CN104136571A - 三元共聚物作为固井中的降失水剂的用途 - Google Patents
三元共聚物作为固井中的降失水剂的用途 Download PDFInfo
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Abstract
提出了包含5-95mol％的2-丙烯酰胺-2-甲基丙烷磺酸，5-95mol％的N,N-二甲基丙烯酰胺以及5-12mol％的丙烯酸的三元共聚物作为固井中的降失水剂的用途。丙烯酸作为固井中的降失水剂。
Description
本发明涉及2-丙烯酰胺-2-甲基丙烷磺酸、丙烯酸和N,N-二甲基丙烯酰胺的三元共聚物作为固井(well cementing)中的降失水剂(fluid lossadditive)的用途。
在建筑化学领域，多种共聚物通常用作保水助剂，其也称作“降失水剂”。本文中用途的特定领域为在地下矿物油和天然气储藏的开发、开采和完井中以及深井中的固井。
保水助剂或降失水剂具有降低水由水泥浆中释放的功能。这在矿物油和天然气勘探领域中尤其重要，原因在于主要由水泥和水组成的水泥浆在固井过程中通过套管和井壁之间的环形空间泵送。在这一过程中，大量的水可以从水泥浆释放到地下岩层中。在固井过程中，当水泥浆流经多孔岩石地层时尤其如此。然后，源自水泥浆的碱性水可以引起地层中粘土膨胀，并与来自天然气或矿物油中的二氧化碳形成碳酸钙沉积物。这些效应降低了沉积物的渗透性，因此对生产速率也有不利的影响。
此外，由于水释放至多孔的地下岩层，水泥浆不再均匀固化，其结果是可透过气体、液态烃和水。这随后可导致化石能源载体通过填充有多孔水泥的环状空间逸出。
因此，长期以来，已致力于将所使用的水泥浆中的水损失降低至可容忍的最小值。
例如，EP 0 116 671 A1记载了用于深井的水泥浆，其中据记载共聚物的含量可降低水损失。所使用的共聚物的重要的组份由丙烯酰胺且特别是2-丙烯酰胺-2-甲基丙烷磺酸形成。根据该文献，水泥浆应包含0.1至3重量％的合适的共聚物。
EP 1 375 818 A1也讨论了固井及适合于固井的组合物。在该情况下，为控制失水量，使用聚合物添加剂，其除了包含以外还包含额外的马来酸、N-乙烯基己内酰胺和4-羟基丁基乙烯基醚。
US 4,015,991的共聚物同样基于和部分水解的丙烯酰胺。据记载该发明中描述的共聚物同样可改善水泥基复合材料中的保水能力(water retention capacity)。所提及使用的主要领域是固井。
在US 4,515,635中，还记载了2-丙烯酰胺-2-甲基丙烷磺酸和N,N-二甲基丙烯酰胺(DMAA)的共聚物用作固井中的降失水剂的用途。相似的共聚物还可见于US 4,555,269中。
US 6,395,853 B1的水溶性共聚物尤其包含丙烯酰胺和该文献的前面记载的内容为用于降低用来获得矿物油的浆料中水损失的方法。关于此，特别提及固井和完井，以及特别提及实施这些方法步骤的井浆料。
US 4,700,780的中间部分记载了用于降低水泥基复合材料中的水损失的方法，所述水泥基复合材料还包含特定的盐浓度。该保水助剂仍是的聚合物或聚合物盐，在这种情况下，还应存在苯乙烯和丙烯酸单元。
2-丙烯酰胺-2-甲基丙烷磺酸、丙烯酸和N,N-二甲基丙烯酰胺的三元共聚物也构成现有技术的一部分。例如，US 4,554,081讨论了这些三元共聚物及其在石油和天然气生产领域中在具有高密度的完井液、钻井泥浆和修井液中作为降失水剂的用途，所述三元共聚物优选由16.8mol％73.2mol％DMAA和10mol％丙烯酸组成。
此外，Plank等(J.Appl.Polym.Sci.106,3889-3894,2007-DOI:10.1002/app.26897)描述了具有低比例丙烯酸(约1重量％或约3.6mol％)的三元共聚物。在该出版物中，比较了和DMAA的共聚物与所述三元共聚物在固井中作为降失水剂的效果。发现所述共聚物的效果与具有低比例丙烯酸的三元共聚物的效果没有差别。
这些已知的共聚物和三元共聚物各自具有不同性能特点，即具有特定优点和缺点。多数这些离子聚合物的固有的共同缺点在于，在高盐浓度存在下(在海水中通常发生这种情况)其保水作用下降，而海水通常用于制备海上油井和气井中的水泥浆。对于二价阳离子如Mg2+和Ca2+的盐尤其如此。
因此，长期以来，已经致力于提供保水容量稳定的新的分子或聚合物，尤其是提供在高盐浓度下、特别是在油气开采领域和深井中保水容量稳定的新的分子或聚合物。
该目的通过独立权利要求中的特征实现。从属权利要求涉及优选的实施方案。
现出人意料地发现，具有约5至12mol％丙烯酸含量的2-丙烯酰胺-2-甲基丙烷磺酸、N,N-二甲基丙烯酰胺和丙烯酸的三元共聚物就作为固井中的降失水剂的效果而言具有明显的优势。
本发明提供一种三元共聚物作为固井中的降失水剂的用途，所述三元共聚物包含5-95mol％的2-丙烯酰胺-2-甲基丙烷磺酸，5-95mol％的N,N-二甲基丙烯酰胺以及5-12mol％的丙烯酸。
所述三元共聚物优选包含8-12mol％且更优选包含10-11mol％的丙烯酸。
尽管2-丙烯酰胺-2-甲基丙烷磺酸与N,N-二甲基丙烯酰胺的摩尔比不特别关键，但本发明的上下文中优选2-丙烯酰胺-2-甲基丙烷磺酸与N,N-二甲基丙烯酰胺的摩尔比在50:50至80:20之间，特别是在60:40至70:30之间。
本发明的三元共聚物可适合地通过上述共聚单体的自由基共聚而制备。由于所述共聚单体的离子特性和亲水特性，共聚可适合地在水溶液中进行。2-丙烯酰胺-2-甲基丙烷磺酸与丙烯酸可以完全或部分地以碱金属盐、碱土金属盐或其混合物的形式存在，特别是以Na盐、K盐、Mg盐和/或Ca盐的形式存在。这些盐可直接用于共聚。这些盐还可以仅在所形成的三元共聚物的后续中和中形成。用于将所述盐引入三元共聚物中的这两种路径可彼此单独地采用或彼此结合地采用。
本发明的三元共聚物的分子量优选在500 000至4 000 000g/mol的范围内且特别是在1 000 000至2 000 000g/mol的范围内。
在矿物油和天然气开采领域以及在深井中，如在开篇已提及的，用于固井的主要由水泥和水组成的水泥浆通过套管和井壁之间的环形空间泵送。目前，为实现这一目的，仍通常使用硅酸盐水泥(portland cement)。因此，本发明的用途选优地特征在于，所述三元共聚物用作包含硅酸盐水泥的水泥浆中的降失水剂。
由于本发明的三元共聚物的高耐盐性，这些三元共聚物可有利地用作包含海水或由海水制备的水泥浆中的降失水剂。
在矿物油生产领域中，通常使用所谓的增重液(weighting fluid)，这些通常由浓缩的碱金属和/或碱土金属的盐的水溶液构成。因此，在固井过程中，可至少部分地混合增重液和水泥浆。由于发明三元共聚物的高耐盐性，即使在这种水泥浆中，其作用也不会消失。
总之，可表明，本发明的三元共聚物适合且有利地在地下矿物油和天然气矿藏的开发、开采和完井中以及深井中的固井中用作降失水剂，而且，鉴于现有技术，出人意料的是，本发明的三元共聚物尤其对于高盐浓度的耐受性是显著的。
现通过以下实施例详细说明本发明。
实施例1：
在搅拌下，将2200g自来水和158g20％NaOH初始进料至带有钢搅拌器的玻璃反应器中。随后，边冷却边加入135g使温度不超过30℃。此后，混入95g DMAA和13.5g丙烯酸(相当于约10.6mol％)并在100ml自来水中洗涤。在下一步中，使用NaOH或调节pH至7.6。在一小时之内，在氮气保护下将反应混合物加热至62℃。一达到恒定温度，通过加入溶解在约10ml H2O中的0.65g四亚乙基五胺(TEPA)和5g Na2S2O8引发聚合反应。观察到放热反应，反应过程中温度升至70-74℃。反应已开始之后，在没有任何其他外部加热下搅拌混合物1小时。终产物为浅黄色、粘稠溶液，pH为7-7.5，固体含量为10-12重量％且Brookfield粘度为6000mPa*s。
实施例2：
根据API推荐的方法10B，在190°F(88℃)下测定实施例1的三元共聚物在以下加入或不加入盐的水泥浆中的液体损失(“LL”)和流变性，并与市售的共聚物(购自BASF ConstructionPolymers GmbH的FL34)比较：
800g G类水泥(购自Dyckerhoff)
352g水
0.6bwoc％的降失水剂
1.0g消泡剂(三异丁基磷酸酯)
在表1和2中列出结果，表1涉及FL34，表2涉及实施例1的三元共聚物。盐的量以克和重量百分比(基于水含量计)记录；“bwoc”意指基于水泥计的重量百分比。
表1(FL34)：
表2(三元共聚物)：
可清楚地看出，与市售的FL34相比，同样剂量的实施例1的三元共聚物的液体损失低得多。此外，与FL34相比，即使是对于海盐，实施例1的三元聚合物的耐盐性高得多。
所述结果的出人意料之处还在于，现有技术(Plank et al.，J.Appl.Polym.Sci.106，3889-3894，2007)中表明，丙烯酸的加入对作为降失水剂的AMPS/DMAA共聚物的效果没有影响。而显然本文中所述比例的丙烯酸是关键的。
此外，发现与FL34相比，实施例1的三元共聚物对水泥浆的硬化时间仅具有并不显著的推迟效应(如果存在的话)。
Claims (8)
1.三元共聚物作为固井中的降失水剂的用途，所述三元共聚物包含：
5-95mol％的2-丙烯酰胺-2-甲基丙烷磺酸，
5-95mol％的N,N-二甲基丙烯酰胺以及
5-12mol％的丙烯酸。
2.权利要求1的用途，其特征在于，所述三元共聚物包含8-12mol％的丙烯酸且优选包含10-11mol％的丙烯酸。
3.权利要求1或2的用途，其特征在于，2-丙烯酰胺-2-甲基丙烷磺酸与N,N-二甲基丙烯酰胺的摩尔比在50:50至80:20之间，优选在60:40至70:30之间。
4.权利要求1-3中任一项的用途，其特征在于，2-丙烯酰胺-2-甲基丙烷磺酸和丙烯酸完全地或部分地以碱金属盐、碱土金属盐或其混合物的形式存在，特别是以Na盐、K盐、Mg盐和/或Ca盐的形式存在。
5.权利要求1-4中任一项的用途，其特征在于，所述三元共聚物的分子量在500 000至4 000 000g/mol的范围内且特别是在1 000 000至2000 000g/mol的范围内。
6.权利要求1-5中任一项的用途，其特征在于，所述三元共聚物用作包含硅酸盐水泥的水泥浆中的降失水剂。
7.权利要求1-6中任一项的用途，其特征在于，所述三元共聚物用作包含海水的水泥浆中的降失水剂。
8.权利要求1-7中任一项的用途，其特征在于，所述三元共聚物用作地下矿物油和天然气矿藏的开发、开采和完井中以及深井中的固井中的降失水剂。
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| EP12155128 | 2012-02-13 | ||
| EP12155128.7 | 2012-02-13 | ||
| PCT/EP2013/050275 WO2013120636A1 (en) | 2012-02-13 | 2013-01-09 | Use of terpolymers as fluid loss additives in well cementing |
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| US (1) | US20150007992A1 (zh) |
| EP (1) | EP2814903A1 (zh) |
| CN (1) | CN104136571A (zh) |
| CA (1) | CA2863731A1 (zh) |
| MX (1) | MX2014009251A (zh) |
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| CN105601826A (zh) * | 2015-12-24 | 2016-05-25 | 江苏苏博特新材料股份有限公司 | 一种降粘型减水剂的制备方法 |
| CN106811184A (zh) * | 2015-11-30 | 2017-06-09 | 中国石油天然气股份有限公司 | 一种用于油井堵水的复合无机堵剂及其制备方法 |
| CN114292634A (zh) * | 2022-01-19 | 2022-04-08 | 成都欧美克石油科技股份有限公司 | 一种多级吸附聚合物降失水剂及其制备方法 |
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| US9957433B2 (en) | 2015-04-23 | 2018-05-01 | Saudi Arabian Oil Company | Preparation and use of drilling fluids with date seed powder fluid loss additive |
| EP3310736B1 (de) * | 2015-06-17 | 2019-01-30 | Clariant International Ltd | Wasserlösliche oder wasserquellbare polymere als wasserverlustreduzierer in zementschlämmen |
| WO2017220512A1 (en) | 2016-06-20 | 2017-12-28 | Clariant International Ltd | Compound comprising certain level of bio-based carbon |
| EP3551163B1 (en) | 2016-12-12 | 2021-02-17 | Clariant International Ltd | Use of bio-based polymer in a cosmetic, dermatological or pharmaceutical composition |
| EP3551680A1 (en) | 2016-12-12 | 2019-10-16 | Clariant International Ltd | Polymer comprising certain level of bio-based carbon |
| US11542343B2 (en) | 2016-12-15 | 2023-01-03 | Clariant International Ltd | Water-soluble and/or water-swellable hybrid polymer |
| WO2018108663A1 (en) | 2016-12-15 | 2018-06-21 | Clariant International Ltd | Water-soluble and/or water-swellable hybrid polymer |
| WO2018108664A1 (en) | 2016-12-15 | 2018-06-21 | Clariant International Ltd | Water-soluble and/or water-swellable hybrid polymer |
| US11339241B2 (en) | 2016-12-15 | 2022-05-24 | Clariant International Ltd. | Water-soluble and/or water-swellable hybrid polymer |
| US10988676B1 (en) | 2019-11-29 | 2021-04-27 | Halliburton Energy Services, Inc. | Methods of making and using a high temperature wellbore servicing fluid |
| US11352545B2 (en) | 2020-08-12 | 2022-06-07 | Saudi Arabian Oil Company | Lost circulation material for reservoir section |
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| DE3302168A1 (de) | 1983-01-24 | 1984-07-26 | Hoechst Ag, 6230 Frankfurt | Zementschlaemme fuer tiefbohrungen mit einem gehalt an copolymerisaten zur verminderung des wasserverlustes |
| US4515635A (en) | 1984-03-23 | 1985-05-07 | Halliburton Company | Hydrolytically stable polymers for use in oil field cementing methods and compositions |
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2013
- 2013-01-09 CN CN201380009095.7A patent/CN104136571A/zh active Pending
- 2013-01-09 WO PCT/EP2013/050275 patent/WO2013120636A1/en active Application Filing
- 2013-01-09 EP EP13700093.1A patent/EP2814903A1/en not_active Withdrawn
- 2013-01-09 RU RU2014137021A patent/RU2014137021A/ru not_active Application Discontinuation
- 2013-01-09 MX MX2014009251A patent/MX2014009251A/es unknown
- 2013-01-09 US US14/378,277 patent/US20150007992A1/en not_active Abandoned
- 2013-01-09 CA CA2863731A patent/CA2863731A1/en not_active Abandoned
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106811184A (zh) * | 2015-11-30 | 2017-06-09 | 中国石油天然气股份有限公司 | 一种用于油井堵水的复合无机堵剂及其制备方法 |
| CN106811184B (zh) * | 2015-11-30 | 2019-05-07 | 中国石油天然气股份有限公司 | 一种用于油井堵水的复合无机堵剂及其制备方法 |
| CN105601826A (zh) * | 2015-12-24 | 2016-05-25 | 江苏苏博特新材料股份有限公司 | 一种降粘型减水剂的制备方法 |
| CN105601826B (zh) * | 2015-12-24 | 2018-01-02 | 江苏苏博特新材料股份有限公司 | 一种降粘型减水剂的制备方法 |
| CN114292634A (zh) * | 2022-01-19 | 2022-04-08 | 成都欧美克石油科技股份有限公司 | 一种多级吸附聚合物降失水剂及其制备方法 |
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| CA2863731A1 (en) | 2013-08-22 |
| RU2014137021A (ru) | 2016-04-10 |
| MX2014009251A (es) | 2014-10-14 |
| WO2013120636A1 (en) | 2013-08-22 |
| US20150007992A1 (en) | 2015-01-08 |
| EP2814903A1 (en) | 2014-12-24 |
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