CN1729345A - 控制粘弹性表面活性剂基流体流变性的方法 - Google Patents

控制粘弹性表面活性剂基流体流变性的方法 Download PDF

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CN1729345A
CN1729345A CNA2003801069112A CN200380106911A CN1729345A CN 1729345 A CN1729345 A CN 1729345A CN A2003801069112 A CNA2003801069112 A CN A2003801069112A CN 200380106911 A CN200380106911 A CN 200380106911A CN 1729345 A CN1729345 A CN 1729345A
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杰西·李
埃里克·纳尔逊
凯文·英格兰
菲利普·沙利文
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Abstract

向粘弹性表面活性剂基体系中加入聚合物使得能够调节基液的流变性。尤其是，一方面根据加入的聚合物的浓度与粘弹性表面活性剂浓度之比，另一方面根据加入聚合物的分子量，同一聚合物或者相同类型的聚合物可以起到不同作用如粘度增强剂、降粘剂或粘度恢复增强剂。

Description

控制粘弹性表面活性剂基流体流变性的方法
技术领域
本发明涉及用于调节粘弹性表面活性剂(VES)流体的流变性的组合物和方法，尤其是用于处理地下地层和油气井(oil and gas wells)的组合物和方法。
发明背景
通常，通过在水介质中混合适量合适的表面活性剂如阴离子、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。粘弹性表面活性剂流体的流变，尤其是溶液粘度的增加，归因于在流体中组分所形成的三维结构。当表面活性剂浓度明显超过临界值，并且最终在电解质的存在下时，表面活性剂分子聚结并形成诸如胶束的结构，这种胶束能够相互作用形成表现出粘弹特性的网络。该说明书的剩余部分中，术语“胶束”将用作组织化的互相作用物质(organized interacting species)的通称。
粘弹性表面活性剂溶液通常是通过将某些试剂添加至表面活性剂的浓溶液中而形成的，所述表面活性剂的浓溶液常由例如十六烷基三甲基溴化铵(CTAB)等长链季铵盐构成。在表面活性剂溶液中产生粘弹性的常用试剂是盐，例如氯化铵、氯化钾、水杨酸钠和异氰酸钠以及非离子有机分子，例如氯仿。表面活性剂溶液的电解质含量也是它们的粘弹性的重要控制因素。
人们对于将这种粘弹性表面活性剂用于井筒维护(wellbore service)应用具有浓厚的兴趣。例如，参见美国专利4,685,389，4,725,372，5,551,516，5,964,295和5,979,557。
表面活性剂水性混合物的流变性是由它们向溶剂孤立它们的疏水部分和暴露它们的亲水部分的趋势决定的。这种行为通常形成称作胶束的三维网络结构。特别是根据这些胶束的结构，流体粘度会或多或少地增加，并且流体既表现出粘性又表现出弹性。
开发新型的粘弹性表面活性剂体系的常规方法是筛选大量表面活性剂-和表面活性剂混合物-，直到有一种满足规定的性能指标。显然，这种方法费时。此外，井筒维护流体倾向于在多种条件，尤其是温度、盐度和剪切应力下使用。不幸地是，粘弹性表面活性剂基流体通常对于上述参数的改变非常敏感。因此，“筛选”方法容易产生可适合规定条件的多种体系。这存在后勤问题并且需要广泛地培训现场人员。
因此，希望具有一种体系，能够调节其性能以满足多种指标。例如，考虑在宽的温度范围内使用特殊粘弹性表面活性剂体系的可能性。已知，对粘弹性表面活性剂基流体的流变性产生作用的胶束，一般在窄的温度范围内是稳定的。具有较长的疏水性碳原子链(多于18个碳原子)的表面活性剂使流体在较高温度下稳定。然而，碳链增长也削弱表面活性剂的亲水性；因此，表面活性剂的完全溶解比短链相应物需要多得多的时间。因此，需要一种在高温下能够“激发(boost)”短链体系粘度的方法。还应当强调地是，有些较便宜的粘弹性表面活性剂可以提供这种粘度的增加，但是对于某些应用所希望的来说还不够。提供这种粘度迅速增加的方法将是允许使用“不完美”产品的方法，或者限制加入到体系中的表面活性剂的量，由此降低体系的总费用。
粘弹性表面活性剂基体系的另一种性能是它们的剪切敏感性。例如，在采油业，往往有利地是一种流体，其在低剪切或无剪切下具有高粘度，而在高剪切下具有低粘度。这种流体容易泵送，而当放在井中后非常粘稠。尽管剪切敏感性是大多数粘弹性体系的内在性能，但是独立的性能是流体不再经受高剪切时的粘度恢复(viscosity-recovery)或再恢复(rehealing)的程度。控制再聚集(reassembling)(再恢复)的程度对于使用于不同应用中的表面活性剂体系的特性最佳化是必要的。例如，水力压裂时，当流体离开管子中的高剪切区并进入水力压裂裂缝中的低剪切环境时，对于流体来说尽可能快地恢复粘度是重要的。另一方面，在挠性管清除(coiled turbing cleanup)中，为了更有效地将固体从井底“喷射”到环形物(annulus)中，稍微延迟恢复全部粘度是有利的。一旦在环形物中，恢复的粘度将确保，固体被有效地输送到表面。因此，希望改善粘度恢复并最小化恢复所需要的时间。
最后，众所周知，在粘弹性表面活性剂基体系中加入某些组分能够引起流体粘度的剧烈降低，称作“破裂(breaking)”。通过改变已经存在于流体中的水或电解质或其它组分的含量也能够发生破裂。粘弹性表面活性剂流体的粘度被减小或损失；该粘度的减小或损失实现油藏、裂缝或其它处理区域的清理。
然而，在一些情况下，例如，当需要在特定时间或条件下破裂流体时，当需要加速粘度减小时或当储层流体的自然流入(例如，在干天然气储层(dry gas reservoirs)中)没有破裂或没有充分破裂粘弹性表面活性剂流体时，对破裂进行更好的控制将是合适的。。
本说明书描述了用于使包括增稠量的粘弹性表面活性剂的水性溶液改变流变的组合物和方法。
UK专利GB2332223，Hughes、Jones和Tustin的标题为“用作油井加注液的粘弹性表面活性剂基胶体组合物(Viscoelastic surfactant based fellingcomposition for wellbore service fluids)”中，描述了延迟和控制粘弹性表面活性剂基胶凝组合物粘度和胶凝作用的积聚(build-up)的方法。这些方法被用于帮助将延迟的(“预凝胶化”)流体放入多孔介质中，然后现场(in-situ)引起粘弹性胶体的形成。
Rose等人在美国专利4735731中描述了通过在表面干涉(intervention)可逆破裂粘弹性表面活性剂基溶液的粘度的几种方法。这些方法包括加热/冷却流体、调节pH值或者使有效量的可混溶的或不混溶的油气(hydrocarbon)与该流体接触，然后使该流体位于一定条件下，以使流体的粘度基本上得以恢复。Rose的可逆处理对钻井液有用，因此泵送至井内的流体足够粘以携带钻屑至表面，而又能够在脱除固体颗粒的表面上破裂。Rose讨论的破裂方法不能用来沿着井向下(down a well)破裂粘弹性溶液，而且还表现出对流体的粘度有直接的影响。
2001年4月4日提交并且公开号为20020004464的美国专利申请09/826,127描述了不同类型的降粘剂(breaking agent)和实现井下延迟释放降粘剂的不同方法，以使含水流体的流变性能在表面或注射步骤(phase)过程中不改变。2002年7月12日提交的美国专利申请10/194,522还公开了，有些聚合物，尤其是有些聚电介质能够用作降粘剂。
然而，还发现，有些类型的聚合物还对包括增稠量的粘弹性表面活性剂的水性溶液的流变性具有完全不同的影响。因此，还需要在预定时间或条件下，在地下油井或气井处理后，破裂/增强/恢复粘弹性表面活性剂流体的方法。
发明简述
本发明的发明人发现，在给定的粘弹性表面活性剂浓度下，根据分子量和在流体中的浓度，或者更准确地说，根据加入的聚合物的浓度与粘弹性表面活性剂的浓度之比，聚合物可以起到不同作用(降粘剂，粘度增强剂或恢复粘度增强剂(viscosity recovery enhancer))。
根据本发明第一方面，加入的聚合物具有低的分子量，通常低于约25,000。此时，发现聚合物主要起到降粘剂的作用。
根据本发明第二方面，加入的聚合物的分子量高于约25,000。此时发现，在低浓度(相对于粘弹性表面活性剂的量)时，聚合物促进了剪切降低(shear-degradation)后粘度的快速恢复，而在较高浓度(通常约7wt％)时，聚合物能够使含水流体粘度增加。
本发明方法集中于，但不限于粘弹性表面活性剂体系的流变性改性剂，其中所述粘弹性表面活性剂体系基于阳离子表面活性剂如瓢儿菜基甲基二(2-羟乙基)氯化铵(EMHAC)；两性离子表面活性剂如内胺盐(betaine)表面活性剂；和阴离子表面活性剂如油酸衍生物。然而，本发明所述方法和组合物还用于调节基于阴离子、阳离子、非离子和两性离子表面活性剂的粘弹性表面活性剂流体的粘度。
本发明一方面提供了方法和组合物，用于延迟调节粘弹性表面活性剂胶凝组合物的粘度，而不明显破坏或基本上不破坏压裂处理过程中用于支撑剂悬浮和输送所需要的初始流体性能。因此，本发明涉及通过沿着井向下注入含水流体来处理地下地层的方法，所述含水流体包括增稠量的粘弹性表面活性剂，并且还包括粘度调节剂或其前体。优化的配方确保了，在表面条件下快速形成粘弹性凝胶，并在泵入和放置在裂缝的过程中保持稳定。这样，随后，通过加入聚合物明显改变凝胶粘度。
根据用途的需要，能够对粘弹性体系流体的剪切敏感性和水合进行微调。这能够通过调节同一聚合物的分子量分布或者换为另一种聚合物来实现。在某些温度范围内，在100sec-1剪切速率下，聚合物的加入还增加了粘弹性流体的粘度。
本发明又一方面涉及利用聚电介质作为粘弹性表面活性剂基溶液的降粘剂。用于本发明的聚电介质可以是阴离子、阳离子、非离子或两性离子的。尽管应当明白，可以使用任何合适的聚电介质，但是优选磺化聚萘、磺化聚苯乙烯和磺化笨乙烯/马来酸酐聚合物。更具体地说，优选聚乙二醇(PEG)、聚丙二醇(PPG)、PEG和PPG的嵌段共聚物、聚萘磺酸盐和聚苯乙烯磺酸盐。
还应当明白，本发明的压裂(fraction)组合物可以含有水、电介质、表面活性剂和降粘剂之外的组分。这些附加组分是，例如酸、碱、缓冲剂、用于控制多价阳离子的螯合剂、防冻剂等。
即使本申请集中于处理碳氢化合物油井，但是本发明方法和组合物还能够用于其它应用，包括但不限于水井、煤床甲烷的回收、和地表水或地下水污染的保持或修复。
附图简述
图1是聚合物分子量对聚合物与粘弹性表面活性剂重量比的图，并表示了聚合物的加入对包括所述粘弹性表面活性剂的水性溶液的作用。
图2是表示在70°F至310°F的温度范围内，低分子量聚苯乙烯磺酸钠对甜菜碱类VES流体的作用。
图3是表示在70°F至310°F的温度范围内，低分子量聚苯乙烯磺酸钠对甜菜碱类VES流体的作用。
图4是表示在50°F至300°F的温度范围内，高浓度下的高分子量聚萘磺酸钠对甜菜碱类VES流体的作用。
图5是表示在150°F至230°F的温度范围内，高浓度下的高分子量聚苯乙烯磺酸钠对甜菜碱类VES流体的作用。
图6是表示在50°F至250°F的温度范围内，高浓度下的高分子量聚苯乙烯磺酸钠对阳离子季铵类VES流体的作用。
图7是表示粘度剪切降低后，低浓度下的高分子量聚苯乙烯磺酸钠对阳离子季铵类VES流体的作用。
图8是表示粘度剪切降低后，低浓度下的高分子量聚萘磺酸钠对甜菜碱类VES流体的作用。
图9是表示粘度剪切降低后，低浓度下的高分子量聚萘磺酸钠对甜菜碱类VES流体的作用。
图10是表示在70°F至310°F的温度范围内，低分子量聚丙二醇对甜菜碱类VES流体的作用。
详述
实施例1：加入聚合物以调节粘度
在结合聚合物应用包括粘弹性表面活性剂的粘弹性表面活性剂基胶凝组合物时，根据聚合物的分子量和加入的聚合物与粘弹性表面活性剂的重量比，可以得到完全不同的结果。
例如，向包括表面活性剂(在测试A至F和I中，是两性离子表面活性剂芥子基酰胺丙基二甲基甜菜碱(erucic amidopropyl dimethyl betaine)，记做Z1；在测试G和H中，是阳离子的季铵)的水性溶液中加入不同类型的聚合物(PNS：聚萘磺酸盐，或PSS：聚苯乙烯磺酸盐，或PPG：聚丙二醇)，其分子量列在下表I中。表I中，聚合物与表面活性剂的重量比以wt％表示。
表I
  测试编号   表面活性剂   聚合物   分子量   Wt％  作用
  A   Z1   PNS   30000   17.5  激发剂(booster)
  B   Z1   PNS   100000   10  激发剂
  C   Z1   PNS   30000   2.5  恢复剂
  D   Z1   PNS   70000   2.5  恢复剂
  E   Z1   PSS   15000   2.5  降粘剂
  F   Z1   PSS   3000   2.5  降粘剂
  G   C1   PNS   30000   10  激发剂
  H   C1   PNS   30000   5  恢复剂
  I   Z1   PPG   4000   12.5  降粘剂
基于上面的数据，图1是以加入聚合物的分子量作为X轴，以重量比wt％作为Y轴对不同测试进行作图。该图可以分为三个部分。加入较低分子量的聚合物，粘度下降(broken)。加入较高分子量聚合物，溶液粘度或者增加(如果聚合物浓度足够高)或者促进了剪切降低后粘度的恢复(恢复作用)。
实施例2：聚合物作为降粘剂
通过在水中加入2.4wt％的芥子基酰胺丙基二甲基甜菜碱来制备基液。向溶液中加入0.06wt％(重量百分比)聚苯乙烯磺酸盐(估计分子量在15000至20000之间)，以使wt％值等于2.5％。在100sec-1和70°F至310°F下测试包括或不包括聚合物添加剂的流体粘度，并做图2。图2表示，当存在聚笨乙烯磺酸盐降粘剂时，观察到流体粘度明显降低。这种流体粘度的降低是永久的。
实施例3：聚合物作为降粘剂
通过在水中加入2.4wt％的芥子基酰胺丙基二甲基甜菜碱来制备基液。向溶液中加入0.06wt％聚苯乙烯磺酸盐(估计分子量在3000至5000之间)，以使wt％值等于2.5％。在100sec-1和70°F至310°F下测试包括或不包括聚合物添加剂的流体粘度，并做图3。图3表示，当加入聚苯乙烯磺酸盐降粘剂时，流体粘度明显降低。这种流体粘度的降低是永久的。
实施例4：聚合物作为粘度激发剂
通过在水中加入2.4wt％的芥子基酰胺丙基二甲基甜菜碱来制备基液。向溶液中加入0.42wt％聚萘磺酸盐(估计分子量约30000)，以使wt％值等于17.5％。在100sec-1和50°F至300°F下测试包括或不包括聚合物添加剂的流体粘度，并做图4。图4表示，通过加入聚合物，流体粘度明显升高，并且这种增加在约200至220°F的温度下尤其明显。
实施例5：聚合物作为粘度激发剂
通过在水中加入2.wt％的芥子基酰胺丙基二甲基甜菜碱来制备基液。向溶液中加入0.24wt％聚苯乙烯磺酸盐(估计分子量约1,000,000)，以使wt％值等于10％。在100sec-1和150°F至230°F下测试包括或不包括聚合物添加剂的流体粘度，并做图5。通过加入聚合物再次实现了流体粘度的明显增加。
实施例6：聚合物作为粘度激发剂
通过在水中加入4wt％的阳离子季铵和4％的氯化钾来制备基液。以20lb/1000加仑基液的浓度加入聚苯乙烯磺酸盐(分子量约30,000)，对应的重量比为10％。在100sec-1和50°F至260°F下测试包括或不包括聚合物添加剂的基液的粘度，并做图6。在较高温度和较低温度下都观察到粘度的明显增加。在中间温度范围内观察到一定程度的粘度降低。
实施例7：聚合物作为恢复剂
通过在水中加入4wt％的阳离子季铵和4％的氯化钾来制备基液。以10lb/1000加仑基液的浓度加入聚苯乙烯磺酸盐(分子量约30,000)，对应的重量比为5％。将流体在5,000sec-1剪切下进行剪切3分钟。在1sec-1和70°F下测试包括或不包括聚合物添加剂的基液的粘度，并对时间做图7。聚合物的加入当高剪切停止时，提供了粘度的快速恢复。
实施例8：聚合物作为恢复剂
通过在水中加入2wt％的芥子基酰胺丙基二甲基甜菜碱来制备基液。向溶液中加入0.06wt％的聚苯乙烯磺酸盐(估计分子量约30,000)，以使wt％值等于2.5％。将流体在5,000sec-1剪切下进行剪切3分钟。在1sec-1和70°F下测试包括/不包括聚合物添加剂的基液的粘度，并对时间做图8。聚合物的加入当高剪切停止时，提供了粘度的快速恢复。
实施例9：聚合物作为恢复剂
通过在水中加入2.4wt％的芥子基酰胺丙基二甲基甜菜碱来制备基液。向溶液中加入0.06wt％的聚萘磺酸盐(估计分子量约70,000)，以使wt％值等于2.5％。将流体在5,000sec-1剪切下进行剪切3分钟。在1sec-1和70°F下测试包括/不包括聚合物添加剂的基液的粘度，并对时间做图9。无剪切时，聚合物的加入提供了粘度的快速恢复。
实施例10：聚合物作为降粘剂
通过在水中加入6wt％的芥子基酰胺丙基二甲基甜菜碱VES流体来制备基液。向溶液中加入0.3wt％的聚丙二醇(估计分子量约4,000)，以使wt％值等于12.5％。在100sec-1下测试包括/不包括聚合物添加剂的基液的粘度，并对温度做图10。聚合物的加入降低了粘度。
上面对本发明具体实施方案的描述不是要全部列出本发明所有可能的实施方案。本领域技术人员将知道，能够在本发明范围内对所述具体实施方案进行改变。尤其是，尽管本发明的不同实施方案对于水力压裂应用来说最好，但是本发明还可以用于利用表面活性剂基复合流体的多种其它油田应用中，如酸化、砾石充填、挠性管清除、和其它新的化学处理。

Claims (10)

1.处理地下地层的方法，包括下述步骤：
(a)沿着井向下注入包含增稠量的粘弹性表面活性剂的含水流体；
(b)提供在井下条件下引起该流体的流变性变化的聚合物添加剂。
2.根据权利要求1的方法，其中所述聚合物添加剂是聚电解质。
3.根据权利要求2的方法，其中所述聚电解质是包封的。
4.根据权利要求2或3的方法，其中所述聚合物添加剂选自磺化聚萘、磺化聚苯乙烯和磺化苯乙烯/马来酸酐聚合物。
5.根据权利要求4的方法，其中所述聚合物添加剂选自聚乙二醇、聚丙二醇、聚乙二醇和聚丙二醇的嵌段共聚物、聚萘磺酸盐和聚苯乙烯磺酸盐。
6.根据权利要求1至5中任一项的方法，其中所述粘弹性表面活性剂选自阴离子表面活性剂、阳离子表面活性剂和两性离子表面活性剂。
7.根据权利要求6的方法，其中所述粘弹性表面活性剂选自二十二碳烯基甲基二(2-羟乙基)氯化铵(EMHAC)、内胺盐表面活性剂和油酸衍生物。
8.根据权利要求1至7中任一项的方法，其中所述聚合物添加剂引起该流体的粘度降低，并且分子量低于约25,000。
9.根据权利要求1至7中任一项的方法，其中所述聚合物添加剂引起该流体的粘度增加，并且分子量大于约25,000，且聚合物与粘弹性表面活性剂的重量比大于7％。
10.根据权利要求1至7中任一项的方法，其中所述聚合物添加剂促进了剪切降低后该流体的粘度的恢复，并且分子量大于约25,000，且聚合物与粘弹性表面活性剂的重量比低于7％。
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