CN1969108A - 用粘弹性表面活性剂胶凝的含水流体的体系稳定剂和性能增强剂 - Google Patents
用粘弹性表面活性剂胶凝的含水流体的体系稳定剂和性能增强剂 Download PDFInfo
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Abstract
用有效量的碱土金属氧化物和/或碱土金属氢氧化物将用粘弹性表面活性剂(VES)胶凝的含水粘弹性流体稳定并且改进。特别是在升高的温度下，这些流体更加稳定并且具有减少的或者没有沉淀的趋势。这些添加剂还可以将粘度升高至其中需要较少的VES以保持给定的粘度的点下。例如在水力压裂中，可以将这些稳定的、增强的含水粘弹性流体用作地下烃地层的处理流体。
Description
发明领域
[0001]本发明涉及在烃回收操作期间使用的含水粘弹性流体，并且在一个实施方案中更特别地涉及用于稳定和改进该含水粘弹性流体的方法和添加剂。
发明背景
[0002]水力压裂是一种利用泵送速率和水压使地下地层断裂或破裂的方法。一旦制造了裂缝，则将相对于地层渗透性而言高渗透性的支撑剂泵送到裂痕中以将裂缝撑开。当施加的泵送速率和压力降低或者从地层中除去时，裂缝或裂痕不能完全地闭合或合拢，因为高渗透性的支撑剂将裂缝保持敞开。支撑的裂缝或裂痕提供了一条将开采的井眼与较大的地层区域相连而提高烃产量的高渗透性路径。
[0003]合适的压裂流体的开发是一项复杂的技术，因为该流体必须同时满足许多条件。例如，它们必须在可能造成在压裂操作结束之前流体分解并且使支撑剂过早沉淀的高温和/或高的泵送速率和剪切速率下稳定。已经开发出了多种流体，但大多数商业使用的压裂流体是被胶凝或发泡的水基流体。当将流体胶凝时，通常使用聚合物胶凝剂，例如溶剂化多糖，其可以是交联的或可以是不交联的。增稠或胶凝的流体有助于在压裂操作期间将支撑剂保持在流体内。
[0004]尽管在过去已经将聚合物用作压裂流体中的胶凝剂以将固体颗粒支承或悬浮于盐水中；但这些聚合物需要被注入单独的破胶剂组分以降低粘度。另外，即使在胶凝的流体被破胶之后这些聚合物也容易在支撑剂上留下涂层，该涂层可能妨碍支撑剂的作用。研究还表明，在某些聚合物胶凝的载体流体上存在的“鱼眼”和/或“微凝胶”将堵塞孔喉，导致了破损的泄漏并且造成地层破坏。常规的聚合物还是阳离子或阴离子性的，其表现出可能损坏开采地层的缺点。
[0005]用粘弹性表面活性剂(VES)胶凝的含水流体在本领域中也是公知的。然而，在某些条件下例如在高温下，VES-胶凝的流体将随着时间的流逝而分离和/或沉淀。如果可以设计出用于稳定和增强在处理流体例如压裂流体的注入中使用的含水的VES-胶凝流体的一种组合物和方法，则将是所希望的。
发明概述
[0006]因此，本发明的一个目的是提供一种用稳定的非-聚合物粘弹性表面活性剂(VES)稠化的含水处理流体，例如在烃回收操作中使用的那些。
[0007]本发明的另一个目的是提供一种使用稳定并且抑制沉淀的含水粘弹性流体处理地下地层的方法。
[0008]本发明的仍然另一个目的是提供一种在相对高的温度下稳定并且抑制沉淀的用VES胶凝的含水粘弹性流体。
[0009]在实施本发明的这些和其他目的中，在一个形式中提供了一种处理地下地层的方法，该方法包括提供一种含水粘弹性处理流体。该流体包括：含水基础流体，粘弹性表面活性剂(VES)胶凝剂，和一定量的有效增加稳定性和/或减少沉淀的添加剂。该添加剂可以是碱土金属氧化物和/或碱土金属氢氧化物。另外，在本方法中将该含水粘弹性表面活性剂处理流体穿过井眼注入到地下地层内。然后用该流体处理地下地层。
[0010]在本发明的另一个非限定性实施方案中进一步提供了一种含水粘弹性处理流体，所述处理流体包括：含水基础流体，粘弹性表面活性剂(VES)胶凝剂，和一定量的有效增加稳定性和/或减少沉淀的添加剂。同样，该添加剂可以是碱土金属氧化物和/或碱土金属氢氧化物。
附图简述
[0011]图1是在含有和不含有5.0pptg MgO稳定剂的情况下10％VES含水压裂体系在270(132℃)下随着时间流逝的表观粘度的图；和
[0012]图2是表示含有加载在同一种盐水中的同一种VES的两种流体的照片，其中不含有MgO的流体表现出VES沉淀，含有MgO的流体没有表现出VES沉淀。
发明详述
[0013]已经发现，将碱土金属氧化物例如氧化镁和碱土金属氢氧化物例如氢氧化钙加入到用VES胶凝的含水流体中提高了流体的粘度，稳定了流体，并且防止或抑制了固体在这些盐水中的沉淀。特别地，该VES-胶凝的含水流体在高温下例如在200或更高温度下更加稳定。该发现将使得该VES体系能够在较高的温度下使用，并且将有助于使水力压裂操作之后的地层损坏最小化。可能的是，将这些添加剂引入VES体系中可以减少用于获得进行VES应用或处理所需的流体粘度而需要的VES表面活性剂的量。
[0014]在本发明的方法中，作为一个非限定性的例子，首先通过将VES共混到含水流体中来制备含水压裂流体。含水基础流体可以是例如水、盐水、水基泡沫或者水-醇混合物。盐水基础流体可以是常规的或者被开发的任何盐水，其起到了用于各种浓缩组分的合适介质的作用。对于非限定性的例子而言，为方便起见，在许多情况下盐水基础流体可以是在完井液所使用的位置上可以得到的盐水。
[0015]可以使用盐来制备可用于本发明的流体的盐水，这些盐包括，但不一定限于，NaCl、KCl、CaCl2、MgCl2、NH4Cl、CaBr2、NaBr2、甲酸钠、甲酸钾，以及其他普遍使用的增产和完井盐水的盐。用于制备盐水的盐的浓度可以约为水的0.5wt％直至给定的盐在新鲜水中的饱和度附近，例如为以水的重量计的10％、20％、30％和更高百分比的盐。作为非限定性的例子，盐水可以是一种或多种所述盐的组合，例如使用NaCl和CaCl2或者NaCl、CaCl2和CaBr2制备的盐水。
[0016]可以将任何合适的混合装置用于该过程。在分批混合的情况下，将VES和含水流体共混足以形成胶凝或稠化的溶液的一段时间。可用于本发明的VES可以是与在钻井服务行业中的那些类似的VES体系的任何一种，并且可以包括，但不限于，胺、胺盐、季铵盐、酰氨基胺氧化物、胺氧化物、其混合物等。合适的胺、胺盐、季铵盐、酰氨基胺氧化物和其他的表面活性剂描述于美国专利No.5,964,295；No.5,979,555和No.6,239,183中，这些在此引入作为参考。
[0017]通过使用不含聚合物的体系，粘弹性表面活性剂提高了压裂流体性能。这些体系提供了改进的减粘裂化、更高的砂石运输能力、在处理之后更容易回收，并且相对而言不会破坏油层。在油田操作中这些体系还更容易被混合在飞轮(fly)上，并且不像一些现有体系那样在流体体系中需要许多助添加剂。
[0018]适用于本发明的粘弹性表面活性剂包括，但不一定限于，非离子、阳离子、两性和两性离子表面活性剂。两性离子/两性表面活性剂的特定例子包括，但不一定限于，得自于某些蜡、脂肪和油的二羟基烷基氨基乙酸酯、烷基两性乙酸酯或丙酸酯、烷基甜菜碱、烷基酰氨基丙基甜菜碱和烷基亚氨基单-或二丙酸酯。季胺表面活性剂通常是阳离子的，甜菜碱通常是两性离子的。可以将增稠剂与无机水溶性盐或有机添加剂例如邻苯二甲酸、水杨酸或它们的盐组合使用。
[0019]一些非离子流体与阳离子流体类型相比本质上更少地损坏开采的地层，并且与阴离子胶凝剂相比每磅更加有效。胺氧化物粘弹性表面活性剂具有每磅提供更多胶凝能力的潜能，这使得其比该类型的其他流体更便宜。
[0020]胺氧化物胶凝剂RN+(R′)2O-可以具有以下结构(I)：
其中R是平均约8-24个碳原子的烷基或烷基酰氨基，R′独立地是平均约1-6个碳原子的烷基。在一个非限定性实施方案中，R是平均约8-16个碳原子的烷基或烷基酰氨基，R′独立地是平均约2-3个碳原子的烷基。在一个作为选择的非限定性实施方案中，胺氧化物胶凝剂是牛脂酰氨基丙胺氧化物(TAPAO)，其由于两个R′基团均是丙基而因此将被理解为是二丙胺氧化物。
[0021]按照美国专利No.5,864,285出售的材料包括ClearFRACTM，该材料还可以包含大于10％的二醇。一种优选的VES是胺氧化物。如所述的那样，一种特别优选的胺氧化物是作为SurFRAQTMVES被BakerOil Tools出售的牛脂酰氨基丙胺氧化物(TAPAO)。SurFRAQ是一种VES液体产品，其为50％的TAPAO和50％的丙二醇。这些粘弹性表面活性剂能够将水溶液胶凝而形成胶凝的基础流体。本发明的添加剂还可以用于作为一种VES体系的、类似于SurFRAQ的、含有由Baker Oil Tools出售的VES破胶剂的Diamond FRAQTM。
[0022]包含在压裂流体中的VES的量取决于两个因素。在压裂流体的非限定性情况下，一个涉及到产生足够的粘度以控制流体泄漏到裂痕孔隙中的速度，第二个涉及到产生足够高的粘度以在流体注入步骤期间保持悬浮于其中的支撑剂颗粒。因此，取决于应用而将VES以全部含水流体的体积的约0.5-12.0％(5-120加仑/千加仑(gptg))的浓度加入到含水流体中。在另一个非限定性实施方案中，本发明的范围为约1.0-约6.0体积％的VES产品。在本发明的一个作为选择的非限定性形式中，VES的量为2-约10体积％。
[0023]本发明的添加剂包括，但不一定限于，碱土金属氧化物或碱土金属氢氧化物或其混合物。在一个非限定性实施方案中，这些添加剂中的碱土金属是镁、钙、钡和/或锶。在一个非限定性实施方案中，添加剂的量为约0.5-约40磅/千加仑(pptg)含水流体。在另一个非限定性变型中，该量为约2-约10pptg。
[0024]如所述的那样，已经发现用这些添加剂处理的含水粘弹性处理流体与没有添加剂存在的其他相同流体相比具有提高的稳定性。在升高的例如等于或大于约200或以上的温度特别如此。作为选择，该温度可以等于或大于约220或以上，或者在另一个非限定性实施方案中等于或大于约230或以上。另外或者作为选择，含有该添加剂的含水粘弹性处理流体与没有添加剂存在的其他相同流体相比具有减少的沉淀。将理解的是，沉淀不一定完全被消除对于本发明而言将被认为是成功的，尽管防止沉淀的确是一个目标。
[0025]还发现使用本发明的添加剂可以提高VES-胶凝的含水流体的粘度。由此，由于粘弹性表面活性剂相对更贵，因此可以将与常规相比更少的VES与本发明的添加剂一起使用而获得相同的粘度，由此降低了胶凝流体的总成本。
[0026]在水力压裂应用中，通常在加入VES之后将支撑剂加入到基础流体中。支撑剂包括，但不限于，例如石英砂颗粒、玻璃和陶瓷珠粒、铝矾土颗粒、胡桃壳碎片、铝片、尼龙片等。支撑剂通常以约1-14磅/加仑(120-1700kg/m3)压裂流体组合物的浓度使用，但是根据压裂设计需要，可以采用更高或更低的浓度。基础流体还可以含有钻井服务行业中常用的其他常规添加剂，例如水湿润表面活性剂、非-乳化剂等。在本发明中，基础流体还可以含有可促进VES流体的凝胶破胶(降低粘度)的添加剂。
[0027]尽管在本文中最通常地将本发明的粘弹性流体描述为用于压裂流体，但我们预期它们将在酸化流体、砂砾填充流体、增产流体等中找到用途。当然，当处理流体是压裂流体时，该流体还含有至少有效量的支撑剂以撑开裂痕，并且在充足和有效的水压和泵送速率下将流体注入地层以使地层断裂。当处理流体是酸化流体时，其进一步含有有效量的、足够强度的无机或有机酸以将地层酸化。当将粘弹性表面活性剂用于砂砾填充流体时，该胶凝剂有助于在流体中含有有效量的砂砾。如果将粘弹性表面活性剂用于另一种钻井增产流体，则使用有效量的任意附加的增产剂。当将粘弹性表面活性剂用于失液控制应用时，使用有效量的盐或者容易除去的固体，并且胺氧化物胶凝剂有助于盐或固体悬浮在流体中。处理流体的这些其他组分是本领域非常公知的。
[0028]在本发明的另一个实施方案中，处理流体可以含有其他的稠化剂、其他的表面活性剂、粘土稳定添加剂、除垢剂、生物聚合物降解添加剂和其他的常用组分。
[0029]支撑剂、固体颗粒或砂砾可以是适用于其预定目的例如作为栅网或支撑剂等的任何固体颗粒物质。合适的材料包括，但不一定限于，砂石、烧结铝矾土、碳酸钙颗粒、盐粒、陶瓷珠粒等，和其组合。这些固体还可用于失液控制应用。
[0030]一种基本方法是从输送例如砂砾填充流体的常规泵的下游将支撑剂注入载体流体或处理盐水中。为此，将支撑剂悬浮于稠化的盐水中。因此，可以在用于输送砂砾填充流体或其他处理流体的泵下游的注入点下通过小的注射泵将支撑剂注入载体流体。
[0031]将相对于以下实施例进一步描述本发明，这些实施例并不意在限制本发明，而是进一步解释各种实施方案。
实施例1-2
[0032]在270(132℃)下在10.5ppg(1.26kg/升)氯化钙盐水中试验本发明。实施例1不含任何碱土金属添加剂。在表I中示出的时间间隔下在所示的剪切速率下在Grace Instrument Company M5500HTHP粘度计上测量粘度。可以看出，对于每一剪切速率而言，该温度下的粘度作为时间的函数迅速下降。在仅仅40分钟之后停止试验。
[0033]对于实施例2，将5.0pptg MgO体系稳定剂加入到实施例1的体系中，并且随着时间的流逝在相同的剪切速率下进行试验。然而，可以看出随着时间的流逝粘度仅仅稍微降低。在2小时之后中断试验，因为看起来所处理的VES-胶凝的含水流体是稳定的。图1是对于100sec-1剪切速率而言实施例1和实施例2的粘度数据作为时间的函数的图，其示出了这两个之间的对比以及由添加剂产生的稳定性的极大提高。
表I
在270(132℃)下的10％VES体系
实施例1：在270(132℃)下10.5PPg CaCl2盐水中的
10％VES(没有添加剂)
| 时间(min) | 511sec-1 | 170sec-1 | 100sec-1 | 40sec-1 |
| 0 | 75 | 107 | 127 | 170 |
| 20 | 34 | 46 | 53 | 68 |
| 40 | 8 | 10 | 12 | 15 |
实施例2：在270(132℃)下10.5PPg CaCl2盐水中的
10％VES(5.0pptg体系稳定剂)
| 时间(min) | 511sec-1 | 170sec-1 | 100sec-1 | 40sec-1 |
| 0 | 78 | 110 | 131 | 176 |
| 20 | 63 | 88 | 103 | 136 |
| 40 | 72 | 102 | 121 | 162 |
| 60 | 73 | 104 | 123 | 164 |
| 80 | 73 | 103 | 122 | 163 |
| 100 | 71 | 101 | 119 | 159 |
| 120 | 71 | 101 | 119 | 169 |
实施例3
[0034]图2的照片中示出了具有相同VES加载量的两种其他的相同盐水流体。左边的流体含有本发明的氧化镁稳定添加剂，而右边的流体不含。在大于200(93℃)的温度下试验之后，不含氧化镁的流体表现出VES表面活性剂沉淀，而含有氧化镁的流体没有表现出VES表面活性剂沉淀。
[0035]在前述说明书中，已经参照其特定实施方案描述了本发明，并且已经证明了其有效地提供了具有稳定的表面活性剂凝胶粘度的处理流体。然而，将明显的是可以对其作出各种改进和改变，只要不偏离在附属的权利要求书中阐述的本发明的更宽泛的精神或范围。因此，本说明书将被看作是说明性的，而不是限制意义的。例如，盐水、粘弹性表面活性剂、碱土金属氧化物和碱土金属氢氧化物以及落入所述参数内但没有在特定组成中特别地识别或试验的其他组分的特定组合被预期处于本发明的范围内。
Claims (24)
1.一种处理地下地层的方法，所述方法包括：
提供含水粘弹性处理流体，所述含水粘弹性处理流体包含：
含水基础流体；
粘弹性表面活性剂(VES)胶凝剂；和
一定量的有效增加稳定性和/或减少沉淀的添加剂，其中所述添加剂选自碱土金属氧化物、碱土金属氢氧化物，和其混合物；
将含水粘弹性表面活性剂处理流体穿过井眼注入到地下地层内；和
处理地下地层。
2.权利要求1的方法，其中含水基础流体是盐水。
3.权利要求1的方法，其中添加剂中的碱土金属选自镁、钙、锶、钡和其混合物。
4.权利要求1的方法，其中添加剂的有效量为约0.5-约40.0pptg含水粘弹性处理流体。
5.权利要求1的方法，其中
该含水粘弹性处理流体与没有添加剂存在的其他相同流体相比具有提高的稳定性，
该含水粘弹性处理流体与没有添加剂存在的其他相同流体相比具有减少的沉淀，
或者两者。
6.权利要求1的方法，其中VES选自非离子、阳离子、两性和两性离子表面活性剂。
7.权利要求1的方法，其中VES选自胺、胺盐、季铵盐、酰氨基胺氧化物和胺氧化物。
8.权利要求1的方法，其中VES以约0.5-约25vol％的比例存在于含水基础流体中。
9.权利要求1的方法，其中VES是非离子胺氧化物表面活性剂。
10.权利要求9的方法，其中非离子胺氧化物表面活性剂胶凝剂具有结构式RN+(R′)2O-，其中R是平均约8-24个碳原子的烷基或烷基酰氨基，R′独立地是平均约1-6个碳原子的烷基。
11.权利要求9的方法，其中非离子胺氧化物表面活性剂胶凝剂是牛脂酰氨基丙胺氧化物(TAPAO)。
12.权利要求1的方法，其中处理地下地层选自：
在有效压力下使地层断裂，其中含水粘弹性处理流体进一步包含支撑剂；
将地层酸化，其中含水粘弹性处理流体进一步包含酸；
用砂砾填充地层，其中含水粘弹性处理流体进一步包含砂砾；
使地层增产，其中含水粘弹性处理流体进一步包含增产剂；
控制失液，其中含水粘弹性处理流体进一步包含盐或容易除去的固体；和其混合物。
13.权利要求1的方法，其中在该方法期间的一段时间流体处于约200或以上的温度。
14.一种含水粘弹性处理流体，所述处理流体包含：
含水基础流体；
粘弹性表面活性剂(VES)胶凝剂；和
一定量的有效增加稳定性和/或减少沉淀的添加剂，其中所述添加剂选自碱土金属氧化物、碱土金属氢氧化物，和其混合物。
15.权利要求14的含水粘弹性处理流体，其中含水基础流体是盐水。
16.权利要求14的含水粘弹性处理流体，其中添加剂中的碱土金属选自镁、钙、锶、钡和其混合物。
17.权利要求14的含水粘弹性处理流体，其中添加剂的有效量为约0.5-约40.0pptg含水粘弹性处理流体。
18.权利要求14的含水粘弹性处理流体，其中
该含水粘弹性处理流体与没有添加剂存在的其他相同流体相比具有提高的稳定性，
该含水粘弹性处理流体与没有添加剂存在的其他相同流体相比具有减少的沉淀，
或者两者。
19.权利要求14的含水粘弹性处理流体，其中VES选自非离子、阳离子、两性和两性离子表面活性剂。
20.权利要求14的含水粘弹性处理流体，其中VES选自胺、胺盐、季铵盐、酰氨基胺氧化物和胺氧化物。
21.权利要求14的含水粘弹性处理流体，其中VES以约0.5-约25Vol％的比例存在于含水基础流体中。
22.权利要求14的含水粘弹性处理流体，其中VES是非离子胺氧化物表面活性剂。
23.权利要求22的含水粘弹性处理流体，其中非离子胺氧化物表面活性剂胶凝剂具有结构式RN+(R′)2O-，其中R是平均约8-24个碳原子的烷基或烷基酰氨基，R′独立地是平均约1-6个碳原子的烷基。
24.权利要求22的含水粘弹性处理流体，其中非离子胺氧化物表面活性剂胶凝剂是牛脂酰氨基丙胺氧化物(TAPAO)。
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| CN106268496A (zh) * | 2016-07-21 | 2017-01-04 | 西南石油大学 | 一种双子两性粘弹性表面活性剂及其制备方法和以其为稠化剂的清洁压裂液 |
| CN108368422A (zh) * | 2015-10-14 | 2018-08-03 | 罗地亚经营管理公司 | 胶凝液体及相关使用方法 |
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- 2005-05-10 RU RU2006143843/03A patent/RU2369736C2/ru not_active IP Right Cessation
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- 2005-05-10 GB GB0624109A patent/GB2429998B/en not_active Expired - Fee Related
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103328765A (zh) * | 2010-11-19 | 2013-09-25 | 普拉德研究及开发股份有限公司 | 创建连接油井中的水力裂缝网路的高传导性裂缝的方法 |
| CN103328765B (zh) * | 2010-11-19 | 2016-08-10 | 普拉德研究及开发股份有限公司 | 创建连接油井中的水力裂缝网路的高传导性裂缝的方法 |
| CN108368422A (zh) * | 2015-10-14 | 2018-08-03 | 罗地亚经营管理公司 | 胶凝液体及相关使用方法 |
| CN106268496A (zh) * | 2016-07-21 | 2017-01-04 | 西南石油大学 | 一种双子两性粘弹性表面活性剂及其制备方法和以其为稠化剂的清洁压裂液 |
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| CA2566449A1 (en) | 2005-12-01 |
| GB2429998B (en) | 2008-12-17 |
| EP1766185A2 (en) | 2007-03-28 |
| US7343972B2 (en) | 2008-03-18 |
| WO2005112580A2 (en) | 2005-12-01 |
| GB2429998A (en) | 2007-03-14 |
| GB0624109D0 (en) | 2007-01-10 |
| NO20065541L (no) | 2007-01-19 |
| US20050252658A1 (en) | 2005-11-17 |
| CA2566449C (en) | 2011-01-25 |
| EP1766185B1 (en) | 2009-10-21 |
| RU2369736C2 (ru) | 2009-10-10 |
| AU2005244811B2 (en) | 2010-07-15 |
| RU2006143843A (ru) | 2008-06-20 |
| AU2005244811A1 (en) | 2005-12-01 |
| WO2005112580A3 (en) | 2006-05-04 |
| CN100575661C (zh) | 2009-12-30 |
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