠的具有衍生自聚乙二醇二丙烯酸酯的交联键的共聚物。示例性阳离子聚合物包括阳离子丙烯酰胺共聚物。示例性非离子聚合物包括聚乙烯醇、聚乙酸乙烯酯或包含前述中的至少一种的组合。具有三维网络的超吸收性材料中的阳离子或非离子聚合物的量可为以具有三维网络的超吸收性材料的总重量计约0.1重量%至约30重量%或0.5重量%至20重量%。
在另一实施方案中,已发现可使用涂布的超吸收性聚合物来减慢水合速率,并且减少对含有超吸收性聚合物的流体的剪切破碎,由此增加超吸收性聚合物的支撑剂运送能力。
涂布的超吸收性聚合物的涂层包括有机化合物、热固性或热塑性聚合物或蜡。有机化合物包括环氧树脂、酚醛树脂、聚氨酯、聚碳二酰亚胺、聚酰胺、聚酰胺酰亚胺、呋喃树脂或其组合。酚醛聚合物为例如由苯酚、双酚或其衍生物与多聚甲醛的反应获得的苯酚甲醛树脂。示例性热塑性材料包括聚乙烯、丙烯腈-丁二烯苯乙烯、聚苯乙烯、聚氯乙烯、氟塑料、聚硫化物、聚丙烯、苯乙烯丙烯腈、尼龙以及亚苯基氧化物。示例性热固性材料包括环氧树脂、酚醛树脂(真正的热固性聚合物,诸如甲阶树脂(resole)或由硬化剂赋予热固性的热塑性树脂)、聚酯树脂、聚氨酯、环氧改性酚醛聚合物以及其衍生物。特别提及蜡。
任选地,可视所使用的特定涂布材料而定将涂层固化。用于涂层的合适的固化剂为含氮化合物,诸如胺和其衍生物;含氧化合物,诸如羧酸封端的聚酯、酸酐、苯酚-甲醛树脂、氨基-甲醛树脂、苯酚、双酚A以及甲酚酚醛清漆、酚封端的环氧树脂;含硫化合物,诸如聚硫化物、聚硫醇;以及催化固化剂,诸如叔胺、路易斯酸、路易斯碱;或其组合。可使用本领域中已知用于涂布固体粒子或纤维的任何方法。
水力压裂组合物还可包含低剂量粘度改性剂,即在低剪切速率下具有大粘度的聚合物,诸如黄原胶、尤坦胶,以进一步提高其支撑剂悬浮能力。此外,添加粘弹性表面活性剂(VES)胶凝剂也增强支撑剂悬浮。其他聚合物包括淀粉-丙烯腈接枝聚合物水解产物、羧甲基纤维素、交联聚丙烯酸酯、磺化聚苯乙烯、水解聚丙烯酰胺、聚乙烯醇、聚氧化乙烯、聚乙烯吡略烷酮、聚丙烯腈或包含前述中的至少一种的组合。特别提及尤坦胶、淀粉-丙烯腈接枝聚合物水解产物、磺化聚苯乙烯、聚乙烯醇、聚乙烯吡略烷酮以及聚丙烯腈。在一些实施方案中,粘度改性剂未交联。如果使用,那么粘度改性剂可以每一千加仑的压裂组合物约1至30磅或约4至约20磅的量存在。
适合用于本文中的粘弹性表面活性剂包括但不必限于非离子、阳离子、两性以及两性离子表面活性剂。这些表面活性剂可单独使用或与无机盐或其他表面活性剂组合以产生有序结构,这使得基于水性物质的流体的粘度增加。两性离子/两性表面活性剂的具体实例包括但不必限于甘氨酸二羟基烷基酯、烷基两性乙酸酯或丙酸酯、烷基甜菜碱、烷基酰胺基丙基甜菜碱以及衍生自某些蜡、脂肪以及油的烷基亚氨基单丙酸酯或烷基亚氨基双丙酸酯。季胺表面活性剂通常为阳离子的,而甜菜碱通常为两性离子的。当表面活性剂为阳离子表面活性剂时,它与负反离子或与芳族有机阴离子缔合,所述负反离子可为无机阴离子,诸如硫酸根、硝酸根、高氯酸根或卤离子,诸如Cl、Br;所述芳族有机阴离子为诸如水杨酸根、萘磺酸根、对氯苯甲酸根和间氯苯甲酸根、3,5和3,4和2,4-二氯苯甲酸根、叔丁基苯酚根和乙基苯酚根、2,6和2,5-二氯苯酚根、2,4,5-三氯苯酚根、2,3,5,6-四氯苯酚根、对甲基苯酚根、间氯苯酚根、3,5,6-三氯吡啶甲酸根(trichloropicolinate)、4-氨基-3,5,6-三氯吡啶甲酸根、2,4-二氯苯氧基乙酸根。当表面活性剂为阴离子表面活性剂时,它与例如Na+或K+等正反离子缔合。当它为两性离子表面活性剂时,它既与负反离子缔合也与负反离子缔合,例如Cl和Na+或K+。美国专利号7,081,439和7,279,446中已描述了其他粘弹性表面活性剂。粘弹性表面活性剂可与无机水溶性盐或有机添加剂(诸如邻苯二甲酸、水杨酸或其盐)结合使用。
还可使用胺氧化物粘弹性表面活性剂。胺氧化物胶凝剂RN+(R′)2O-可具有以下结构:
其中R为平均约8至24个碳原子的烷基或烷基酰胺基,并且R′独立地为平均约1至6个碳原子的烷基。在一个非限制性实施方案中,R为平均约8至16个碳原子的烷基或烷基酰胺基,并且R′独立地为平均约2至3个碳原子的烷基。在一个替代性非限制性实施方案中,胺氧化物胶凝剂为牛脂酰胺基丙胺氧化物(TAPAO),其应被理解为二丙胺氧化物,因为两个R′基团均为丙基。
超吸收性聚合物是从非离子、阴离子、阳离子单体或包含前述中的至少一种的组合聚合而来。聚合可经由自由基聚合、溶液聚合、凝胶聚合、乳液聚合、分散聚合或悬浮聚合来进行。此外,聚合可在水相中、在反相乳液中或在反相悬浮液中进行。
用于制备预成形的合成聚合物的非离子单体的实例包括(甲基)丙烯酰胺、烷基取代的(甲基)丙烯酰胺、氨基烷基取代的(甲基)丙烯酰胺、烷基亚胺基烷基取代的(甲基)丙烯酰胺、乙烯醇、乙酸乙烯酯、烯丙醇、(甲基)丙烯酸C1-8烷基酯、(甲基)丙烯酸羟基C1-8烷基酯,诸如(甲基)丙烯酸羟乙酯、N-乙烯基甲酰胺、N-乙烯基乙酰胺以及(甲基)丙烯腈。如本文所用,“聚((甲基)丙烯酰胺)”包括包含衍生自以下物质的单元的聚合物:(甲基)丙烯酰胺;烷基取代的(甲基)丙烯酰胺,诸如N-C1-8烷基(甲基)丙烯酰胺和N,N-二(C1-8烷基)(甲基)丙烯酰胺;氨基烷基取代的(甲基)丙烯酰胺,诸如N,N-二(氨基(C1-8烷基))取代的(甲基)丙烯酰胺;以及(N,N-二烷基氨基)烷基取代的(甲基)丙烯酰胺,诸如(N,N-二(C1-8烷基)氨基)(C1-8烷基)(甲基)丙烯酰胺。前述单体的具体实例包括甲基丙烯酰胺、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-二甲氨基丙基丙烯酰胺、N,N-二甲氨基乙基丙烯酰胺、N-叔丁基丙烯酰胺或包含前述中的至少一种的组合。在一个实施方案中,聚((甲基)丙烯酰胺)为甲基丙烯酰胺与马来酸酐、乙酸乙烯酯、环氧乙烷、乙二醇或丙烯腈或包含前述中的至少一种的组合的共聚物。
阴离子单体的实例包括具有酸性基团或其盐的烯属不饱和阴离子单体,例如羧酸基、磺酸基、膦酸基、其盐、相应酸酐或酰基卤化物或包含前述酸性基团中的至少一种的组合。举例来说,阴离子单体可为(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、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-甲基丙磺酸、烯丙基磺酸、乙烯基磺酸、烯丙基膦酸、乙烯基膦酸、其盐或包含前述中的至少一种的组合。
阳离子单体的实例包括(N,N-二(C1-8烷基氨基)(C1-8烷基)(甲基)丙烯酸酯(例如丙烯酸N,N-二甲氨基乙酯和甲基丙烯酸N,N-二甲氨基乙酯)(其中氨基被季铵化至例如甲基氯化物季铵盐形式)、氯化二烯丙基二甲基铵或前述烷基取代的(甲基)丙烯酰胺和二烷基氨基烷基取代的(甲基)丙烯酰胺中的任一种,诸如(N,N-二(C1-8烷基)氨基)C1-8烷基丙烯酰胺和其季铵盐形式,诸如氯化丙烯酰胺基丙基三甲基铵。
超吸收性聚合物可含有阳离子取代基与阴离子取代基两者。阳离子取代基和阴离子取代基以各种化学计量比例存在,例如约1∶1的比率,或一种单体可以比另一种单体大的化学计算量存在。代表性的两性聚合物包括非离子单体、阴离子单体以及阳离子单体的三元共聚物。
在一个实施方案中,超吸收性聚合物包括衍生自丙烯酸酯、丙烯酸或其盐、丙烯酰胺、乙烯基吡略烷酮、乙烯酯(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。
超吸收性聚合物包括超吸收性聚合物的聚合物链之间的多个交联键。根据一个实施方案,交联键为共价的并且由超吸收性聚合物内的交联产生。在一个实施方案中,交联剂为烯属不饱和单体,所述烯属不饱和单体含有例如两个烯属不饱和位点(即两个烯属不饱和双键)、烯属不饱和双键以及对超吸收性聚合物的聚合物链的一个官能团(例如酰胺基)具反应性的一个官能团或对超吸收性聚合物的聚合物链的诸多官能团具反应性的若干官能团。在一个实施方案中,对本文中的超吸收性聚合物的交联度加以选择以控制超吸收性聚合物的膨胀(即流体吸收或体积扩大)的量。
示例性交联剂包括二胺的二(甲基)丙烯酰胺,诸如哌嗪的二丙烯酰胺;C1-8亚烷基双丙烯酰胺,诸如亚甲基双丙烯酰胺和亚乙基双丙烯酰胺;不饱和酰胺的N-羟甲基化合物,诸如N-羟甲基甲基丙烯酰胺或N-羟甲基丙烯酰胺;二羟基、三羟基或四羟基化合物的(甲基)丙烯酸酯,诸如乙二醇二丙烯酸酯、聚(乙二醇)二(甲基)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(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯)、乙氧基化甘油三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、乙氧基化季戊四醇四(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯);二乙烯基或二烯丙基化合物,诸如烯丙基(甲基)丙烯酸酯、烷氧基化烯丙基(甲基)丙烯酸酯、2,2’-偶氮双(异丁酸)的二烯丙基酰胺、氰尿酸三烯丙酯、异氰尿酸三烯丙酯、马来酸二烯丙酯、聚烯丙酯、四烯丙基氧基乙烷、三烯丙基胺以及四烯丙基乙二胺;二醇多元醇、羟基烯丙基或丙烯酸酯化合物;以及磷酸或亚磷酸的烯丙酯。特别提及水溶性二丙烯酸酯,诸如聚(乙二醇)二丙烯酸酯(例如PEG 200二丙烯酸酯或PEG400二丙烯酸酯)。还可使用包含上文所描述的交联剂中的任一种的组合。US 2014/0332213、US 2014/0332214以及US 2015/0096751中描述了其他交联键。
在一个实施方案中,SAP为包括存在于SAP外部至内部的表面交联键的粒子(或纤维或其他模式)。表面交联键例如因添加表面交联剂至SAP粒子和热处理而产生。表面交联键相对于SAP内部的交联密度使SAP在其表面附近的交联密度增加。一些表面交联剂具有对SAP的聚合物链的基团(例如酸或酰胺基团)具反应性的官能团。表面交联剂为前面提到的交联剂中的一种并且包括诸如醇、胺、醛或羧酸酯基等官能团。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、聚氨基醇以及碳酸亚烷基酯。表面交联剂还为SAP提供SAP的聚合物链在表面交联之前不具有的化学特性,并且控制SAP的化学特性,例如疏水性、亲水性或SAP对其他材料的粘着性,诸如矿物质(例如硅酸盐)或其他化学品,诸如石油化合物(例如烃、沥青质等)。优选地,在SAP与水性载体和支撑剂粒子组合之前形成内部和外部交联键。因此,压裂流体可不含交联剂。在一个实施方案中,SAP仅具有内部交联键而不含任何外部交联键。
此类超吸收性聚合物的非限制性实例为聚((甲基)丙烯酸羟基C1-8烷基酯),诸如(丙烯酸2-羟基乙酯)、聚(甲基)丙烯酰胺、聚(乙烯吡略烷)、聚(乙酸乙烯酯)、聚丙烯腈的淀粉-丙烯腈接枝共聚物、羧甲基纤维素、交联聚丙烯酸酯、磺化聚苯乙烯、水解聚丙烯酰胺、聚乙烯醇、聚氧化乙烯、聚乙烯吡略烷酮、聚丙烯腈、聚丙烯酸、聚丙烯酸盐等。前述内容包括共聚物,例如(甲基)丙烯酰胺与马来酸酐、乙酸乙烯酯、环氧乙烷、乙二醇或丙烯腈或包含前述中的至少一种的组合的共聚物。可使用不同聚合物的组合。作为一个具体实例,超吸收性聚合物为具有作为聚乙二醇二丙烯酸酯的交联键的聚丙烯酰胺。作为另一具体实例,超吸收性聚合物为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。超吸收性聚合物的一个具体实例为具有作为聚乙二醇二丙烯酸酯的交联键的聚丙烯酰胺。在一些实施方案中,超吸收性聚合物为聚丙烯酸均聚物或共聚物,其中交联键为乙烯酯低聚物。在一个实施方案中,超吸收性聚合物为丙烯酸和丙烯酸钠的具有衍生自聚乙二醇二丙烯酸酯的交联键的共聚物。
未膨胀的超吸收性聚合物的尺寸可具有10μm至100,000μm、具体地说50μm至10,000μm并且更具体地说150μm至1,000μm的平均最大直径。如本文所用,“尺寸”是指最大线性尺寸,例如球形粒子的直径。超吸收性聚合物可呈多种模式,包括粒子(例如粉末)、纤维、丝线、编织物等或其组合。SAP的粒子为任何形状,包括球形的、有棱角的以及多面体的。
超吸收性聚合物包括涂布的超吸收性聚合物、具有三维网络的超吸收性材料或其组合,以10磅超吸收性聚合物/一千加仑的压裂流体(ppt)至200ppt、具体地说20ppt至100ppt并且更具体地说30ppt至80ppt的质量浓度存在。
除了超吸收性聚合物组分,压裂组合物还包含载体流体,诸如水性载体。水性载体流体可为淡水、盐水(包括海水)、酸水溶液(例如矿物酸或有机酸)、碱水溶液或包含前述中的至少一种的组合。应了解,可将诸如醇和二醇等其他极性液体单独或与水一起用于载体流体中。
盐水可为例如海水、采出水(produced water)、完井盐水或包含前述中的至少一种的组合。盐水的特性可取决于盐水的身份和组分。海水除典型的含卤盐外例如可含有许多组分,包括硫酸盐、溴以及微量金属。采出水可为从生产储层(例如烃储层)萃取或从地面产生的水。采出水还可以指储层盐水并且含有包括钡、锶以及重金属的组分。除天然存在的盐水(例如海水和采出水)外,可通过添加各种盐(例如KCl、NaCl、ZnCl2、MgCl2或CaCl2)以增加盐水的密度(诸如每加仑的CaCl2盐水约1至约0.6磅)来从淡水合成完井盐水。完井盐水通常提供经过优化以对抗井下储层压力的静水压力。可改变以上盐水以包括一种或多种其他盐。盐水中所包括的其他盐可为NaCl、KCl、NaBr、MgCl2、CaCl2、CaBr2、ZnBr2、NH4Cl、甲酸钠、甲酸铯以及包含前述中的至少一种的组合。盐可以按流体的重量计约0.5至约50重量百分比(重量%)、具体地说约1至约40重量%并且更具体地说约1至约25wt%的量存在于盐水中。
水性载体流体可为矿物酸水溶液,所述矿物酸包括盐酸、硝酸、磷酸、硫酸、硼酸、氢氟酸、氢溴酸、高氯酸或包含前述中的至少一种的组合。流体可为有机酸水溶液,所述有机酸包括羧酸、磺酸或包含前述中的至少一种的组合。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、间位以及对位异构体)等。示例性磺酸包括C1-20烷基磺酸,其中烷基可为分支或未分支的并且可为取代的或未取代的;或为C3-20芳基磺酸,其中芳基可为单环或多环的,并且任选包含1至3个杂原子(例如N、S或P)。烷基磺酸可包括例如甲磺酸。芳基磺酸可包括例如苯磺酸或甲苯磺酸。在一些实施方案中,芳基可为C1-20烷基取代的,即为烷基亚芳基,或经由C1-20亚烷基(即芳基亚烷基)附接至磺酸部分,其中烷基或亚烷基可为取代的或未取代的。
水力压裂组合物还包含支撑剂粒子。支撑剂粒子包括陶瓷、砂、矿物质、坚果壳、砂砾、玻璃、树脂粒子、聚合粒子或其组合。在一个实施方案中,视水力压裂组合物的特定应用来选择支撑剂粒子。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,基于氧化物的陶瓷为二氧化硅(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、氧化磷以及/或者氧化钛或其组合。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、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)、稀土元素(例如镧、铈等)或卤素(例如氟、氯等)。示例性陶瓷包括氧化锆、稳定化氧化锆、莫来石、氧化锆增韧氧化铝、尖晶石、硅铝酸盐(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、氧氮化铝、氧氮化硅铝、钛酸铝、碳化钨、氮化钨、皂石等或其组合。
适合用于支撑剂粒子的砂的实例包括但不限于亚利桑那沙(Arizona sand)、威斯康星砂(Wisconsin sand)、内布拉斯加砂(Nebraska sand)、獾州砂(Badger sand)、贝迪砂(Brady sand)以及渥太华砂(Ottawa sand)。在一个实施方案中,将由诸如铝土矿等矿物质制成的支撑剂粒子烧结以获得硬质材料。在一个实施方案中,铝土矿或烧结铝土矿具有相对高的渗透性,诸如美国专利号4,713,203中所公开的铝土矿材料,该专利的内容以引用的方式整体并入本文中。
天然存在的支撑剂粒子包括坚果壳,诸如胡桃、椰子、山核桃、扁桃、象牙果、巴西坚果等;诸如李子、橄榄、桃、樱桃、杏等水果的种子壳;其他植物的种子壳,诸如玉米(例如玉米棒或玉米粒);木质材料,诸如衍生自橡树、山核桃、胡桃、白杨、桃花心木等的那些。此类材料为通过压碎、研磨、切割、切削等形成的粒子。这些支撑剂粒子为相对轻重量的和/或基本上中性浮力的支撑剂颗粒,US 6,364,018中已对其进行了描述。“相对轻重量”意味着颗粒具有基本上小于水力压裂操作中所采用的常规支撑剂颗粒材料(例如砂)的密度,或具有类似于这些材料的密度。“基本上中性浮力”意味着颗粒具有足够接近所选择的未胶凝或弱胶凝载体流体(例如未胶凝或弱胶凝完井盐水、其他基于水性物质的流体或其他合适的流体)的密度的密度,从而允许使用所选择的未胶凝或弱胶凝载体流体来泵送和满意地放置支撑剂颗粒。相对轻重量和基本上中性浮力的支撑剂粒子可以LitePropTM形式从BakerHughes Inc.商购获得。
在一个实施方案中,支撑剂粒子为例如用树脂涂布的。也就是说,单个的支撑剂粒子具有涂覆于其上的涂层。以这种方式,如果在例如压裂期间或在例如压裂后在大到足以从支撑剂粒子产生精细粒子的压力下压缩支撑剂粒子,那么精细粒子保持固结在涂层内,以致其不释放至地层中。预期精细粒子减少烃(或其他流体)通过裂缝或裂缝中的孔隙的传导,并且通过涂布支撑剂粒子得以避免。支撑剂粒子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。将支撑剂粒子上的涂层固化是在将支撑剂粒子设置于SAP中之前或之后或者在例如将水力压裂组合物设置到井下之前或之后进行。
在一个实施方案中,涂层为包括环氧树脂、酚醛树脂、聚氨酯、聚碳二酰亚胺、聚酰胺、聚酰胺酰亚胺、呋喃树脂或其组合的有机化合物。酚醛树脂为例如通过苯酚、双酚或其衍生物与多聚甲醛的反应获得的苯酚甲醛树脂。示例性热塑性材料包括聚乙烯、丙烯腈-丁二烯苯乙烯、聚苯乙烯、聚氯乙烯、氟塑料、聚硫化物、聚丙烯、苯乙烯丙烯腈、尼龙以及亚苯基氧化物。示例性热固性材料包括环氧树脂、酚醛树脂(真正的热固性树脂,诸如甲阶树脂或由硬化剂赋予热固性的热塑性树脂)、聚酯树脂、聚氨酯、环氧改性酚醛树脂以及其衍生物。
在一个实施方案中,用于涂层的固化剂为含氮化合物,诸如胺和其衍生物;含氧化合物,诸如羧酸封端的聚酯、酸酐、苯酚-甲醛树脂、氨基-甲醛树脂、苯酚、双酚A以及甲酚酚醛清漆、酚封端的环氧树脂;含硫化合物,诸如聚硫化物、聚硫醇;以及催化固化剂,诸如叔胺、路易斯酸、路易斯碱;或其组合。
在一个实施方案中,支撑剂粒子包括交联的涂层。交联的涂层通常为支撑剂粒子提供压碎强度或抗性,并且即使在高压和高温条件下也防止支撑剂粒子聚结。在一些实施方案中,支撑剂粒子具有可固化涂层,所述可固化涂层在亚表面(例如在井下或在裂缝中)固化。可固化涂层在高压和高温条件下在亚表面储层中固化。因此,在高压和高温条件下使用具有可固化涂层的支撑剂粒子。
根据一个实施方案,通过在容器(例如反应器)中混合来将涂层设置于支撑剂粒子上。将单个的组分,例如支撑剂粒子和树脂材料(例如用于形成例如环氧树脂或聚酰胺涂层的反应性单体)在容器中组合以形成反应混合物并且搅拌以混合各组分。此外,将反应混合物在与形成涂层相称的温度或压力下加热。在另一实施方案中,经由喷涂诸如通过使支撑剂粒子与涂布材料的喷雾接触来将涂层设置于粒子上。将涂布的支撑剂粒子加热以诱导涂层的交联。
支撑剂粒子具有1μm至2000μm、具体地说10μm至1000μm并且更具体地说10μm至500μm的尺寸。此外,支撑剂粒子具有任何形状,包括球形、有棱角的以及多面体的,并且为单分散或多分散的,平均粒度分布为单峰或多峰的,例如为双峰的。
在水力压裂组合物中,支撑剂粒子以有效撑开裂缝而裂缝的几何形状当支撑剂从超吸收性聚合物释放时在地层沉降期间不会改变的量存在。在一个特定实施方案中,支撑剂粒子以按组合物的总体积计0.1磅/加仑(lb/gal)至20lb/gal、具体地说0.25lb/gal至16lb/gal并且更具体地说0.25lb/gal至12lb/gal的质量浓度存在。在水力压裂组合物中,任何比率的支撑剂粒子的量与SAP的量均适用,只要支撑剂粒子悬浮在由超吸收性聚合物形成的凝胶中即可。
在一些实施方案中水力压裂组合物还可包括破碎剂。破碎剂接触超吸收性聚合物以破碎超吸收性聚合物。在一个实施方案中,破碎剂接触超吸收性聚合物并且破碎超吸收性聚合物的聚合物链的主链中的键、交联剂中的键、交联剂与超吸收性聚合物的聚合物链之间的键或其组合。也就是说,破碎超吸收性聚合物包括诸如通过破碎超吸收性聚合物的主链中的键、破碎超吸收性聚合物的链之间的交联键、改变超吸收性聚合物的几何构象或其组合来崩解、分解或解离超吸收性聚合物。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,破碎剂破碎超吸收性聚合物以形成分解的聚合物,诸如具有低于超吸收性聚合物的分子量的多个片段。
破碎剂包括氧化剂,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。
任选将破碎剂封装于封装材料中以防止破碎剂接触超吸收性聚合物。封装材料被配置成响应于破碎条件而释放破碎剂。破碎剂为固体或液体。作为固体,破碎剂为例如结晶或粒状材料。在一个实施方案中,将固体用涂层封装或与涂层一起提供以延迟其释放或与SAP接触。封装材料与上文关于支撑剂粒子所提到的涂布材料相同或不同。将封装材料设置于破碎剂上的方法与将涂层设置于支撑剂粒子上相同或不同。在一个实施方案中,将液体破碎剂溶解于水溶液或另一合适的溶剂中。
为将压裂组合物或流体的益处最大化,应将流体破碎至极小的粘度并且在生产之前允许其流回。“潜伏性”破碎剂或后期注射破碎剂为优选的,因为当在井下运送支撑剂时流体可仿佛不存在破碎剂一般发挥作用。在压裂处理完成之后,可触发对超吸收性聚合物的破碎,使得流体可流回到裂缝,并且地层破碎极小。
在一个实施方案中,通过在超吸收性聚合物颗粒或纤维的内部或外部包括缓释酸来改变水力压裂组合物以降低pH并且在稍后阶段加速破碎。在形成裂缝之后,水力压裂组合物将支撑剂粒子运输至裂缝中。因此,超吸收性聚合物被配置成在支撑剂放置之后被破碎。如果pH降低,那么压裂流体的粘度将降低。在已将支撑剂粒子放置于裂缝中之后,缓释酸会降低pH值,从而允许压裂组合物变稀并流回到表面。酸可为乙二醛、固体酸、封装的酸或其组合。乙二醛为可经由坎尼扎罗型(Cannizzaro-type)自歧化反应缓慢释放酸的二醛。酸的缓慢释放可胜过缓冲剂(如果存在),并且使得流体pH值逐渐降低,直到达到适合于破碎超吸收性聚合物的所选pH值。
在一个实施方案中,提供超吸收性聚合物与缓释破碎剂的复合物。可使用本文所公开的超吸收性聚合物中的任一种。缓释破碎剂包括如本文所公开的缓释酸。形成复合物的方法没有特别的限制。在一个实施方案中,将缓释破碎剂与超吸收性聚合物混配,然后挤出,从而形成在复合物的单个的团粒或粒子内部含有缓释破碎剂的团粒或粒子。压裂组合物可含有不同超吸收性聚合物组分的组合。举例来说,基于聚乙烯醇(PVA)的超吸收性聚合物与缓释酸的复合物可与SAP粒子内部未加载有任何破碎剂的超吸收性聚合物一起使用。
破碎剂可以按流体的总体积计0.1ppt至20ppt、具体地说0.2ppt至15ppt并且更具体地说0.25ppt至10ppt的质量浓度存在于水力压裂组合物中。
还已发现在低温井(即温度小于约200°F的井)中可通过使用高温破碎剂来控制对破碎超吸收性聚合物的时间设定。如本文所用,高温破碎剂是指在大于约250°F的温度下在不存在任何活化剂的情况下有效破碎超吸收性聚合物的化合物。此类高温破碎剂的一个具体实例为溴酸钠。有利地,在存在诸如以下的活化剂:山梨酸;亚铁盐;铜(I)盐;或异抗坏血酸或其盐(诸如异抗坏血酸钠);或包含前述中的至少一种的组合的情况下,高温破碎剂可被活化并且在小于约200°F(例如约170°F至约180°F)的温度下有效破碎超吸收性聚合物。
在一个实施方案中,高温破碎剂和封装的活化剂均被包括在压裂组合物中,并且同时被递送至地下地层。在小于200°F的井下温度下,高温破碎剂不破碎超吸收性聚合物。一旦将支撑剂放置于裂缝中,活化剂即从封装剂释放并且活化高温破碎剂,使得高温破碎剂或其衍生物在小于约200°F的温度下破碎超吸收性物质。封装剂可与上文关于支撑剂粒子所提到的涂布材料相同。压裂组合物包含每一千加仑的压裂组合物约1磅至约10磅的破碎剂和约1磅至约4磅的封装的活化剂。
或者,可将高温破碎剂与含有超吸收性聚合物的压裂流体一起泵送。然后,注射加载有针对高温破碎剂的活化剂的第二流体以活化高温破碎剂。当然,可将活化剂与含有超吸收性聚合物的压裂流体一起注射,并且随后可注射含有高温破碎剂的第二流体以破碎超吸收性聚合物。高温破碎剂可以每一千加仑的含破碎剂组合物约1磅至约10磅的量存在,并且活化剂可以每一千加仑的含活化剂组合物约1磅至约4磅的量存在。
在其他实施方案中,用不含破碎剂的压裂组合物处理地下地层,然后可注射含有载体和低温破碎剂的流体以在温度小于约200°F的井下环境中破碎超吸收性聚合物。如本文所用,低温破碎剂是指在小于约200°F的温度下有效破碎超吸收性聚合物而不使用任何活化剂的破碎剂。低温破碎剂可为以下各项中的一种或多种: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;或其衍生物。示例性低温破碎剂包括过硫酸钠;过硫酸铵以及过硫酸钾。
水力压裂组合物还可包含已知用于压裂组合物中的其他组分,例如增粘剂、增粘剂交联剂、pH控制剂、表面活性剂、破碎剂、润滑剂、流体损失剂、粘土稳定剂、杀菌剂、酸、腐蚀抑制剂、氧清除剂或包含前述中的至少一种的组合。对这些其他组分加以选择,以避免赋予水力压裂组合物不利的特征、避免对与压裂组合物接触的设备的损坏以及避免损坏井筒或地下地层。添加剂以及添加剂的量为已知的,并且在例如U.S.2014/03322123和U.S.2014/0332214中已有描述。
压裂组合物可为液体或泡沫。可用液体烃或诸如以下的气体或液化气体使载体流体起泡:氮气、二氧化碳、天然气、空气或包含前述中的至少一种的组合。可通过包括非气体起泡剂进一步使流体起泡。非气体起泡剂可为两性的、阳离子的或阴离子的。合适的两性起泡剂包括烷基甜菜碱、烷基磺基甜菜碱以及烷基羧酸盐。合适的阴离子起泡剂可包括烷基醚硫酸盐、乙氧基化醚硫酸盐、磷酸酯、烷基醚磷酸盐、乙氧基化醇磷酸酯、烷基硫酸盐以及α烯烃磺酸盐。合适的阳离子起泡剂可包括烷基季铵盐、烷基苯甲基季铵盐以及烷基酰胺基胺季铵盐。泡沫系统主要用于压裂低压或水敏感性地层。
在另一实施方案中,超吸收性聚合物是用作常规类型压裂工艺的流体损失添加剂。使用添加流体损失添加剂来改善压裂期间的压裂流体效率以减少流体泄漏到地层中的量,并且在这样做时保存所形成的裂缝宽度,产生所述裂缝宽度是为了将所需量的支撑剂替换至地层中。可在独立的应用中使用超吸收性聚合物来处理基于水的与不基于水的压裂流体两者。对于诸如水、油(烃)甲醇、甘油、CO2、天然气等压裂流体,可向处理中添加在载体溶液中浆化的水合或部分水合超吸收性聚合物。这对用于基于烃的流体中特别有利,其中水的缺乏常常需要使用极低效的流体损失替代品(诸如二氧化硅流体)来运行,此归因于材料的破碎性特征而为棘手的。因此,公开一种压裂被井穿过的地下地层的方法,所述方法包括:形成压裂组合物,所述压裂组合物包含载体流体、线性瓜尔胶、以在压裂操作期间有效减少流体损失的量存在的超吸收性聚合物以及任选存在的针对瓜尔胶的交联剂;以及将水力压裂组合物泵送至地下地层中以形成或扩大裂缝。超吸收性聚合物的量为每一千加仑的压裂组合物约5磅至约100磅、具体地说约10磅至约70磅。
以下阐述本公开的各种实施方案。
实施方案1.一种压裂被井穿过的地下地层的方法,所述方法包括:形成压裂组合物,所述压裂组合物包含载体流体;以及超吸收性聚合物组分,所述超吸收性聚合物组分包含以下中的一种或多种:支撑剂与呈未水合形式的第一超吸收性聚合物的第一复合物,所述第一超吸收性聚合物至少部分嵌入所述支撑剂的空隙区域中;涂布的超吸收性聚合物;具有三维网络的超吸收性材料;或第二超吸收性聚合物与缓释破碎剂的第二复合物;以及将所述水力压裂组合物泵送至所述地下地层中以形成或扩大裂缝。
实施方案2.如实施方案1所述的方法,其中所述压裂组合物包含每一千加仑的所述压裂组合物约30磅至约80磅的所述第一复合物。
实施方案3.如实施方案1或实施方案2所述的方法,其中所述第一复合物中的所述支撑剂具有小于约2.4的表观比重。
实施方案4.如实施方案1所述的方法,其中所述第二复合物中的所述缓释破碎剂包含以下中的一种或多种:乙二醛或封装的酸。
实施方案5.如实施方案1或实施方案4所述的方法,其中所述第二复合物包含缓释破碎剂和交联的基于聚乙烯的超吸收性聚合物。
实施方案6.如实施方案1所述的方法,其中具有三维网络的所述超吸收性材料包含键合至阳离子或非离子聚合物或其组合的具有负电荷的超吸收性聚合物。
实施方案7.如实施方案6所述的方法,其中具有负电荷的所述超吸收性聚合物为丙烯酸与丙烯酸酯的交联共聚物。
实施方案8.如实施方案6或实施方案7所述的方法,其中所述阳离子聚合物为阳离子丙烯酰胺共聚物;并且所述非离子聚合物包含聚乙烯醇、聚乙酸乙烯酯或其组合。
实施方案9.一种压裂被井穿过的地下地层的方法,所述方法包括:形成压裂组合物,所述压裂组合物包含载体流体;支撑剂;每一千加仑的所述压裂组合物约10磅至约100磅的超吸收性聚合物;以及每一千加仑的所述压裂组合物约1磅至约30磅的粘度改性剂,所述粘度改性剂包括以下中的一种或多种:尤坦胶;淀粉-丙烯腈接枝聚合物水解产物;磺化聚苯乙烯;聚乙烯醇;聚乙烯吡略烷酮;或聚丙烯腈;以及将所述水力压裂组合物泵送至所述地下地层中以形成或扩大裂缝。
实施方案10.一种压裂被井穿过的地下地层的方法,所述方法包括:形成压裂组合物,所述压裂组合物包含载体流体;支撑剂;约30磅至约80磅的聚合物,所述聚合物包括以下中的一种或多种:魔芋葡甘露聚糖;淀粉-丙烯腈接枝聚合物水解产物;羧甲基纤维素;交联聚丙烯酸酯;磺化聚苯乙烯;水解聚丙烯酰胺;聚乙烯醇;聚乙酸乙烯酯;聚氧化乙烯;聚乙烯吡略烷酮;或聚丙烯腈。
实施方案11.一种压裂被井穿过的地下地层的方法,所述方法包括:形成压裂组合物,所述压裂组合物包含载体流体、线性瓜尔胶、以在压裂操作期间有效减少流体损失的量存在的超吸收性聚合物、任选存在的针对所述线性瓜尔胶的交联剂;以及将所述水力压裂组合物泵送至所述地下地层中以形成或扩大裂缝。
实施方案12.如实施方案11所述的方法,其中所述载体流体为油基载体,并且所述超吸收性聚合物呈水合或部分水合形式。
实施方案13.如实施方案11所述的方法,其中所述载体流体为泡沫,所述泡沫包含液体烃、气体、液化气体或包含前述中的至少一种的组合。
实施方案14.如实施方案11至13中任一种所述的方法,其中所述压裂流体包含每一千加仑的所述压裂组合物约30磅至约80磅的所述超吸收性聚合物。
实施方案15.一种压裂被井穿过的地下地层的方法,所述方法包括:形成压裂组合物,所述压裂组合物包含载体流体、支撑剂、超吸收性聚合物、在大于约250°F的温度下在不存在任何活化剂的情况下有效破碎所述超吸收性聚合物的破碎剂、包含封装于封装剂内的活化剂的封装的活化剂,所述活化剂有效活化所述破碎剂,使得所述破碎剂或其衍生物在小于约200°F的温度下破碎所述超吸收性物质;将所述水力压裂组合物泵送至所述地下地层中以形成或扩大裂缝;允许所述活化剂从所述封装剂中扩散出来;以及破碎所述超吸收性聚合物。
实施方案16.如实施方案15所述的方法,其中所述地下地层具有小于约200°F的环境温度。
实施方案17.如实施方案15或实施方案16所述的方法,其中所述破碎剂为溴酸钠。
实施方案18.如实施方案15至17中任一种所述的方法,其中所述压裂组合物包含每一千加仑的所述压裂组合物约1磅至约10磅的所述破碎剂。
实施方案19.如实施方案15至18中任一种所述的方法,其中所述活化剂包含以下中的一种或多种:山梨酸;亚铁盐;铜(I)盐;或异抗坏血酸或其盐。
实施方案20.如实施方案15至19中任一种所述的方法,其中所述压裂组合物包含每一千加仑的所述压裂流体约1磅至约4磅的所述封装的活化剂。
实施方案21.如实施方案15至19中任一种所述的方法,其中所述压裂组合物包含所述超吸收性聚合物与所述支撑剂的复合物。
实施方案22.一种压裂被井穿过的地下地层的方法,所述方法包括:将第一压裂组合物注入所述地下地层,所述第一压裂组合物包含第一载体流体、支撑剂、超吸收性聚合物以及破碎剂和针对所述破碎剂的活化剂中的一种;将第二压裂组合物注入所述地下地层,所述第二压裂组合物包含第二载体流体以及所述第一压裂组合物中未包括的所述破碎剂或所述活化剂;并且在注射所述第二压裂组合物之后在小于约200°F的温度下破碎所述超吸收性聚合物。
实施方案23.如实施方案22所述的方法,其中所述破碎剂为溴酸钠。
实施方案24.如实施方案22或实施方案23所述的方法,其中所述第一或第二压裂组合物包含每一千加仑的所述第一或第二压裂组合物约1磅至约10磅的所述破碎剂。
实施方案25.如实施方案22至24中任一种所述的方法,其中所述活化剂包括以下中的一种或多种:山梨酸;亚铁盐;铜(I)盐;或异抗坏血酸或其盐。
实施方案26.如实施方案22至25中任一种所述的方法,其中所述第一或第二压裂组合物包含每一千加仑的所述第一或第二压裂流体约1磅至约4磅的所述活化剂。
实施方案27.如实施方案22至26中任一种所述的方法,其中所述第一压裂组合物包含所述超吸收性聚合物与所述支撑剂的复合物。
实施方案28.一种压裂被井穿过的地下地层的方法,所述方法包括:将第一压裂组合物注入所述地下地层中,所述第一压裂组合物包含第一载体流体、支撑剂以及超吸收性聚合物,所述第一压裂组合物不含针对所述超吸收性聚合物的破碎剂;将第二压裂组合物注入所述地下地层,所述第二压裂组合物包含第二载体流体以及在小于约200°F的温度下有效破碎所述超吸收性聚合物的破碎剂;以及在注射所述第二压裂组合物之后破碎所述超吸收性聚合物。
实施方案29.如实施方案28所述的方法,其中所述破碎剂为以下各项中的一种或多种: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;或其衍生物。
实施方案30.如实施方案28或实施方案29所述的方法,其中所述破碎剂为以下各项中的一种或多种:过硫酸钠;过硫酸铵;或过硫酸钾。
实施方案31.如实施方案28至30中任一种所述的方法,其中所述第一压裂组合物包含所述超吸收性聚合物与所述支撑剂的复合物。
本文所公开的所有范围包括端点,并且端点可彼此独立地组合。“或”意指“和/或”。如本文所用,“组合”包括共混物、混合物、合金、反应产物等。所有参考文献均以引用的方式并入本文中。
除非本文另外指明或者与上下文明显相悖,否则在描述本发明的上下文中(尤其在以下权利要求书的上下文中)使用术语“一个/种”、“所述”以及类似的指代语应理解为涵盖单数和复数。此外,应进一步注意,术语“第一”、“第二”等在本文中不表示任何顺序、数量或重要性,而是用于将一个元件与另一个区分开。结合数量使用的修饰语“约”包括所陈述的值,并且具有上下文所规定的含义(例如它包括与特定量的测量相关的误差度)。
虽然已出于说明的目的阐述典型的实施方案,但是前面的描述不应被视为对本文范围的限制。因此,本领域技术人员可想到各种修改、改变以及替代,而不会脱离本文的精神和范围。
Claims (15)
1.一种压裂被井穿过的地下地层的方法,所述方法的特征在于:
形成压裂组合物,所述压裂组合物包含
载体流体;以及
超吸收性聚合物组分,所述超吸收性聚合物组分包含以下中的一种或多种:
支撑剂与呈未水合形式的第一超吸收性聚合物的第一复合物
所述第一超吸收性聚合物至少
部分嵌入所述支撑剂的空隙区域中;
涂布的超吸收性聚合物;
具有三维网络的超吸收性材料;或
第二超吸收性聚合物与缓释破碎剂的第二复合物;
以及
将所述水力压裂组合物泵送至所述地下地层中以形成或扩大裂缝。
2.如权利要求1所述的方法,其中所述压裂组合物包含每一千加仑的所述压裂组合物约30磅至约80磅的所述第一复合物。
3.如权利要求1所述的方法,其中所述第二复合物中的所述缓释破碎剂包含以下中的一种或多种:乙二醛或封装的酸。
4.如权利要求1所述的方法,其中所述第二复合物包含缓释破碎剂和交联的基于聚乙烯的超吸收性聚合物。
5.如权利要求1所述的方法,其中具有三维网络的所述超吸收性材料包含具有负电荷的超吸收性聚合物,所述具有负电荷的所述超吸收性聚合物键合至阳离子或非离子聚合物或其组合。
6.如权利要求5所述的方法,其中具有负电荷的所述超吸收性聚合物为丙烯酸与丙烯酸酯的交联共聚物。
7.如权利要求5或6所述的方法,其中所述阳离子聚合物为阳离子丙烯酰胺共聚物;并且所述非离子聚合物包括聚乙烯醇、聚乙酸乙烯酯或其组合。
8.一种压裂被井穿过的地下地层的方法,所述方法的特征在于:
形成压裂组合物,所述压裂组合物包含
载体流体;
支撑剂;
每一千加仑的所述压裂组合物约10磅至约100磅的超吸收性聚合物;以及
每一千加仑的所述压裂组合物约1磅至约30磅的粘度改性剂,所述粘度改性剂包括以下中的一种或多种:尤坦胶;淀粉-丙烯腈接枝聚合物水解产物;磺化聚苯乙烯;聚乙烯醇;聚乙烯吡略烷酮;或聚丙烯腈;以及
将所述水力压裂组合物泵送至所述地下地层中以形成或扩大裂缝。
9.如权利要求8所述的方法,其中所述粘度改性剂包括淀粉-丙烯腈接枝聚合物水解产物或磺化聚苯乙烯。
10.一种压裂被井穿过的地下地层的方法,所述方法的特征在于:
形成压裂组合物,所述压裂组合物包含
载体流体;
支撑剂;
约30磅至约80磅的聚合物,所述聚合物包括以下中的一种或多种:魔芋葡甘露聚糖;淀粉-丙烯腈接枝聚合物水解产物;羧甲基纤维素;交联聚丙烯酸酯;磺化聚苯乙烯;水解聚丙烯酰胺;聚乙烯醇;聚乙酸乙烯酯;聚氧化乙烯;聚乙烯吡略烷酮;或聚丙烯腈。
11.如权利要求10所述的方法,其中所述聚合物包括魔芋葡甘露聚糖或淀粉-丙烯腈接枝聚合物水解产物。
12.一种压裂被井穿过的地下地层的方法,所述方法的特征在于:
形成压裂组合物,所述压裂组合物包含
载体流体,
线性瓜尔胶,
超吸收性聚合物,所述超吸收性聚合物以在压裂操作期间有效减少流体损失的量存在,
任选针对所述线性瓜尔胶的交联剂;以及
将所述水力压裂组合物泵送至所述地下地层中以形成或扩大裂缝。
13.如权利要求12所述的方法,其中所述载体流体为油基载体,并且所述超吸收性聚合物呈水合或部分水合形式。
14.如权利要求12所述的方法,其中所述载体流体为泡沫,所述泡沫包含液体烃、气体、液化气体或包含前述中的至少一种的组合。
15.如权利要求12至14中任一项所述的方法,其中所述压裂流体包含每一千加仑的所述压裂组合物约30磅至约80磅的所述超吸收性聚合物。
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