CN104919021B - 在非水性液体的增粘中使用的活化剂 - Google Patents
在非水性液体的增粘中使用的活化剂 Download PDFInfo
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- E21—EARTH OR ROCK DRILLING; MINING
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- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
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- E—FIXED CONSTRUCTIONS
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Abstract
一种用于使非水性基础液增粘的组合物。所述组合物含有具有以下通式的烷氧基化醇:X‑O‑(CnH2nO)y‑(C2H4O)z‑H,其中X是具有3至40个碳原子的有机基团,n是2、3或4,y是0至6,并且z是3‑20,和亲有机性粘土。所述基础液是在25℃下为液体并且基本不可混合在水中的油质液体。
Description
相关申请的交叉引用
本申请要求于2012年10月29日提交的美国申请号61/719,753的优先权,其公开内容通过引用结合在本文中用于全部目的。
发明背景-发明领域
本发明涉及包含亲有机性粘土的非水性液体的增粘,并且更具体地涉及井眼液的增粘。尤其是,本发明涉及一种活化剂,其用于将在多种用途(例如井眼液)中使用的亲有机性粘土剥离。
发明背景-现有技术描述
亲有机性粘土广泛地在多种溶剂体系中用作流变控制剂。尤其是,亲有机性粘土已经发现了在井眼液中的广泛用途,在与天然油气藏的开采、完井和生产相关的操作中的用途。此类操作的典型实例包括钻井、压裂地下地层、改变地下地层的渗透性、测井操作、防砂、封隔液等。
尤其是,在深井钻井中,在油基泥浆中使用亲有机性粘土具有一定优势,尽管它们初始成本明显较高。在水敏感性地层,例如溶胀性页岩、不溶盐地层中,以及在高温下,油基液体的优势是明显的。这些液体还用于钻柱润滑,尤其是在对曲线井或斜井进行钻井中,用于腐蚀保护,并且它们具有可再利用这一另外优势。
在油基井眼液中,以及在水基配制物中,亲有机性粘土的主要功能之一是起增粘剂的作用。然而,公知的是,为了亲有机性粘土在非水性井眼液中溶胀或使非水性井眼液增粘,必须首先将它们剥离。这通常利用少量作为活化剂的极性分子完成。典型的用于与粘土型触变性增粘剂如亲有机性粘土一起使用的活化剂包括水、乙醇、甲醇、二醇、硅酸钠、氟化钠、硅氟化镁、碳酸钙、极性疏质子化合物等。特别优选的并且广泛使用的活化剂是碳酸亚丙酯。
发明概述
在一个方面中,本发明提供一种活化剂,用于与亲有机性粘土一起在非水性液体尤其是非水性井眼液中使用。
在另一个方面中,本发明提供用于在非水性液体中使用的增粘包装。
在又一个方面中,本发明提供由非水性液体,例如烃系液体、亲有机性粘土和烷氧基化醇组成的井眼液。
在此外另一个方面中,本发明提供处理井眼的方法。
根据以下详细描述,本发明的这些和另外的特征和优点将会变得显而易见,其中参照了附图中的图。
优选实施方案详述
术语“井眼液”或类似的术语是指在来自地下地层的油和/或气的勘探、钻井或生产的任何阶段中使用的任何液体。
本发明的活化剂是烷氧基化醇或具有以下通式的烷氧基化醇的共混物:
X-O-(CnH2nO)y-(C2H4O)z-H I
其中X是具有3至40个碳原子的有机基团(organyl group),
n是2、3或4,
y是0至6,
并且z是3-20。
有机基团被定义为是醇的残基并且可以具有其他取代基的任何有机取代基,所述其他取代基例如-OH、NH2-、Cl等。
在优选的实施方案中,本发明的活化剂是烷氧基化醇或具有以下通式的烷氧基化醇的共混物:
CH3(CxH2x)-O-(CnH2nO)y-(C2H4O)z-H II
其中x是3至31,
n是2、3或4,
y是0至6,
并且
z是3-20。
烷氧基化醇可以通过本领域技术人员所公知的任何方法制备。以下美国专利教导了此类方法:U.S.8,329,609、U.S.5,627,121、U.S.5,220,077、和U.S.4,775,653,其全部通过引用结合在本文中用于全部目的。
一般来说,可用于本发明的醇烷氧基化物的功效可以借助具体烷氧基化物的亲水-亲脂平衡(hydrophilic-lipophilic balance,HLB)值来估算。如公知的,烷氧基化醇的HLB可以按照分子的烷氧基化部分的重量百分数除以5来估算,如由Rosen,Milton,J.和Kunjappu,Joy T.“Surfactants and Interfacial Phenomena(表面活性剂和界面现象)”John Wiley&Sons,2012年第四版,第357页教导的。因此,对于具有以下通式的乙氧基化物来说:
CH3(CH2)x-O-(CH2CH2O)n-H
可以如下粗略计算HLB:
HLB=100.44n/(5-(32+14x+44n))
一般来说,可用于本发明的醇烷氧基化物的HLB将会是约8至约16,约12至约15的HLB是优选的。
可用于本发明的醇烷氧基化物的醇或醇的共混物包括,但不限于,C6醇、C8醇、C8-C10直链醇、C10-C12直链醇、C12-C13氧代-醇、异十三烷醇、2-乙基-己醇、2-丙基-庚醇、2-丁基-辛醇、2-己基-癸醇、2-辛基-十二烷醇、2-癸基-十四烷醇、2-十二烷基-十六烷醇、直链伯醇、以及直链和/或支链仲醇二者。特别优选的是具有4至32个碳原子的支链醇。
可以在本发明的组合物中使用的基础油或液体包括但不限于油质液体。如在本文中所使用的,术语“油质液体”意指在25℃下为液体并且基本不可混合在水中的烃或油。在本文中适合使用的油质液体通常包括下列物质:如柴油,矿物油(包括较低芳族含量的矿物油),合成油如费歇尔-托普希(FT)衍生烃、聚烯烃或异构化聚烯烃,酯油,脂肪酸甘油酯,脂族酯,脂族醚,脂族乙酰、或其他此类烃和这些液体的组合。特别优选的是主要为直链的烃液体,尤其是衍生自包括FT反应的过程,例如气体到液体(GTL)过程的此类烃液体。通常,优选的是,本发明的基础油具有较低的芳族含量,例如以重量计小于约2%的芳族化合物。表1示出了可以使用的多种基础油。
表1
亲有机性粘土可以是任何对有机液体来说可用的触变增粘剂。适合的亲有机性粘土包括绿土(smectite)型、锂蒙脱石粘土或其他粘土与有机阳离子即季铵阳离子(有时被称为亲有机性粘土胶凝剂)的反应产物;绿土粘土;高岭土粘土;等等。根据本发明的一个方面,用作触变增粘剂的优选的亲有机性粘土是选自由下列各项组成的组的绿土型粘土:膨润土、锂蒙脱石、蒙脱石、绿脱石、贝得石(biedellite)、皂石、富镁蒙脱石、及其混合物,最优选膨润土或锂蒙脱石。在所使用的粘土是粘土和季铵化合物的反应产物的情况下,优选的季铵阳离子选自由下列各项组成的组:甲基三氢化牛脂铵、二甲基脱氢牛脂铵、二甲基苄基氢化牛脂铵、甲基苄基脱氢牛脂铵、和它们的混合物。适合用于与在本文中所描述的组合物一起使用的示例性的有机粘土和粘土胶凝剂在以下美国专利中给出,其所有相关部分通过引用结合在本文中:美国专利号2,531,427;美国专利号2,966,506;美国专利号4,105,578;和美国专利号4,208,218。适合与在本文中所描述的组合物一起使用的示例性的可商购亲有机性粘土是可从Southern Clay Products,Inc.,Gonzalez,Tex.,U.S.A.获得的CLAYTONE.RTM.IMG 400 Claytone ER、Claytone EM、和Claytone II,或者Bentone 34、Bentone 150和BENTONE.RTM.38Organoclay(商用锂蒙脱石系产品,可从许多供应厂商获得)。
以下表2和3示出了在含有非水性基础液ODC FT-140(GTL柴油)和作为ClaytoneII由Southern Clay Products销售的亲有机性粘土的组合物中典型的醇乙氧基化物的HLB的作用。
表2
表3
表2和3表明,至少对于所示的醇乙氧基化物来说,在基础液、亲有机性粘土类型和温度的这种特定体系中,约12至约15的HLB是优选的。
本发明的增粘包装包含活化剂和亲有机性粘土,二者如上所述。一般来说,本发明的活化剂将会以基于亲有机性粘土的约30重量%至约50重量%的量在增粘包装中存在,亲有机性粘土以50重量%至70重量%的量存在。当增粘包装在井眼液中存在时,其将为井眼液的约0.2至约4.0重量%的量。
以下表4示出了含有由Sasol North America,Inc.销售的非水性基础液LPA-170和作为Claytone II由Southern Clay Products销售的亲有机性粘土的组合物中多种醇乙氧基化物的作用。
表4
醇 | EO摩尔数 | 峰粘度(CP) |
NOVEL 6 | 2 | 0 |
NOVEL 6 | 4 | 11747.636 |
NOVEL 6 | 6 | 0 |
NOVEL 6 | 12 | 29369.09 |
NOVEL 23 | 5 | 0 |
NOVEL 23 | 9 | 17621.454 |
NOVEL 23 | 15 | 5873.818 |
NOVEL TDA<sup>4</sup> | 12 | 35242.908 |
N810<sup>5</sup> | 2 | 0 |
N810 | 4.5 | 0 |
N1012<sup>6</sup> | 9 | 0 |
ISALCHEM 123<sup>7</sup> | 9 | 0 |
ALFONIC TDA<sup>8</sup> | 9 | 35242.908 |
PPC/NOVEL 6(80/20)<sup>9</sup> | 12 | 29369.09 |
PPC/NOVEL 6(50/50) | 12 | 35242.908 |
PPCT/NOVEL 6(80/20) | 12 | 64,612 |
ISOFOL 12<sup>10</sup> | 9 | 29369.09 |
LIAL 123<sup>11</sup> | 12 | 11747.636 |
表4显示,不同的活化剂在不同的溶剂中具有不同的效果。因此,应当调节活化剂以适应所讨论的溶剂。以下非限制性实施例进一步阐明了本发明。
实施例1
在实施例1中,将1.5mL的活化剂NOVEL 8-612以缓慢的速度混合至100mL的溶剂中。所测试的四种溶剂是低温费歇尔-托普希(LTFT)馏出液ODC-140、LTFT馏出液SA-140、LTFT馏出液SA-170、和HF-1000共混物。在混合后,加入3.0克的亲有机性粘土Claytone II。将混合机变阻器增加至100并且将混合物混合20分钟。将粘土储存在玻璃罐中过夜。在环境静态老化16小时后,记录任何分离或沉降,并且将混合物重新均化30秒。之后使用适当的轴(spindle)以0.3rpm在3分钟内测量低剪切速率粘度。结果在图1中示出。如示出的,NOVEL8-6利用SA 170获得了最高粘度。
实施例2
重复实施例1的实验,但是所使用的活化剂是NOVEL 1012-913。结果在图2中示出并且表明利用ODC-140样品获得了最高粘度。
实施例3
重复实施例1的实验,但是所使用的活化剂是NOVEL23-914。结果在图3中示出并且表明利用SA-140获得了最高粘度。
在以上实验中,全部三种活化剂都实现了亲有机性粘土的粘度的增加,但是各自对特定的溶剂是最适合的。因此,可以针对溶剂的最佳性能调节本发明的活化剂的选择。
尽管以上提到本发明的基础组合物是非水性的,应该理解的是,在某些情况中,加入少量的水作为共活化剂可以进一步增强所得到的亲有机性粘土悬浮液介质的悬浮特性。当使用时,水通常将会以基于亲有机性粘土的约30重量%至约50重量%的量在组合物中存在。
尽管在以上描述中提到与在井眼液中使用的亲有机性粘土一起使用本发明的活化剂,应理解的是,本发明不限于此。如本领域技术人员公知的,活化的亲有机性粘土因其在许多类型有机液体中的胶凝和粘度增加能力而众所周知。因此,除了井眼液(例如钻井液)之外,它们还发现了在涂料、油脂和玻璃纤维树脂中的广泛用途。它们也可以在化妆品、墨水和抛光剂中使用。
应认识到的是,当用作井眼液时,本发明的组合物可以含有根据井眼液中的特定用途而调节的某些成分或添加剂。因此,例如,如果井眼液是用于密封地下区域的密封组合物,则还可以使用水溶性粘土、交联剂、分散剂、水泥、填料等。在适用于控压钻井(MPD)的粘度井处理液组合物的情况中,组合物还可以包含乳化剂、润湿剂、滤失控制添加剂和加重材料。此外,如公知的,完井液通常由含有如氯化铵、氯化钠、溴化钠等这样的材料的澄清盐水组成。可以使用本发明的组合物改善所得到的完井液的添加剂的分散,使得悬浮粒子在被引入至完井液之前保持较长时间的悬浮或在较高温度下的悬浮。根据本发明的压裂液除了增粘包装之外可以包含支撑剂、某些聚合物材料和其他成分。针对某些目的采用多种井眼液的方法是本领域技术人员公知的并且也是本发明所预期的。通常,本发明的井眼液可以包含选自由下列各项组成的组的添加剂:乳化剂、润湿剂、增粘剂、增重剂、滤失控制剂、支撑剂、和用于形成砾石充填的颗粒剂。
尽管已经在本文中一些细节方面描述了本发明的具体实施方案,这仅是出于解释本发明的多个方面的目的而完成的,并且并非意在限制如以下权利要求中所定义的本发明的范围。本领域技术人员将会理解,所示出和描述的实施方案是示例性的,并且在不背离其范围的情况下,可以在本发明的实施中做出多种其他替换、变更和修改,包括但不限于在本文中具体讨论的那些设计替代方案。
Claims (12)
1.一种井眼液,所述井眼液包含:
油质液体,所述油质液体在25℃下为液体并且基本不可混合在水中,具有小于约2%的芳族化合物并且主要是直链的,其中所述油质液体包括烃液体并且其中所述烃液体衍生自包括费歇尔-托普希反应的过程;
具有8至16的HLB并且具有以下通式的烷氧基化醇:
X-O-(CnH2nO)y-(C2H4O)z-H
其中X是具有3至40个碳原子的有机基团,n是2、3或4,y是0至6,并且z是3-20;和
绿土型的亲有机性粘土。
2.根据权利要求1所述的井眼液,其中:
所述烷氧基化醇具有以下通式:
CH3(CxH2x)-O-(CnH2nO)y-(C2H4O)z-H
其中x是3至31,n是2、3或4,y是0至6,并且z是3-20;和
亲有机性粘土。
3.根据权利要求1所述的井眼液,其中所述烷氧基化醇具有12至15的HLB。
4.根据权利要求1所述的井眼液,其中所述烷氧基化醇以基于所述亲有机性粘土的30重量%至50重量%的量存在。
5.根据权利要求1所述的井眼液,其中所述烷氧基化醇由支链醇制成。
6.根据权利要求1所述的井眼液,其中所述亲有机性粘土选自由下列各项组成的组:膨润土、锂蒙脱石、蒙脱石、绿脱石、贝得石、皂石、富镁蒙脱石、和它们的混合物。
7.根据权利要求1所述的井眼液,其中所述烷氧基化醇和所述亲有机性粘土以基于所述井眼液的0.2%至4.0%的量存在。
8.根据权利要求1所述的井眼液,所述井眼液还包含:
基于所述亲有机性粘土的量为30至50%的水。
9.一种处理井眼的方法,所述方法包括:
向所述井眼中引入根据权利要求1所述的井眼液和添加剂,所述添加剂包括乳化剂、润湿剂、增粘剂、增重剂、滤失控制剂、支撑剂、和用于形成砾石充填的颗粒剂中的至少一种。
10.根据权利要求9所述的方法,其中所述处理包括钻井。
11.根据权利要求9所述的方法,其中所述处理包括将井压裂。
12.根据权利要求9所述的方法,其中所述处理包括形成砾石充填。
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