CN102782080A - Csh悬浮液在固井中的应用 - Google Patents
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Abstract
本发明涉及用于无机粘合料的促凝剂组合物在地下石油和天然气储集层的开发、开采和完井以及深孔钻井中的用途，所述促凝剂组合物包括至少一种适合作为水硬性粘合料的减水剂的水溶性梳状聚合物，以及硅酸钙水合物颗粒。根据本发明的用途不仅加速水泥浆的凝固和硬化，而且缩短硬化水泥浆的静胶凝强度从100lb/100ft2(4.88kg/m2)增加到500lb/100ft2(24.4kg/m2)的时间。
Description
本专利申请要求2010年2月21日提交的序列号为61/326253的未决的美国临时专利申请的优先权，该临时专利申请全文以引用的方式纳入本说明书。
本发明涉及CSH悬浮液在地下矿物油和天然气储集层的开发、开采和完井以及深孔钻井中的用途。
地下矿物油、天然气和水储集层通常处于高压下。在这样的岩层钻井要求循环井液的压力足够高以有效地抵消地下岩层的压力从而阻止岩层流体无控制地进入井中。
通常，井内分段排有钢管。井套管和地下岩层之间的环隙用水泥填充。这可以通过使水泥浆直接进入环隙或通过施加压力使水泥浆穿过井套管进入井中然后再回流进入环隙实现。硬化的水泥首先阻止了岩层流体无控制地进入井中，其次阻止了岩层流体无阻碍地渗入其它岩层中。
储集层的温度条件有很大的不同。在永冻层区（例如，阿拉斯加、加拿大和西伯利亚）的近表面区域，以及在高纬度的近海井中，温度可能低于冰点，而在地热井中，温度可高达400°C。为此，所用水泥浆的凝固性质必须要适应普遍条件。高温时通常需要缓凝剂，而低温时经常不得不用促凝剂。此外，在所用水泥浆中加入现有技术中已知的高效减水剂（superplasticizers）和/或降失水剂（fluid loss additives）会导致凝固时间延长，这也使得使用促凝剂成为必然。
根据Erik B.Nelson,Well Cementing,Schlumberger EducationalServices,Sugar Land,Texas,1990,chapter 3-3，氯化钙无疑是最常用、最有效和最经济的卜特兰水泥的促凝剂。CaCl2通常以2-4%bwoc(重量%，基于水泥部分)的浓度使用。遗憾的是，在浓度大于6%bwoc时结果是不可预知的，且可能会发生过早的凝固反应。此外，氯离子有腐蚀套管柱的危险。
因此本发明的目的主要是避免现有技术的缺点。特别是，需要没有上述缺点的可替代的促凝剂。
该目的是由权利要求1的特征实现的。从属权利要求涉及优选的实施方案。
WO 2010/026155A1描述的固化促进剂组合物中除了适合在水硬性粘合料中作为高效减水剂的水溶性梳状聚合物外，还包括大小合适的硅酸钙水合物颗粒（例如参见该WO说明书的权利要求40-52）。
出乎意料的是，上述组合物被发现也可作为无机粘合料中的促凝剂组合物，用于地下矿物油和天然气储集层的开发、开采和完井及用于深孔钻井。
因而，本发明涉及无机粘合料中的促凝剂组合物在地下矿物油和天然气储集层的开发、开采和完井以及深孔钻井中的用途，所述促凝剂组合物包括至少一种适合作为水硬性粘合料的高效减水剂的水溶性梳状聚合物，以及硅酸钙水合物颗粒。
本发明的促凝剂组合物以悬浮液，优选以水悬浮液的形式，或者以粉末的形式使用。
梳状聚合物优选是除存在于主链上的酸官能团外还具有含聚醚官能团的侧链的共聚物。它可以通过，例如，酸单体和聚醚大分子单体的自由基共聚反应得到，该共聚物整体含有至少45mol%，优选至少80mol%的衍生自酸单体和/或聚醚大分子单体的结构单元。
梳状聚合物优选地包含的结构单元衍生自（甲基）丙烯酸、马来酸、聚烷撑二醇乙烯基醚、聚烷撑二醇烯丙基醚和/或聚烷撑二醇（甲基）丙烯酸酯。对合适的结构单元的详细论述参考WO 2010/026155A1中权利要求47-49。合适的梳状聚合物有利地具有的平均分子量（Mw）为5000-200000g/mol，优选10000-80000g/mol，特别是20000-70000g/mol，其通过凝胶渗透色谱法测得。
除了所述梳状聚合物外，缩聚物也可能存在，特别是WO2010/026155A1的权利要求28-33和50公开的类型的缩聚物。
在所用的硅酸钙水合物中，钙相对于硅的摩尔比优选为0.6-2.0，特别是1.1-1.8。硅酸钙水合物中钙相对于水的摩尔比优选为0.6-6，特别优选为0.6-2.0，特别是0.8-2.0。
有利的是，所用的硅酸钙水合物颗粒由水溶性的钙化合物与水溶性的硅酸盐化合物反应得到，该反应优选在适合作为水硬性粘合料的高效减水剂的水溶性梳状聚合物的水溶液存在下进行。合适的制备方法的更多细节参考WO 2010/026155A1中权利要求1-38。
合适的硅酸钙水合物颗粒有利地小于5μm，优选小于1μm，更优选小于500nm，特别优选小于200nm，特别是小于100nm。
优选地，卜特兰水泥、铝酸钙水泥、石膏（gypsum）、硬石膏（anhydrite）、高炉渣、矿渣砂、粉煤灰（fly ash）、硅尘、偏高岭土、天然和合成的火山灰和/或煅烧的油页岩，优选卜特兰水泥，适合作为根据本发明促进其凝固过程的无机粘合料。
有利的是，所述粘合料以水泥浆的形式使用，水/水泥的值优选在0.2-1.0的范围内，特别是在0.3-0.6的范围内。
本发明特别考虑的一个使用领域是矿物油和天然气井的固井，特别是在永冻层区和近海区。
此处，本发明的用途是加速水泥浆的凝固。同时，水泥浆的硬化速率也有利地增加。此外，硬化水泥浆的静胶凝强度从100lb/100ft2(4.88kg/m2)增加到500lb/100ft2(24.4kg/m2)的时间有利地缩短。这在固井中是尤为有利的，因为由于上升的气泡，硬化水泥浆易于在胶凝强度的中间范围时裂开。依据本发明，该范围被快速通过。
依据本发明，促凝剂组合物有利地与固井中常用的其它添加剂，特别是高效减水剂、保水剂和/或流变改进添加剂，一起使用。
现将基于以下工作实施例并参考图1对本发明作更详细的解释。其中：
图1示出了不同水泥浆的抗压强度随时间的增加。
用途实施例1
按照API Specification 10,Section 5和Appendix A制备水泥浆。为此，将以下物质均匀混合：
700g水泥(Lafarge,H级)
266g自来水
3.5gK3F(高效减水剂,BASF Construction PolymersGmbH的产品)
3.5g
FL34(降失水剂,BASF Construction PolymersGmbH的产品)
1.0g磷酸三丁酯(消泡剂)。
样品中或者无添加剂（空白值），或者加入0.80%bwoc的CaCl2，或加入不同量的
100（BASF Construction Polymers GmbH的产品；硅酸钙水合物水悬浮液，颗粒大小<100nm，固体含量约21重量％，活性硅酸钙水合物的比例约7重量％，所用的梳状聚合物：MVA2500和EPPR312，同样是BASF的商品）。
100以0.07%bwoc、0.15%bwoc、0.30%bwoc和1.50%bwoc的量加入，所述量各自基于活性硅酸钙水合物的比例。
在静胶凝强度分析仪（Chandler Engineering）中于23°C的温度和1000psi(约69bar)的压力下对样品进行检测。表1列出了样品的静胶凝强度从100lb/100ft2(4.88kg/m2)增加到500lb/100ft2(24.4kg/m2)的时间。
表1
| 样品 | 时间[分钟] |
| 空白值 | 76.5 |
| 0.80%bwoc的CaCl2 | 44.0 |
| 0.07%bwoc的X-Seed 100 | 52.5 |
| 0.15%bwoc的X-Seed 100 | 38.0 |
| 0.30%bwoc的X-Seed 100 | 13.5 |
| 1.50%bwoc的X-Seed 100 | 15.5 |
此外，测定了抗压强度随时间的变化。结果以图表的形式在图1中示出。
显然，硅酸钙水合物悬浮液与CaCl2相比，以更低的剂量、在更大程度上加速了抗压强度的增加，同时，样品的静胶凝强度通过临界范围的时间被大幅度地缩短。
Claims (17)
1.一种用于无机粘合料的促凝剂组合物的用途，用于地下矿物油和天然气储集层的开发、开采和完井以及深孔钻井中，所述促凝剂组合物包括至少一种适合作为水硬性粘合料的高效减水剂的水溶性梳状聚合物，以及硅酸钙水合物颗粒。
2.权利要求1所述的用途，其中所述促凝剂组合物以悬浮液，优选以水悬浮液的形式使用。
3.权利要求1所述的用途，其中所述促凝剂组合物以粉末的形式使用。
4.权利要求1至3中任一项所述的用途，其中所述梳状聚合物以共聚物的形式存在，所述共聚物除存在于主链的酸官能团外还具有含聚醚官能团的侧链。
5.权利要求1至4中任一项所述的用途，其中所述梳状聚合物以共聚物的形式存在，所述共聚物可通过酸单体和聚醚大分子单体的自由基共聚反应获得，所述共聚物整体含有至少45mol%，优选至少80mol%的衍生自酸单体和/或聚醚大分子单体的结构单元。
6.权利要求1至5中任一项所述的用途，其中所述梳状聚合物包含衍生自（甲基）丙烯酸、马来酸、聚烷撑二醇乙烯基醚、聚烷撑二醇烯丙基醚和/或聚烷撑二醇（甲基）丙烯酸酯的结构单元。
7.权利要求1至6中任一项所述的用途，其中所述梳状聚合物的平均分子量（Mw）为5000-200000g/mol，优选10000-80000g/mol，特别是20000-70000g/mol，其通过凝胶渗透色谱法测得。
8.权利要求1至7中任一项所述的用途，其中所述硅酸钙水合物中钙相对于硅的摩尔比为0.6-2.0，优选1.1-1.8。
9.权利要求1至8中任一项所述的用途，其中所述硅酸钙水合物中钙相对于水的摩尔比为0.6-6，优选0.6-2.0，特别是0.8-2.0。
10.权利要求1至9中任一项所述的用途，其中所述硅酸钙水合物颗粒由水溶性钙化合物与水溶性硅酸盐化合物反应获得，该反应在适合作为水硬性粘合料的高效减水剂的水溶性梳状聚合物的水溶液存在下进行。
11.权利要求1至10中任一项所述的用途，其中所述硅酸钙水合物颗粒小于5μm，优选小于1μm，更优选小于500nm，特别优选小于200nm，特别是小于100nm。
12.权利要求1至11中任一项所述的用途，其中将卜特兰水泥、铝酸钙水泥、石膏、硬石膏、高炉渣、矿渣砂、粉煤灰、硅尘、偏高岭土、天然和合成的火山灰和/或煅烧的油页岩，优选卜特兰水泥，用作无机粘合料。
13.权利要求12所述的用途，其中所述粘合料以水泥浆的形式使用，水/水泥的值优选在0.2-1.0的范围内，特别是在0.3-0.6的范围内。
14.权利要求1至13中任一项所述的用途，用于矿物油和天然气井的固井，特别是在永冻层区和近海区。
15.权利要求1至14中任一项所述的用途，用于加速水泥浆的凝固。
16.权利要求1至15中任一项所述的用途，用于缩短硬化水泥浆的静胶凝强度从100lb/100ft2(4.88kg/m2)增加到500lb/100ft2(24.4kg/m2)的时间。
17.权利要求1至16中任一项所述的用途，与固井中常用的其它添加剂，特别是高效减水剂、保水剂和/或流变改进添加剂，一起使用。
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| PCT/EP2011/051138 WO2011131378A1 (de) | 2010-04-21 | 2011-01-27 | Verwendung von csh-suspensionen in der bohrlochzementierung |
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| CN105555889A (zh) * | 2013-07-18 | 2016-05-04 | 巴斯夫欧洲公司 | 包含含氧化铈磨料粒子的cmp组合物 |
| CN107162469A (zh) * | 2017-05-26 | 2017-09-15 | 中建商品混凝土有限公司 | 一种超小粒径胶束溶液早强剂及其制备方法 |
| CN110746551A (zh) * | 2019-10-09 | 2020-02-04 | 中国石油天然气股份有限公司 | 一种含双聚氧乙烯醚支链结构的共聚物及其制备和应用 |
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| US8561701B2 (en) * | 2010-12-21 | 2013-10-22 | Halliburton Energy Services, Inc. | Methods for cementing in a subterranean formation using a cement composition containing calcium silicate hydrate seeds |
| EP2759337A1 (de) * | 2013-01-25 | 2014-07-30 | Basf Se | Additiv für hydraulisch abbindende Massen |
| PL2878585T3 (pl) | 2013-11-27 | 2017-12-29 | Fundacíon Tecnalia Research & Innovation | Sposób wytwarzania cementowych ziaren c-s-h |
| US10793471B2 (en) | 2016-03-22 | 2020-10-06 | Sika Technology Ag | Composition based on calcium oxide |
| DE102016207858A1 (de) | 2016-05-06 | 2017-11-09 | Baustoffwerke Löbnitz GmbH & Co. KG | Dämmstoff |
| CN106747130B (zh) * | 2016-11-09 | 2019-08-02 | 嘉华特种水泥股份有限公司 | 一种耐高温油井封堵剂 |
| DE102017205822A1 (de) | 2017-04-05 | 2018-10-11 | Baustoffwerke Löbnitz GmbH & Co. KG | Verfahren und Vorrichtung zur Herstellung von porösem mineralischen Baumaterial |
| DE102018212322A1 (de) | 2018-07-24 | 2020-01-30 | Baustoffwerke Löbnitz GmbH & Co. KG | Verfahren zur Herstellung von porösem mineralischem Baumaterial mit verbesserter Festigkeit |
| RU2710862C1 (ru) * | 2019-07-31 | 2020-01-14 | Публичное акционерное общество «Татнефть» имени В.Д. Шашина | Состав для изоляции водопритока в скважину |
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| CN107162469A (zh) * | 2017-05-26 | 2017-09-15 | 中建商品混凝土有限公司 | 一种超小粒径胶束溶液早强剂及其制备方法 |
| CN107162469B (zh) * | 2017-05-26 | 2019-10-25 | 中建商品混凝土有限公司 | 一种超小粒径胶束溶液早强剂及其制备方法 |
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| DK2561034T3 (da) | 2019-08-12 |
| BR112012026716A2 (pt) | 2016-07-12 |
| MX2012009398A (es) | 2012-09-12 |
| RU2598945C2 (ru) | 2016-10-10 |
| RU2012149412A (ru) | 2014-05-27 |
| EP2561034B1 (de) | 2019-05-22 |
| CN102782080B (zh) | 2015-07-29 |
| CA2788620A1 (en) | 2011-10-27 |
| EP2561034A1 (de) | 2013-02-27 |
| WO2011131378A1 (de) | 2011-10-27 |
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