CN104540920A - 作为粘土稳定剂的烷基化聚醚胺 - Google Patents
作为粘土稳定剂的烷基化聚醚胺 Download PDFInfo
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- CN104540920A CN104540920A CN201380042778.2A CN201380042778A CN104540920A CN 104540920 A CN104540920 A CN 104540920A CN 201380042778 A CN201380042778 A CN 201380042778A CN 104540920 A CN104540920 A CN 104540920A
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- C—CHEMISTRY; METALLURGY
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- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
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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
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
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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
- C09K8/02—Well-drilling compositions
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
- C07C217/08—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom
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- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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- C09K8/60—Compositions for stimulating production by acting on the underground formation
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- 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
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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
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- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
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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
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
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- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
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Abstract
本发明提供了水基井处理流体,其用于处理地下地层以防止细料的溶胀和/或移动。该水基井处理流体包含含水连续相、由烷基化聚醚胺组成的粘土稳定剂和加重材料。除了抑制溶胀和/或移动之外,该水基井处理流体是热稳定的,在毒理方面是安全的,和具有优越的操作性能。
Description
相关申请的交叉引用
不适用。
涉及联邦资助的研究或开发的声明
不适用。
发明领域
本发明总体上涉及井处理流体和它们的用途。更具体地,本发明涉及在井处理流体中作为粘土稳定剂的烷基化聚醚胺和使用其的方法。
发明背景
从地下地层生产烃经常受到粘土和其他细料的存在的影响,它们会移动并且堵塞或限制烃产品的流动。细料在地下地层中的移动经常是以下的结果:粘土溶胀、盐溶解和/或由引入对地层来说外来的流体造成的细料的扰动。典型地,将这种外来流体(例如钻井流体、压裂流体或稳定化流体)引入到地层中,目的是完成和/或处理该地层以通过例如钻井、压裂、酸化或使井稳定化来使烃增产。
为消除由引入外来流体和地层的组分的溶胀和移动所引起的有害效应所做的尝试包括向该外来流体中添加一种或多种不同的页岩水合抑制剂和/或稳定剂。这些按照将粘土晶格中的阳离子物质替换为钠离子的原则来进行。通常选择阳离子物质以使其水合半径小于钠离子的水合半径。据信,页岩水合抑制剂和稳定剂的分子与水分子为反应位发生竞争。因此,通过它们与地层接触,使溶胀和移动的可能性最小化。结果,减小了地层分裂的可能性,和抑制了溶胀。
氯化钾广泛用作页岩抑制剂/粘土稳定剂。在增产方法中,氯化钾经常用作预冲洗剂(preflush)和/或添加到含水增产方法中,以将粘土转化为不易溶胀的形式。虽然这种盐减小了地层渗透性的降低,但是它们经常对外来流体的其他成分的性能有害。例如,粘土的稳定化典型地需要高浓度的这种盐(典型地6%)。这种盐还产生环境方面不可接受的高氯化物水平。已经使用的其他已知的页岩水合抑制剂/粘土稳定剂包括例如:
WO 98/55733,其公开了使用至少一种有机胺,其选自具有小于8个碳原子的链长的伯二胺和具有小于4个碳原子的链长的烷基伯胺;
WO 05/058986,其教导了使用马来酸酐聚合物的酰亚胺的胺盐;
WO 06/013595,其公开了羧甲基纤维素和有机胺的加合物作为固体页岩抑制剂;
WO 06/013597,其教导了使用0.2-5wt%的1,2-二氨基环己烷来抑制粘土的溶胀;
WO 06/136031,其教导了使用具有不同分子量的胺盐,以能够输送到地层中的微孔、中孔和大孔中,并在其中进行阳离子交换;
WO 10/040223,其公开了在进行钻井的同时,使用双表面活性剂二胺化合物来降低粘土溶胀;
美国专利4,719,021,其教导了向钻井流体中引入多价金属/胍络合物来使胶态白土稳定
美国专利4,988,450,其公开了乙酸乙烯酯的聚合物与钾盐合并,作为用于含水泥浆的添加剂,用来改进井筒稳定性;
美国专利6,706,667,其公开了用于水基钻井流体的页岩稳定添加剂,包含基于烯属不饱和烃与氧化剂基侧链的聚合物;
美国专利6,831,043和6,857,485,其教导了使用聚醚胺作为页岩水合抑制剂;
美国专利7,192,907,其公开了季化合物作为页岩包封剂,来至少部分抑制溶胀和帮助常规页岩抑制剂起作用;
美国专利7,514,392,其教导了使用双环己胺添加剂作为页岩水合抑制剂;
美国专利7,939,473,其公开了单季羟基烷基烷基胺或聚(三羟基烷基烷基季胺)作为用于减少井中粘土溶胀的添加剂;
美国专利8,026,198,其教导了使用丙胺衍生物、氢化聚(丙烯亚胺)树形聚合物和聚胺双晶树形聚合物(twin dendrimer)作为页岩水合抑制剂;
美国专利8,220,565,其教导了使用胍基共聚物来使地下地层稳定;和
美国专利8,252,728,其公开含有了羟基化结构单元的聚合物,其可用于抑制粘土溶胀。
对于开发页岩水合抑制剂/粘土稳定剂存在持续的需求,该页岩水合抑制剂/粘土稳定剂基本上无臭味,通过基本上消除了所有氯化物而对环境威胁小,并且至少与最有效的现有技术的水合抑制剂/稳定剂同样有效。
发明概述
本发明提供了水基井处理流体,其用于引入到地下地层中的井下流体中,该地下地层含有当暴露于水时具有表现出溶胀和/或移动的倾向的粘土地下材料。该井处理流体包含含水连续相、由烷基化聚醚胺组成的粘土稳定剂和加重材料。
另一方面,本发明提供了抑制在对地下地层进行钻井期间遇到的粘土地下材料的溶胀和/或移动的方法。该方法包括在该地下地层中循环水基井处理流体,该水基井处理流体包含含水连续相、由烷基化聚醚胺组成的粘土稳定剂和加重材料。
发明详述
如这里所用的,术语“包括”及其派生词不用于排除任何另外的组分、步骤或程序的存在,无论其是否在这里公开。为避免任何疑义,通过使用术语“包括”在这里要求保护的所有组合物可以包括任何另外的添加剂或化合物,除非有相反说明。相反,术语“基本上由……组成”如果出现在这里,从任何后续限定的范围中排除任何其他的组分、步骤或程序,除了对操作性不重要的那些,并且术语“由……组成”如果使用,排除未具体描述或列举的任何组分、步骤或程序。术语“或”除非另外说明,指的是独立地以及以任意组合列举的成员。
冠词“一个”和“一种”在这里用来指一个/一种或多于一个/一种(即至少一个/一种)该冠词的语法对象。举例来说,“一种烷基化聚醚胺”意为一种烷基化聚醚胺或多于一种烷基化聚醚胺。
“在一个实施方案中”、“根据一个实施方案”和类似短语通常意为跟在该短语后面的特定特征、结构或特性包括在本发明的至少一个实施方案中,并且可以包括在本发明的多于一个实施方案中。重要的是,这些短语不必指相同的实施方案。
如果说明书说明一个组分或特征“可以”、“能够”、“会”或“可能”被包括或具有某种特性,则该特定组分或特征不必须被包括或具有该特性。
短语“地下地层”包括暴露土壤下面的区域,和被水如海洋或淡水覆盖的土壤下面的区域。术语“粘土地下材料”包括砂和/或粘土,其在外来含水井处理流体如钻井流体、增产流体、砾石充填流体等存在下,溶胀、分散、分裂或以其他方式变得瓦解,由此表现出总体积的增大。该术语还包括那些砂和/或粘土,其在没有实际溶胀的情况下分散、分裂或以其他方式变得瓦解。例如,该术语也应当包括这种粘土,其在外来含水井处理流体存在下膨胀,并且可以通过变得松散而瓦解,由此产生向井孔中移动的颗粒。
当氯化钾用作粘土稳定剂,这里定义的由烷基化聚醚胺组成的粘土稳定剂可以用作总的氯化钾替代品。另外,该由烷基化聚醚胺组成的粘土稳定剂可以用在传统上不使用氯化钾或其他无机盐的水基井处理流体和方法中。在一些实施方案中,该粘土稳定剂基本上由烷基化聚醚胺组成,并且可以与氯化钾联合用于水基井处理流体中。当与含水连续相和加重材料合并以得到水基井处理流体时,该由烷基化聚醚胺组成的粘土稳定剂能够减少或基本上消除由可溶涨的和/或移动的粘土地下材料引起的对地下地层的损害。该由烷基化聚醚胺组成的粘土稳定剂的存在消除或减少了该粘土地下材料在与该水基井处理流体接触时溶胀和/或分裂和/或移动的倾向。
取决于用来处该地下地层的水基井处理流体的品质,这种抑制和/或移动可以是临时的或基本上永久的。因此,使用本发明的由烷基化聚醚胺组成的粘土稳定剂的另一优势通过其提供永久的粘土稳定化的能力而得到证明。临时的粘土稳定剂是仅在用水基井处理流体处理地层期间保护地下地层的材料。天然流体遍及地下地层的经时移动转移了外来阳离子,由此使粘土恢复到其天然的溶胀形式。相反,当粘土经时暴露于天然流体时,永久的粘土稳定剂使这种溶胀最小化,而不需要连续添加水基井处理流体。
除了抑制溶胀和/或移动之外,这里公开的由烷基化聚醚胺组成的粘土稳定剂还获得其他益处。例如,该由烷基化聚醚胺组成的粘土稳定剂是热稳定的,在毒理方面是安全的,和具有更好的操作性能。因此,该由烷基化聚醚胺组成的粘土稳定剂可以广泛用于基于地面的钻井操作以及海面的钻井操作。
因此,根据一个实施方案,提供了水基井处理流体,其包含含水连续相、由烷基化聚醚胺组成的粘土稳定剂和加重材料。
水基井处理流体可以为能够将由烷基化聚醚胺组成的粘土稳定剂送入地下地层的任何流体。因此,在一个实施方案中,该水基井处理流体是钻井流体、钻进流体(drill-in-fluid)、增产流体、压裂流体、酸化流体、补救流体(remedial fluid)、修井流体(well reworking fluid)或砾石充填流体。
根据另一实施方案,含水连续相是与井处理流体的配方相容并且也与这里公开的粘土稳定剂相容的任何水基流体相。在一个实施方案中,该含水连续相选自淡水、海水、卤水、水和水溶性有机化合物的混合物,及其混合物。该含水连续相的量应当足以形成水基井处理流体。在一个实施方案中,该含水连续相的量可以为水基井处理流体的近100体积%至小于水基井处理流体的30体积%。在另一实施方案中,该水基连续相的量为水基井处理流体的约95体积%至约30体积%。在又一实施方案中,该水基连续相的量为水基井处理流体的约90体积%至约40体积%。
如上所述,水基井处理流体还包含由烷基化聚醚胺组成的粘土稳定剂。在一个实施方案中,该烷基化聚醚胺为具有式(I)的化合物:
其中R为C2H4或CH(CH)3CH2,
R1为直链或支化的C1至C6烷基,和
x为1至3的整数。在一个实施方案中,R为C2H4,和R1为甲基、乙基、异丙基、正丙基、异丁基或正丁基。根据另一实施方案,R为C2H4和R1为乙基、异丙基或正丙基。在本发明的一个示例性实施方案中,粘土稳定剂为具有式(II)的化合物,或具有式(III)的化合物,或具有式(IV)的化合物:
在本发明的另一示例性实施方案中,粘土稳定剂为具有式(II)的化合物或具有式(IV)的化合物:
通常,粘土稳定剂以足以减少粘土地下材料的基于表面水合的溶胀和/或基于渗透的溶胀中的一种或两种的量存在于水基井处理流体中。具体的水基井处理流体中存在的粘土稳定剂的精确量可以通过对水基井处理流体和所遇到的粘土地层的组合进行测试的试错法来确定。在一个实施方案中,水基井处理流体中本发明的粘土稳定剂的使用量为水基井处理流体的约1至约20磅每桶(lbs/bbl或ppb)。在另一实施方案中,粘土稳定剂在水基井处理流体中的存在量为水基井处理流体的约2至约18ppb。在又一实施方案中,粘土稳定剂在水基井处理流体中的存在量为水基井处理流体的约0.05体积%至约0.5体积%。
水基井处理流体还包含加重材料。该加重材料增加流体的密度,以防止井涌(kick-back)和井喷(blow-out)。适合的加重材料包括固体形式、微粒形式、悬浮在溶液中或溶解在含水连续相中的任何类型的加重材料。在一个实施方案中,该加重材料为硫酸钡、重晶石、赤铁矿、氧化铁、碳酸钙、碳酸镁、有机盐、无机盐或其混合物。加重材料在水基井处理流体中的存在量为有效阻止kick-backs和井喷的量,该量根据处理操作下的地层的性质而改变。在一个具体的实施方案中,加重材料以小于水基井处理流体的800ppb,例如约5ppb至约750ppb或约10ppb至约700ppb的水平包含在水基井处理流体中。
在另一实施方案中,水基井处理流体任选地包含一种或多种常规添加剂。这种添加剂的例子包括但不限于凝胶材料、稀释剂、流体损失控制剂、包封剂、杀菌剂、破胶剂、起泡剂、稳定剂、润滑剂、穿透率增强剂、消泡剂、腐蚀抑制剂、井漏流体(lost circulation fluid)、防穿透成球剂(anti-bit balling agent)、中和剂、pH缓冲剂、表面活性剂、支撑剂和用于砾石充填的砂。
凝胶材料的例子包括但不限于膨润土、海泡石粘土、绿坡缕石粘土、阴离子高分子量聚合物和生物聚合物。
稀释剂的例子包括但不限于木素硫酸盐、改性的木素硫酸盐、多磷酸盐、鞣酸类和低分子量聚丙烯酸酯类。
流体损失控制剂的例子包括但不限于合成有机聚合物、生物聚合物及其混合物、改性的褐煤聚合物、改性淀粉和改性纤维素。
包封剂的例子包括但不限于合成材料、有机材料、无机材料、生物聚合物或其混合物。包封剂可以为阴离子性、阳离子性或非离子性。
可以将本发明的粘土稳定剂和加重材料和任选的添加剂与含水连续相混合,以水基井处理流体。因此,在另一实施方案中,提供了制备水基井处理流体的方法,其包括将由烷基化聚醚胺组成的粘土稳定剂、加重材料和任选的添加剂与含水连续相混合。
在另一实施方案中,提供了抑制在对地下地层进行钻井期间遇到的粘土地下材料的溶胀和/或移动的方法。该方法包括在地下地层中循环水基井处理流体,该水基井处理流体包含含水连续相、由烷基化聚醚胺组成的粘土稳定剂和加重材料。在又一实施方案中,提供了用于使地下地层稳定的方法,其包括用本发明的水基井处理流体接触该地下地层的步骤。接触该地下地层可以在水力压裂哦钻井之前、期间或之后,例如通过将这里公开的水基井处理流体提供至该地下地层来实现。
可以用水基井处理流体进行有效处理的粘土地下材料可以为不同的性质,例如微小的、板状的、管状的和/或纤维状的颗粒,具有极大的表面积。例子包括蒙脱石(绿土)族如蒙脱石、滑石粉、绿脱石、锂蒙脱石和锌蒙脱石,高岭土族如高岭石、珍珠陶土、地开石和埃洛石,含水云母族如水黑云母、海绿石、伊利石和钠伊利石,绿泥石族如绿泥石和鲕绿泥石的粘土矿物,不属于上述族的粘土矿物如蛭石、绿坡缕石和海泡石,以及这些粘土矿物和族的混合层变种。其他矿物组分可以进一步与粘土有关。
在另一实施方案中,抑制粘土地下材料的溶胀和/或移动和使地下地层稳定的材料和方法可以提供为工具包,其包括足量的粘土稳定剂、加重材料和任选的添加剂,用于与含水连续相现场混合。
用这里所述的水基井处理流体使地下地层稳定的结果是,通过移出烃产品的过程从地下地层松脱的粘土地下材料颗粒具有减少的溶胀,具有减少的地下移动,不减少烃产品流,和/或不污染烃产品。没有该水基井处理流体的情况下,粘土地下材料会溶胀和/或移动而抑制或污染烃产品。稳定化效果可以通过对有和没有该水基井处理流体的井进行比较,或者对通过从有和没有该水基井处理流体的地下地层取样的流体(例如油、水或天然气)的流速进行比较。
地下地层可以通过用该水基井处理流体接触它们来稳定化。在一个实施方案中,粘土地下材料溶胀和/或细料移动可以通过用水基井处理流体接触该地下地层来减小,该水基井处理流体包含含水连续相、由烷基化聚醚胺组成的粘土稳定剂、加重材料和任选的添加剂。
在另一实施方案中,先前经水力压裂的地下地层可以通过用水基井处理流体接触该经水力压裂的地下地层来再稳定化,该水基井处理流体包含含水连续相、由烷基化聚醚胺组成的粘土稳定剂、加重材料和任选的添加剂。经水力压裂的地下地层可以为例如已经从中提取烃的经水力压裂的地下地层。优选地,经水力压裂的地下地层是具有矿物内含物的地层,该矿物内含物主要为粘土、页岩、砂和/或其混合物。
在又一实施方案中,水基井处理流体可以用于在钻井期间冲洗井孔的方法。该方法包括在对地下地层进行钻井期间向钻头施用该水基井处理流体。
在再一实施方案中,提供了从含油地下地层提取油的方法,包括通过第一井孔提供加压的本发明的水基井处理流体,和通过第二井孔从该地下地层采收油。优选地,先前对该地下地层进行了经水力压裂和先前提取了油。
实施例
提供以下以说明本发明,但不用于限制其范围。
实施例1
测量毛细管吸升时间(CST)测试,作为对用来形成人造核的经研磨的地层岩石的浆料的相对流动能力的测定。研磨怀俄明州膨润土粘土,将5重量%的经研磨的粘土添加到95重量%的二氧化硅粉,以形成核样品。然后将4克核样品置于40ml的测试流体(该测试流体包含粘土稳定剂和水)中,并在磁力搅拌器上搅拌至少30分钟。然后将5ml的该浆料置于包含CST仪器的滤纸的金属漏斗中,并记录该浆料下降一定距离所需的时间。
这里,将从CST测试获得的数据记录为从下式获得的%变化:
((CST样品/CST空白)–1)×100=____%变化
其中CST空白是不存在核样品的测试流体(溶于水中的5重量%KCl)流动所需距离的CST时间。测试了四种粘土稳定剂:实施例1=2-丙胺、NN’-[1,2-乙烷二基双(氧代-2,1-乙烷二基)]双-(结构II);实施例2=乙胺、NN’-[1,2-乙烷二基双(氧代-2,1-乙烷二基)]双-,(结构IV);对比例3D-230聚醚胺(结构I R=CH(CH3)CH2,R1=H,可获自Huntsman Petrochemical LLC)和对比例4=SD-231聚醚胺(结构1R=CH(CH3)CH2,R1=i-C3H7,可获自Huntsman Petrochemical LLC)。在一些测试流体中,粘土稳定剂首先通过用0.5、0.6或2摩尔冰醋酸或浓HCl(37%)接触20g的该粘土稳定剂来中和。它们在下面记录为纯胺或盐浓度:
表1
注意结果解读。在CST测试中,最好的粘土控制化学物质引起较少的膨润土溶胀;因此测试溶液更快地流过杯,记录的流动时间更短。数字越低(时间和%变化),意味着粘土控制越好。当测试溶液流动快于5%KCl参照溶液时,得到负的百分比变化数值。被测试的化学物质(实施例1和2)的结果总体上显著好于对比化学物质(对比例3和4)的结果。表中的第一行说明无抑制的溶液中的溶胀效应。
尽管上面已经详细描述了本发明的制备和使用的不同实施方案,但是应当理解的是,本发明提供了许多可用的发明构思,其可能体现在广泛多样的具体语境中。这里讨论的具体实施方案仅为制备和使用本发明的具体方式的说明,不确定本发明的范围。
Claims (12)
1.水基井处理流体,其包含含水连续相、由烷基化聚醚胺组成的粘土稳定剂和加重材料。
2.根据权利要求1所述的水基井处理流体,其中该含水连续相选自淡水、海水、卤水、水和水溶性有机化合物的混合物,及其混合物。
3.根据权利要求1所述的水基井处理流体,其中该烷基化聚醚胺为具有式(I)的化合物:
其中R为C2H4,
R1为直链或支化的C1至C6烷基,和
x为1至3的整数。
4.根据权利要求1所述的水基井处理流体,其中该烷基化聚醚胺为具有式(II)的化合物,或具有式(III)的化合物或具有式(IV)的化合物:
5.根据权利要求1所述的水基井处理流体,其中粘土稳定剂在该水基井处理流体中的存在量为该水基井处理流体的约0.05体积%至约0.5体积%。
6.根据权利要求1所述的水基井处理流体,其中该加重材料为硫酸钡、重晶石、赤铁矿、氧化铁、碳酸钙、碳酸镁、有机盐、无机盐或其混合物。
7.根据权利要求1所述的水基井处理流体,进一步包含一种或多种添加剂。
8.制备水基井处理流体的方法,该方法包括将由烷基化聚醚胺组成的粘土稳定剂、加重材料和任选的添加剂与含水连续相混合。
9.根据权利要求8所述的方法制备的水基井处理流体。
10.抑制在对地下地层进行钻井期间遇到的粘土地下材料的溶胀和/或移动的方法,该方法包括在该地下地层中循环水基井处理流体,该水基井处理流体包含含水连续相、由烷基化聚醚胺组成的粘土稳定剂和加重材料。
11.从含油地下地层提取油的方法,该方法包括通过第一井孔提供加压的水基井处理流体,该水基井处理流体包含含水连续相、由烷基化聚醚胺组成的粘土稳定剂和加重材料,以及通过第二井孔从该地下地层采收油。
12.根据权利要求11所述的方法,其中先前对该地下地层进行了水力压裂和先前提取了油。
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Application publication date: 20150422 |