CN101675142A - 水性微粒浆组合物及其制备方法 - Google Patents
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Abstract
本发明公开了砂浆组合物及制备砂浆的方法。该砂浆组合物由砂、水性液体和为砂的表面提供疏水性的化合物组成。该方法包括在制备浆期间或之前，为砂的表面提供疏水性。这种方法及组合物能够应用于不同的工业中，特别是在多种油田应用中。
Description
本发明要求于2007年4月13日提交的第2,585,065号加拿大专利申请的优先权。
领域
本发明通常涉及微粒浆组合物及其制备方法，并具体地涉及砂浆。
背景
砂浆被应用于多种工业中，包括石油、管道、建筑和清洁。大量使用砂浆的一实例是用于提高石油和天然气产量的水力压裂法。在水力压裂法中，压裂液在足够的压力下通过井眼被注入地层，以引起能提高石油和天然气产量的裂缝。被称为支撑剂的微粒经常被悬浮于压裂液中，并作为浆被传送至裂缝。支撑剂包括砂、陶颗粒、玻璃球、矾土(氧化铝)等。其中，砂是到目前为止最常用的支撑剂。常用的压裂液包括各种水性和烃类胶质。液体二氧化碳和氮气也被用于压裂处理中。最常用的压裂液是包含交联聚合物或直链聚合物以将支撑剂有效地传送至地层的水性流体。在压裂处理的最后阶段，使压裂液流回地表而使支撑剂留在产生的裂缝中，以防止其在压力解除后关闭。填充了支撑剂的裂缝提供了允许石油和/或天然气更有效地从中渗出至井眼的高传导性通道。支撑剂充填层的传导性在提高石油和天然气产量中起主要作用。然而，众所周知，来自压裂液的聚合物残留物显著地降低了支撑剂充填层的传导性。
砂的密度为约2.6g/cm3而水的密度为1g/cm3。砂和水之间的高密度差使得砂在水中很快沉淀，甚至在高水湍流的条件下也是如此。一旦沉淀下来，砂不容易被沉淀于其中的水性流体的流动带起。
通常，为了制备在静态或/和动态条件下相对稳定的浆，一般将砂悬浮于粘弹性的流体中。在粘弹性的流体中，屈服应力在使颗粒悬浮中起主要作用。屈服应力是在粘弹性的流体中引起流动所需的最小的剪应力。流体的粘性基本上起降低颗粒沉降速率的作用，而屈服应力有助于悬浮该颗粒。在动态条件下，搅动和湍流进一步帮助稳定浆。因此，为了制备稳定和划算的砂浆，常规方法主要通过向浆中添加足量诸如天然或合成聚合物的增粘剂以调节流体的流变学性质。将聚合物与发泡剂一起使用以提高流变能力并降低成本并不常见。
在必须就地制备浆以将砂运出的诸如油井清洗和管道中砂的清洗的某些应用中，液体介质中增粘剂的存在通常有不利影响。这主要是由于在这些情形下湍流在砂的运送中起关键作用，而增粘剂则趋向于抑制湍流的事实。
浮选法已被用于采矿工程以将磨得很细的贵重矿物与其它矿物分离。将原矿石研磨成很细的粉末并与水、捕收剂、任选地与起泡剂混合。当使空气吹过混合物的时候，疏水的矿物颗粒附着在上浮以在表面形成泡沫的泡上。废料(尾矿)在底部沉淀下来。撇去泡沫，并除去水和化学品，留下干净的浓缩物。该方法又称为泡沫-浮选法，被用于许多矿物中。
这种浮选方法的主要机制是动态条件下微泡与疏水颗粒的选择性聚集，以将该颗粒抬至液体表面。矿物及其相关的尾矿通常不具备足够的疏水性以允许泡附着。捕收剂(collecting agent)，即捕收剂(collector)，是能够选择性地吸附在期望矿物的表面，使其变得疏水以使颗粒与微泡聚集并因此促进分离的化学剂。起泡剂是被添加至混合物中以促进半稳定泡沫生成的化学剂。在所谓的反浮选法中，诸如硅石的非期望矿物自保留在尾矿中的贵重矿物被漂浮走。硅石的反浮选法被广泛用于铁矿石和磷矿石的处理中。
很多种化学剂可用作浮选硅石颗粒的捕收剂和起泡剂。已知诸如简单的伯胺和仲胺、伯醚胺和醚二胺、牛脂胺和牛油脂肪酸/胺缩合物的胺是用于硅石颗粒的有用的捕收剂。这些化合物强烈地吸附于砂的表面并将砂的表面从亲水性改变为疏水性是确立的。实际上，这些化合物被用作捕收剂的原因是由于其将砂的表面疏水化以允许形成稳定的砂/泡聚集体的能力。优选的捕收剂为具有至少约12个碳原子的胺捕收剂。这些捕收剂可购自例如Akzo Nobel或Tomah Products Inc.。其它可能的捕收剂为通常需要诸如Ca++或Mg++的多价阳离子的存在以有效工作的油酸盐。
用作起泡剂的化合物包括低分子量醇，包括甲基异丁基甲醇和乙二醇醚。
这样的浮选法不用于制备砂浆，特别是制备用于多种油田应用的砂浆。
概述
根据一实施方案，本发明涉及包含微粒、水性介质和为该微粒的表面提供疏水性的捕收剂的浆组合物及其制备方法。
在另一实施方案中，本发明涉及包含微粒、水性介质和为该微粒的表面提供疏水性的捕收剂以及起泡剂的浆组合物及其制备方法。
在另一实施方案中，本发明涉及能在动态条件下或“在运行”中就地制备的浆组合物。
在另一实施方案中，本发明涉及包含微粒、水性介质和为该微粒的表面提供疏水性的捕收剂的油井服务流体组合物。该流体还能够包含起泡剂。该流体还能够包含表面活性剂。支撑剂能够是砂。
发明描述
在本发明中，将注意力从包含砂的液体介质的流变学转移，而集中在砂上。虽然在每种情况下，砂的特性(在该实施方案中即其粒度分布和密度)是常数，但是本发明涉及通过“抬升”砂而不是通过液体介质使砂悬浮来改进浆的流动性和稳定性。
在一实施方案中，通过使具有足够稳定性的微泡附着于砂的表面来实现抬升。或者，在相邻的砂粒间制造孔。由于浮力增加，附着于砂表面的微泡或孔帮助将砂抬起。
在本发明中，将反浮选法的基本原理应用于制备运送砂的水性砂浆，所述砂浆用途广泛，特别是在油田中。这些用途包括水力压裂、钻孔、井眼清洗、管道中的砂清洗和砂喷射。用于这些用途的砂的粒径通常为10目至约100目。所有这些应用在通常存在湍流的动态条件下进行。
在本发明中，强烈亲水的砂粒表面被改性成疏水以允许与水性液体(包括水、盐水和包含少量醇或其它有机溶剂的水)中的微泡在动态条件下的聚集。与泡的聚集为砂提供了增加的浮力，并因此在不使用增粘剂的情况下大大改进浆的流动性和稳定性。
有不同的制备本发明的微粒浆的方法。例如，能够首先在水中用捕收剂处理诸如砂的微粒，干燥然后在动态条件下与水混合以制备用于随后的应用的浆。或者能够“在运行”中制备微粒浆，即在动态条件下将砂、捕收剂和水混合在一起。或者，在例如通常应用高速液体流的井眼清洗和管道中砂的清洗中，能够就地制备浆，其中在动态条件下将砂与包含捕收剂的水混合。
除了捕收剂，还能够添加不同的起泡剂以增强浆的流动性和稳定性。起泡剂包括甲基异丁基甲醇、己醇或乙二醇醚。除了捕收剂，还可以添加本身通常不用作捕收剂的常规表面活性剂以增强砂的漂浮。但是，任何添加的表面活性剂必须与捕收剂相容。例如，表面活性剂不应与捕收剂形成沉淀，并且不应明显降低表面张力以允许疏水的砂被水性介质充分浸润。否则，微泡不能与疏水的砂形成稳定的聚集体。
可用于本发明的捕收剂为胺类，包括简单的伯胺和仲胺、伯醚胺和伯醚二胺、牛脂胺和牛油脂肪酸/胺缩合物。这样的捕收剂的实例包括3-壬氧基-丙胺、N-十三烷氧基-3，1-丙二基-1，3-丙二胺、二乙烯四胺与牛油脂肪酸的缩合物、C16-C18牛脂胺、癸胺、十二胺、二己胺、十四烷氧基丙胺、十二烷氧基丙胺、十八/十六烷氧基丙胺(octadecyl/hexadecyloxypropyl amine)、异十二烷氧基丙胺、异十三烷氧基丙胺、十二烷基-1，3-丙二胺、十六烷基-1，3-丙二胺、牛油-1，3-丙二胺、过量脂肪酸与二乙醇胺的缩合物。还能够将诸如C1-6烷醇胺的短碳链烷醇胺或诸如己胺的短碳链胺与长碳链胺捕收剂组合以增强漂浮。用于硅石的这样的捕收剂及相关的组合物是本领域公知的。更多的细节能够在第2,312,387号、第2,322,201号、第2,710,856号、第4,234,414号和第5,124,028号美国专利，S.Takeda和S.Usui，Colloid and Surfaces，29，221-232，1988以及J.L.Scott和R.W.Smith，Minerals Engineering，Vol.4，No.2，141-150，1991中找到，这些文献均并入本文作为参考。
本发明的微粒浆能够在表面或在地层下就地制备，其中将微粒、水性流体和诸如十六烷基-1，3-丙二胺的捕收剂混合在一起。另外，还能够将诸如己醇的起泡剂与捕收剂一起添加至浆中。或者能够首先将微粒与流体和捕收剂混合，然后使液体干燥。然后能够将处理过的颗粒匀浆。
所需的捕收剂的量通常取决于砂的浓度和大小。所添加的捕收剂的量通常为0.01g/kg砂至1g/kg砂。例如，在压裂操作期间，能够在高抽运速率下将捕收剂添加至水中并与砂混合成浆以将砂运送至地层中。在某些情况下，还能够向浆中添加诸如少量的水溶性聚合物的减摩剂以减少摩擦压力。应当注意，减摩剂不应与捕收剂形成沉淀或明显减少泡-砂的聚集体的形成。还能够任选地将氮气或二氧化碳气体混合入浆中。类似地，在井眼的砂清洗中，在高流速下将包含捕收剂的水与砂就地混合，并有效地将砂带出井眼。能够任选地将氮气或二氧化碳气体与流体混合。
下文提供了本发明的若干非限制性实施例。
实施例1
将100ml水与50g美国筛网30/50目的压裂砂添加至两个玻璃瓶(200ml)的每一瓶中。将0.07ml来自Akzo Nobel的牛油烷基-二甲基胺Armeen DMTD添加至其中一瓶中，另外一瓶用作对照。用力摇晃瓶，然后静置使砂沉淀。虽然在对照瓶中没有观察到泡，但是在含有Armeen DMTD的瓶中泡附着在砂粒上，而且，有一层砂漂浮在顶部。比较了两瓶中沉淀的砂的体积。在含有Armeen DMTD的瓶中，沉淀的砂的体积比不含Armeen DMTD的瓶中沉淀的砂的体积约大20％，并且砂更易流动。泡附着在砂粒上。缓慢倾斜瓶时，对照瓶中沉淀的砂倾向于作为单独的砂粒移动，而包含Armeen DMTD的沉淀的砂则倾向于作为凝聚的块移动。
实施例2
将100ml水与50g美国筛网30/50目的压裂砂添加至两个玻璃瓶(200ml)的每一瓶中。将0.07ml来自Akzo Nobel的牛油烷基-二甲基胺Armeen DMTD和0.05ml来自Degussa Corp.的两性烃类表面活性剂辛酰/癸酰氨丙基甜菜碱TEGO Betaine 810添加至其中一瓶中，另外一瓶用作对照。用力摇晃瓶，然后静置使砂沉淀。虽然对照瓶中没有观察到泡，但是在含有Armeen DMTD的瓶中泡附着在砂粒上，而且，有一层砂漂浮在顶部。比较了两瓶中沉淀的砂的体积。在含有ArmeenDMTD的瓶中，沉淀的砂的体积比不含Armeen DMTD的瓶中沉淀的砂的体积约大20％，并且砂更易流动。泡附着在砂粒上。缓慢倾斜瓶时，对照瓶中沉淀的砂倾向于作为单独的砂粒移动，而包含ArmeenDMTD的沉淀的砂则倾向于作为凝聚的块移动。
实施例3
将100ml水与50g美国筛网30/50目的压裂砂添加至两个玻璃瓶(200ml)的每一瓶中。将0.05ml来自Akzo Nobel的牛油烷基-二甲基胺Armeen DMTD和0.3ml己醇添加至其中一瓶中，另外一瓶用作对照。用力摇晃瓶，然后静置使砂沉淀。虽然对照瓶中没有观察到泡，但是在含有Armeen DMTD的瓶中泡附着在砂粒上，而且，有一层砂漂浮在顶部。比较了两瓶中沉淀的砂的体积。在含有Armeen DMTD的瓶中，沉淀的砂的体积比不含Armeen DMTD的瓶中沉淀的砂的体积约大50％，并且砂更易流动。缓慢倾斜瓶时，对照瓶中沉淀的砂倾向于作为单独的砂粒移动，而包含Armeen DMTD的沉淀的砂则倾向于作为凝聚的块移动。
Claims (18)
1.浆组合物，其包含：
微粒，
水性介质，和
为所述微粒的表面提供疏水性的捕收剂。
2.如权利要求1所述的浆组合物，其还包含起泡剂。
3.如权利要求1或2所述的浆组合物，其中所述捕收剂为胺或烷醇胺。
4.如权利要求3所述的浆组合物，其中所述胺为伯胺、仲胺、伯醚胺、醚二胺、牛脂胺或牛油脂肪酸/胺缩合物。
5.如权利要求1或2所述的浆组合物，其中所述捕收剂为3-壬氧基-丙胺、N-十三烷氧基-3，1-丙二基-1，3-丙二胺、二乙烯四胺与牛油脂肪酸的缩合物、C16-C18牛脂胺、癸胺、十二胺、二己胺、十四烷氧基丙胺、十二烷氧基丙胺、十八/十六烷氧基丙胺、异十二烷氧基丙胺、异十三烷氧基丙胺、己胺、十二烷基-1，3-丙二胺、十六烷基-1，3-丙二胺、牛油-1，3-丙二胺、过量脂肪酸与二乙醇胺或油酸盐的缩合物。
6.如权利要求3所述的浆组合物，其中所述捕收剂具有1至12个碳原子。
7.如权利要求3所述的浆组合物，其中所述捕收剂具有1至6个碳原子。
8.如权利要求2至7中任一权利要求所述的浆组合物，其中所述起泡剂为低分子量的醇。
9.如权利要求8所述的浆组合物，其中所述醇为甲基异丁基甲醇或乙二醇醚。
10.如权利要求1至9中任一权利要求所述的浆组合物，其中所述捕收剂的浓度为约0.01g/kg支撑剂至1g/kg支撑剂。
11.如权利要求1至10中任一权利要求所述的浆组合物，其还包含表面活性剂。
12.如权利要求10或11所述的浆组合物，其中所述支撑剂为砂。
13.权利要求1至12中任一权利要求所述的浆组合物作为油田应用流体的用途。
14.如权利要求13所述的浆的用途，其中所述油田应用流体为压裂液、钻井液、喷射液或油井清洗液。
15.油井服务流体组合物，其包含：
微粒，
水性介质，和
为所述微粒的表面提供疏水性的捕收剂。
16.如权利要求15所述的流体，其还包含起泡剂。
17.如权利要求15或16所述的流体，其还包含表面活性剂。
18.如权利要求15至17中任一权利要求所述的流体，其中所述支撑剂为砂。
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| KR100519657B1 (ko) * | 2003-03-13 | 2005-10-10 | 삼성전자주식회사 | 테스트 패드를 갖는 반도체 칩과 그를 이용한 테이프캐리어 패키지 |
| US7066258B2 (en) * | 2003-07-08 | 2006-06-27 | Halliburton Energy Services, Inc. | Reduced-density proppants and methods of using reduced-density proppants to enhance their transport in well bores and fractures |
| CN100575661C (zh) * | 2004-05-13 | 2009-12-30 | 贝克休斯公司 | 处理地下地层的方法和含水粘弹性处理流体 |
| GB2465914B (en) | 2005-05-02 | 2010-08-25 | Trican Well Service Ltd | Method for making transportable aqueous slurries by particulate hydrophobicization |
| US9714371B2 (en) * | 2005-05-02 | 2017-07-25 | Trican Well Service Ltd. | Method for making particulate slurries and particulate slurry compositions |
| CA2585065A1 (en) * | 2007-04-13 | 2008-10-13 | Trican Well Service Ltd. | Aqueous particulate slurry compositions and methods of making same |
| CN101675143B (zh) * | 2007-04-26 | 2013-07-31 | 川汉油田服务有限公司 | 对通过流体输送颗粒的控制 |
| CN101711273B (zh) * | 2007-06-13 | 2013-08-07 | 川汉油田服务有限公司 | 用于地下煤层中颗粒聚集的油井服务组合物 |
| CA2693427C (en) * | 2007-07-18 | 2016-03-08 | Trican Well Service Ltd. | Resin coated proppant slurry compositions and methods of making and using same |
-
2007
- 2007-04-13 CA CA002585065A patent/CA2585065A1/en not_active Abandoned
-
2008
- 2008-04-11 EA EA200901398A patent/EA200901398A1/ru unknown
- 2008-04-11 WO PCT/CA2008/000669 patent/WO2008124919A1/en active Application Filing
- 2008-04-11 BR BRPI0810896-0A2A patent/BRPI0810896A2/pt not_active IP Right Cessation
- 2008-04-11 CN CN200880011919.3A patent/CN101675142B/zh not_active Expired - Fee Related
- 2008-04-11 MX MX2009011026A patent/MX2009011026A/es active IP Right Grant
- 2008-04-11 US US12/595,461 patent/US8105986B2/en active Active
- 2008-04-11 AU AU2008238556A patent/AU2008238556B2/en not_active Ceased
- 2008-04-11 CA CA2683516A patent/CA2683516C/en active Active
- 2008-04-11 AR ARP080101504A patent/AR066031A1/es not_active Application Discontinuation
- 2008-04-11 EP EP08757079A patent/EP2142616A4/en not_active Withdrawn
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2011
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103180404A (zh) * | 2010-08-25 | 2013-06-26 | 普拉德研究及开发股份有限公司 | 地下颗粒材料的传送 |
| CN104007043A (zh) * | 2014-03-27 | 2014-08-27 | 中国华能集团清洁能源技术研究院有限公司 | 一种大型多功能压裂液实验系统 |
| CN115228616A (zh) * | 2022-08-09 | 2022-10-25 | 东北大学 | 一种无需调节酸碱度的铁矿常温反浮选方法 |
| CN115228616B (zh) * | 2022-08-09 | 2024-04-19 | 东北大学 | 一种无需调节酸碱度的铁矿常温反浮选方法 |
| CN116640566A (zh) * | 2023-05-19 | 2023-08-25 | 四川省威沃敦化工有限公司 | 一种压裂用支撑剂改性剂的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| MX2009011026A (es) | 2010-03-15 |
| AU2008238556B2 (en) | 2014-03-06 |
| CA2585065A1 (en) | 2008-10-13 |
| AU2008238556A1 (en) | 2008-10-23 |
| WO2008124919A1 (en) | 2008-10-23 |
| CA2683516A1 (en) | 2008-10-23 |
| US8105986B2 (en) | 2012-01-31 |
| AR066031A1 (es) | 2009-07-15 |
| US20120071371A1 (en) | 2012-03-22 |
| EP2142616A1 (en) | 2010-01-13 |
| EP2142616A4 (en) | 2010-12-01 |
| CN101675142B (zh) | 2014-01-01 |
| US20100204071A1 (en) | 2010-08-12 |
| CA2683516C (en) | 2016-07-19 |
| US9139761B2 (en) | 2015-09-22 |
| EA200901398A1 (ru) | 2010-04-30 |
| BRPI0810896A2 (pt) | 2014-10-29 |
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