CN1604987A - 具有可控可逆粘度的新型流体系统 - Google Patents
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Abstract
本发明涉及处理地下烃类油藏的方法，其包含用处理流体接触地层，该处理流体包含：水溶液、酸、和作为凝胶剂的基本上由瓢儿菜酰胺基丙基甜菜碱组成(或者其质子化/去质子化的同系物或其盐)的表面活性剂。所述处理流体可以还包含用于提高温度稳定性的低级正醇。
Description
发明领域
本发明涉及流体组合物，其粘度可以仔细地调节：从非常低的粘度到成为进一步流动的障碍的足够高的粘度。更具体地，本发明涉及转向流体，其用于增产含烃地层，即增加该地层中油/气的产量。
发明背景
通过钻探穿透含烃地层的井、并且因此产生压力梯度迫使流体从地下的地质地层(即，油藏)中流向该井、可从油藏中获得烃类(石油、天然气等)。通常，井的产量受制于低的渗透率，造成这样的原因是：天然致密地层，或是从诸如钻探、清理等初期井处理中通常产生的地层损伤。
为了增加油藏的净渗透率，通常进行井增产。最普遍的增产技术包括：注入酸、该酸反应并溶解地层损伤或地层的部分，从而为烃类创造出可选的流动路径以从地层中迁移到井中。如果注入速率和压力足够导致引发油藏的地层破裂，这项酸化处理技术可能最终会与破裂联系到一起。
流体灌注是增产处理成功的关键。天然的油藏通常是非均相的，酸性流体会优先进入较高渗透率的地方而不是对最需要处理地区的处理；类似地，由于较低程度的损伤或较高的渗透率，酸处理倾向于去除易于到达的损伤。酸性流体各个所增添的容量沿着阻力较低的路径流动，因而无法去除最重要的损伤。酸反应非常地迅速导致几乎立即被用尽、因而不能提供对未处理地区的处理，通过该事实，流体灌注的关键特征被恶化。
为了控制处理流体灌注，已经应用了各种技术。机械技术包括，例如使用密封球和封隔器、以及使用卷绕油管灌注以在横穿有利的区域上具体地确定流体。非机械技术通常使用凝胶剂作为转向剂，以用于暂时性地损害较高渗透率地区和提高落入低渗透率地区的处理区域的比例。当然，转向剂自身不应损伤油藏，因此，在酸处理后可容易地除去转向剂，使得较高渗透率区域保持不变是重要的。
最商品化的化学转向剂是基于交联的聚合物。不幸的是，这些体系在地层中留下会损伤地层的残余物，导致烃类产量的减少；另外，交联反应容易受到地层化学，泵设备中的污染物等的干扰。
使用自转向酸(self-diverting acid)也是众所周知的，该自转向酸通常由盐酸混合着凝胶剂和pH值敏感交联剂组成。自转向酸通常被设计成在中间的pH值时发生凝胶化，此时酸被部分地消耗掉；自转向体系不是基于交联化学，而是通过交联化学依赖于粘弹性的表面活性剂；自转向体系在美国专利4,695,389中描述过(也参见，美国专利4,324,669和英国专利2,012,830,在此全部引用)---其具有本申请的共同受让人。基于粘弹性的表面活性剂体系表现出非常低的摩擦压力，因而易于用泵送和形成井底凝胶。美国专利4,695,389公开了用于酸压裂(acid fracturing)的基于粘弹性表面活性剂的凝胶剂，特别优选的实施方案是包含N，N-双(2-羟乙基)脂肪胺乙酸盐(凝胶剂)、碱金属乙酸盐、乙酸(该酸实际上从地层里除去损伤)和水的流体。
改进的自转向体系在美国专利申请09/419,842中描述过，其具有本申请的共同受让人以及在相应的国际专利申请WO 01/29369中描述过。这个申请，在此引为参考，提供了适合酸处理的制剂，它包含有两亲表面活性剂，该表面活性剂在活化量的共表面活性剂和通过酸与地层反应而生成的多价阳离子存在下凝胶化；当该凝胶剂与盐酸混合时，共表面活性剂防止溶液凝胶化，当pH值增大到2以上时溶液凝胶化。
在优选的实施方案中，两亲表面活性剂是含有下述分子式的油基丙基甜菜碱，并且共表面活性剂优选地是十二烷基苯磺酸钠，
从美国专利申请09/419,842和其相应的国际专利申请WO 01/29369中已知的组合物，由于温度的限制，其商业应用有限。具体而言，基于油酰胺基丙基甜菜碱和十二烷基苯磺酸钠的制剂只能用于大约200°F(93℃)以下，而碳酸盐酸化处理市场需要的温度高达约300°F(约150℃)。
因此本发明的目的是提供新的具有改进温度稳定性的自转向酸的制剂。
发明概述
根据本发明的第一实施方案，提供增产地下烃类油藏的方法，其包含用处理流体接触地层，该流体由以下组成：酸、瓢儿菜酰胺基丙基甜菜碱(或者其质子化、去质子化，同系物或其盐)、正醇，通常选自甲醇和/或乙醇，最优选地是甲醇。本发明的制剂也可能包含各种标准添加剂如腐蚀抑制剂、非乳化剂和铁控制剂。
如同从美国专利申请09/419,842中已知的组合物，随着将酸加至由水和粘弹性表面活性剂(瓢儿菜酰胺基丙基甜菜碱)组成的碱性流体，本发明的组合物表现出接近类似水的粘度。当酸被消耗在与碳酸盐地层的反应中时，粘性的凝胶开始形成，该凝胶保持高粘度因而在泵送中可以实现连续的转向；这项工作完成后重新开始烃类生产，生产出的烃类使该凝胶的粘度降低到接近于类似水的粘度，不会留下任何残余物。
本发明中最优选的组合物包含甲醇，优选的甲醇浓度按体积计在约0.1％到约10％之间；最优选的甲醇浓度按体积计在约1％到2％之间。甲醇基本上表现两种功能：它补充在混合泵送之前的流体中任何醇类溶剂的流失(接收到的BET-E含有约22％的异丙醇，然而，加入更多的异丙醇将会在高温下对流体粘度产生负作用，被消耗酸中的BET-E需要确定的醇浓度范围以具有最佳的流体性能)和提高高温下高浓度的消耗酸中的BET-E表面活性剂的溶解度，以防止表面活性剂从盐水溶液中潜在的相分离，从而改进高温下的凝胶稳定性。因此，本发明中的体系不需要添加共表面活性剂。在多数情形下，具有较短碳氢链的共表面活性剂降低了高温下凝胶稳定性。
所述酸选自盐酸、盐酸和氢氟酸的混合物、氟硼酸、硝酸、磷酸、马来酸、柠檬酸、乙酸和富马酸。根据本发明的优选实施方案，所述酸是盐酸并且加入的盐酸浓度在按重量计约3％到约28％之间，最典型的浓度在约15％到约28％之间。
根据本发明的优选实施方案，加入的粘弹性的表面活性剂的浓度以按所活性物质的重量计约1％到约4％之间(表面活性剂通常在溶液中释放)，最优选地，表面活性剂在按重量约2到约3％之间的活性浓度下加入。更高的浓度也可以使用，取决于地层的渗透率范围和差别。
在最优选的实施方案中，对于在井底约25℃到约150℃的静态温度范围的应用，推荐包含3％重量的粘弹性表面活性剂和1％体积的甲醇的制剂。
与其他的转向材料不同，本发明的流体可以作为能在一个步骤中增产和转向的单一流体进行泵送，流体可以沿着油管整体向下灌入，或者按照优选实施方案，在注入酸性制剂时使用上下移动的卷绕油管灌注流体。根据另一个实施方案，该流体分几个阶段泵送，与常规的酸阶段交替。
作为酸处理的规则，所述制剂通常包含有腐蚀抑制剂，最优选地基于季铵类。通常可加入的其它试剂，例如非乳化剂和铁还原剂、螯合剂。值得注意的是本发明的制剂对铁敏感，特别是三价铁离子。因此推荐在酸处理前使用铁还原剂和螯合剂预冲洗处理。虽然本发明的制剂能够与小浓度的非乳化试剂相容，但是为防止乳化和淤积，用互溶剂预冲洗井也是好的惯例。优选的互溶剂是低分子量的酯、醚和醇，更优选为乙二醇单丁基醚。
虽然本发明主要针对基岩酸化处理，但它整体适用于紧密相关的增产技术、酸压裂，该技术非常相似但包括在足够破裂地层的压力或在高于此压力(最小原生岩石压)下用泵输送酸。出于方便考虑，此处关注基岩酸化处理。
附图简述
通过参照所附的详细描述和附图，本发明以上或者其他目的、特征和优点将被更好地理解。
图1A和1B显示以作为HCl消耗为函数的，包含瓢儿菜酰胺基丙基甜菜碱的溶液的粘度曲线图(X轴是所消耗掉的HCl的百分比，从15％(1A)和20％(1B)开始，换句话说，图1B所示的8％表明溶液中还有12％的HCl)；
图2显示从室温到约150℃的温度范围内，有或者没有添加甲醇的两种凝胶，在40sec-1的剪切速率下的粘度曲线图；
图3显示以温度和剪切速率函数的，有或者没有添加甲醇的凝胶的粘度曲线图；
图4显示以温度函数的，具有各种浓度的甲醇的各种凝胶的粘度曲线图；
图5显示对于包含有28％的消耗HCl的凝胶而言，没有醇、有甲醇和有乙醇的凝胶的比较粘度曲线图；
图6显示对于包含有15％的消耗HCl的凝胶而言，没有醇、有甲醇和有乙醇的凝胶的比较粘度曲线图；
图7显示以温度函数的，有各种浓度的异丙醇的各种消耗凝胶的粘度曲线图；
图8显示以温度函数的，有各种浓度的甲醇的各种消耗凝胶的粘度曲线图；
具体实施方案
本发明的组合物是瓢儿菜酰胺基丙基甜菜碱，它是具有下述通式的两亲表面活性剂，
图1A和1B说明了在酸消耗过程中包含有瓢儿菜酰胺基丙基甜菜碱的溶液的粘度发展状况。图1A的测试在室温下进行，所用的溶液包含有15％的HCl和3wt％的瓢儿菜酰胺基丙基甜菜碱；对于图1B的第二测试，溶液包含有20％的HCl和3wt％的瓢儿菜酰胺基丙基甜菜碱。需要注意的是在两个图中，X轴是从15％(图1-A)和20％(图1-B)开始表示所消耗掉的HCl的百分比。换句话说，在图1B中，图中所示的8％表明溶液中还有12％的HCl。粘度是在170s-1的剪切速率下测量的，消耗刚一开始，粘度就增加，需要注意的是，在实际中，凝胶后来被地下地层的烃类破坏。
图2-A显示在高温下的凝胶粘度(用对数表示)。该凝胶制备如下：首先向20％的，有或者没有甲醇的HCl中，加入0.6％的腐蚀抑制剂和2％的腐蚀抑制剂辅剂；然后表面活性剂以按重量3％的活性浓度加入；很好地分散后，在180°F下该混合物接着与CaCO3粉末反应直到酸被中，pH值为3.5到4，pH值达到2到2.5时形成粘弹性的凝胶。该凝胶装载到Fann 50流变仪中，在40sec-1的剪切速率下测量特定温度下的粘度(以厘泊或毫帕秒为单位)
不合甲醇的凝胶的粘度曲线用虚线代表，在120°F到130°F(约50℃)的温度范围之间时该凝胶到达粘度峰值。在更高温度下，粘度剧烈下降，紧接着是从150°F到200°F(约65℃到约93℃)的接近100cP的下降的平坦区。甲醇的加入(实线)在较低温度下对凝胶的质量有害，但有助于扩展凝胶表现出最大粘度的温度。
图2-B显示出在升高的温度下、100sec-1的剪切速率下的凝胶粘度。该凝胶制备如下：制备有或者没有甲醇的42％的CaCl2溶液(模拟28％的HCl被CaCO3消耗)，表面活性剂以按重量计3％的活性浓度加入到该溶液。不含甲醇的凝胶的粘度曲线用虚线代表，温度为约150°F和130°F(约65℃)时该凝胶到达粘度峰值。在更高温度下，粘度剧烈下降，紧接着是接近200°F(约93℃)的下降的平坦区。本测试中，甲醇的加入(实线)在较低温度和较高温度下有利于凝胶的质量。
图3中，给出了不同剪切速率下(
40、100和170sec -1)凝胶的粘度。凝胶按照与图2-A的实施例描述的相同方式制备，不同在于起始HCl的浓度，在本实施例中使用的HCl的浓度是28％，而在前面的实施例中消耗前的酸浓度为20％。接着BET-E表面活性剂以按重量3％的活性浓度加入到该溶液。
为了更好地反映出井处理期间凝胶被暴露的剪切环境，流变性用一组对应于不同剪切速率的曲线代表(空心标记表示没有甲醇的凝胶，实心标记表示有甲醇的凝胶；剪切速率分别为
40、70和170的粘度分别用圆圈、正方形和三角形代表)。对于没有甲醇的凝胶，曲线显示从75°F到175°F的平坦的粘度，然后在从175°F到225°F的温度下粘度剧烈下降，紧接着是从225°F到300°F下降的平坦区。第二组曲线代表用10％体积的甲醇制成的凝胶，粘度从75°F增加到200°F时，并且保持在平坦区直到250°F，接着缓慢的下降到300°F。
图4显示了与前图3的凝胶类似的凝胶的粘度，因此含有3％的表面活性剂和28％的HCl，具有不同体积浓度的甲醇。六种测试的组合物分别包含没有甲醇(0％)、1％、4％、6％、8％和10％。加入仅仅1％的甲醇就足够显著提高约200°F到250°F的温度范围下(约93℃到约120℃)的粘度；使用更高的甲醇粘度，温度极限可以扩展到约300°F(约150℃)。对于测试的组合物，含有约6％和8％的甲醇的组合物获得了最好的结果。更高的甲醇浓度导致较低温度下凝胶粘度的下降。
图5显示了乙醇也能扩展使用凝胶的最高温度但是是很小的扩展。图5示出了用类似图3和4所示的凝胶的凝胶所获得的结果。虚线对应于没有醇的凝胶、空心正方形对应于1％的甲醇、实心三角形对应于1％的乙醇。
图6显示了用只含有15％HCl的溶液获得的类似结果。乙醇没有被证明为有效的，测试显示在15％HCl中，当酸消耗时，含有5％乙醇的溶液没有凝胶化。
图7和8显示了用不含盐酸的溶液所获得结果，用以获得与废凝胶类似的粘度曲线。图7显示了加入异丙醇的效果，可以看出，虽然约2％的异丙醇可以取得好的性能，但该流体对异丙醇量的变化非常敏感。作为结果，在工作中任何异丙醇的蒸发将损害流体的性能。另一方面，加入甲醇将最小化溶剂蒸发的影响而不降低流体性能，如图8所示。因此，通常优选甲醇的浓度按体积计在约1％到约8％之间。
Claims (10)
1.处理地下烃类油藏的方法，其包含用处理流体接触地层，该处理流体包含：水溶液、酸、和作为凝胶剂的，基本上由瓢儿菜酰胺基丙基甜菜碱组成(或者其质子化/去质子化的同系物或其盐)的表面活性剂。
2.权利要求1的方法，其中所述酸选自盐酸、盐酸和氢氟酸的混合物、乙酸和富马酸。
3.权利要求2的方法，其中所述酸在所述流体中的浓度按重量计至少为15％。
4.根据上述任何一项权利要求的方法，其中该处理流体还包含有醇。
5.权利要求4的方法，其中所述醇选自甲醇、乙醇和异丙醇。
6.权利要求5的方法，其中所述醇是甲醇并且在所述流体中的浓度按体积计在0.1和10％之间。
7.权利要求4的方法，其中所述酸在所述流体中的浓度按重量计在3和28％之间。
8.根据上述任何一项权利要求的方法，其中该处理流体还包含选自腐蚀抑制剂、非乳化剂、铁还原剂和螯合剂中的至少一种添加剂。
9.权利要求4的方法，其中所述瓢儿菜酰胺基丙基甜菜碱在所述流体中的浓度按重量计在1和4％之间。
10.权利要求4的方法包含用互溶剂接触地层，然后用包含水溶液、酸、甲醇和瓢儿菜酰胺基丙基甜菜碱的处理流体与地层接触。
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| RU2307144C2 (ru) * | 2001-12-03 | 2007-09-27 | Шлюмбергер Текнолоджи Б.В. | Не наносящая ущерба жидкость для снижения поглощения бурового раствора и способ ее применения |
| US7148185B2 (en) * | 2001-12-03 | 2006-12-12 | Schlumberger Technology Corporation | Viscoelastic surfactant fluids stable at high brine concentration and methods of using same |
| US6929070B2 (en) * | 2001-12-21 | 2005-08-16 | Schlumberger Technology Corporation | Compositions and methods for treating a subterranean formation |
| US7119050B2 (en) * | 2001-12-21 | 2006-10-10 | Schlumberger Technology Corporation | Fluid system having controllable reversible viscosity |
| US6903054B2 (en) * | 2002-08-30 | 2005-06-07 | Schlumberger Technology Corporation | Reservoir treatment fluids |
-
2002
- 2002-09-20 US US10/065,144 patent/US7119050B2/en not_active Expired - Lifetime
- 2002-12-06 DE DE60221431T patent/DE60221431D1/de not_active Expired - Lifetime
- 2002-12-06 EP EP02799054A patent/EP1456504B1/en not_active Expired - Lifetime
- 2002-12-06 AU AU2002364282A patent/AU2002364282B2/en not_active Ceased
- 2002-12-06 DK DK02799054T patent/DK1456504T3/da active
- 2002-12-06 CA CA002469259A patent/CA2469259C/en not_active Expired - Fee Related
- 2002-12-06 CN CNB02825239XA patent/CN100335746C/zh not_active Expired - Fee Related
- 2002-12-06 MX MXPA04005480A patent/MXPA04005480A/es active IP Right Grant
- 2002-12-06 WO PCT/EP2002/013848 patent/WO2003054352A1/en active IP Right Grant
- 2002-12-06 EA EA200400842A patent/EA005909B1/ru not_active IP Right Cessation
- 2002-12-06 AT AT02799054T patent/ATE368173T1/de not_active IP Right Cessation
- 2002-12-18 EG EG2002121365A patent/EG23268A/xx active
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2004
- 2004-07-20 NO NO20043106A patent/NO20043106L/no not_active Application Discontinuation
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- 2006-08-18 US US11/465,467 patent/US7288505B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102373054A (zh) * | 2010-08-12 | 2012-03-14 | 中国石油天然气股份有限公司 | 一种粘弹性表面活性剂酸化液 |
| CN102373054B (zh) * | 2010-08-12 | 2013-07-31 | 中国石油天然气股份有限公司 | 一种粘弹性表面活性剂酸化液 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| EA200400842A1 (ru) | 2004-12-30 |
| ATE368173T1 (de) | 2007-08-15 |
| CA2469259C (en) | 2005-04-12 |
| CA2469259A1 (en) | 2003-07-03 |
| EG23268A (en) | 2004-10-31 |
| EP1456504B1 (en) | 2007-07-25 |
| DE60221431D1 (de) | 2007-09-06 |
| CN100335746C (zh) | 2007-09-05 |
| MXPA04005480A (es) | 2005-04-19 |
| US20060276346A1 (en) | 2006-12-07 |
| NO20043106L (no) | 2004-07-20 |
| EA005909B1 (ru) | 2005-06-30 |
| AU2002364282A1 (en) | 2003-07-09 |
| US7288505B2 (en) | 2007-10-30 |
| US20030119680A1 (en) | 2003-06-26 |
| AU2002364282B2 (en) | 2007-11-08 |
| WO2003054352A1 (en) | 2003-07-03 |
| EP1456504A1 (en) | 2004-09-15 |
| US7119050B2 (en) | 2006-10-10 |
| DK1456504T3 (da) | 2007-11-26 |
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