CN106715638A - 用于处理油气井的组合物和方法 - Google Patents
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/40—Spacer compositions, e.g. compositions used to separate well-drilling from cementing masses
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- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
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- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- 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
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
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Abstract
用于油气井中的多种井下操作的组合物。组合物可以包含某些醚和其他组分例如酯、烷氧基化醇、酸化剂和烃助溶剂的多种组合。组合物可用于各种各样的井下应用,尤其是井清洗、滤饼移除和井增产技术,例如酸化。
Description
相关申请的交叉引用
本申请要求于2014年7月15日提交的美国申请号62/024,888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。
发明领域
本发明涉及用于处理油井和/或气井的组合物和方法。更具体地,本发明涉及用于移除不需要的井眼壁残留物和水润湿井眼表面的组合物和方法。最具体地,本发明涉及用于井眼清洗的溶剂共混物和表面活性剂/助表面活性剂组合、隔离液和顶替流体、以及用于滤饼移除的破碎剂(breaker)流体的用途。
发明背景
存在大量与从地面钻孔的油和/或气的钻井、完井、增产和采集结合进行的操作。在几乎全部这些操作中,取决于所进行的操作,采用多种液体/流体组合物实现所需结果。例如,在钻井液配制物中,在完井液中(如在注水泥之前的井眼清洗中),在增产液中(如在水力压裂或酸化配制物中),以及在采集操作中(如在重质原油中的石蜡固体和用于乳液破碎剂的助溶剂的溶解中),采用溶剂作为基础油。
仅作为实例,目前,可以使用通常被称为稀释/清洗隔离剂并且用作单一流体隔离剂或微乳液的溶剂如甲苯和二甲苯进行井眼清洗操作。二甲苯和甲苯由于它们的毒性和致癌性质而引起环境的顾虑。作为在井眼清洗应用中的备选方案,可以采用萜烯。然而萜烯如d-柠檬烯遭遇不稳定的定价和低闪点的缺点。
考虑到安全处理、稳定供应和成本顾虑,从未停止寻找用于涉及油井和或气井的建造的基本上所有操作的无毒、生物可降解、且成本有效的井处理液。
发明概述
在一个方面中,本发明提供用于多种井眼清洗操作的环境安全的组合物。
在另一方面中,本发明提供用于多种井眼清洗操作的拥有高闪点和良好溶解性质的溶剂/组合物。
在又一个方面中,本发明提供用于多种井眼清洗操作的拥有高闪点和良好溶解性质的表面活性剂和溶剂/组合物。
在又一个另外的方面中,本发明提供处理井眼如注水泥操作之前的井眼清洗和/或滤饼移除以提供钢套管和地层之间的良好结合的方法。
根据以下详细描述,其中参照了附图中的图,本发明的这些和另外的特征和优点将会变得显而易见。
附图简述
图1是比较多种组合物的从不锈钢表面移除油状残留物的能力的一系列照片。
优选实施方案详述
如以下更充分描述的,本发明的组合物的特征在于包含醚。
如本领域技术人员已知的,对于用于几乎任何种类的油/气井处理的任何溶剂/组合物来说,具有高闪点的液体是理想的。本发明描述了新型的方法或工艺,其包括使用单独醚、醚/润湿表面活性剂、醚/酯、醚/表面活性剂/酯、和任选的助溶剂以从井眼表面移除不需要的残留物。此前对于醚和酯的任何提及或应用被限制在了它们在油系钻井液配制物中改善润滑性、环境和温度廓线以及增加钻井液的导电率的用途。因此,本发明的组合物采用含有约8至约30个碳原子并且具有以下通式的醚:
R-O-R1 I
其中R和R1各自为可以彼此独立为直链或支链的并且含有约1至约29个碳原子的烷基。在优选的实施方案中,烷基R和R1各自含有5至7个碳原子。
适合的醚的非限制性实例包括二丁基醚、二己基醚、二庚基醚、二辛基醚、二壬基醚、二癸基醚、己基-辛基醚、己基-庚基醚、二(2-乙基己基)醚、二(2-丙基庚基)醚等。因此,醚可以是对称的或非对称的并且可以包含多种醚例如对称醚和非对称醚的混合物。
本发明的组合物的其他基础组分是上述一种或多种醚与酯或表面活性剂的混合物,其可以为(1)具有一个或多于一个酯基的酯、(2)烷氧基化醇、或(3)它们的混合物。
可用于本发明的组合物的基础酯可以具有以下通式:
其中R2至R5是各自具有1至30个碳原子的直链或支链烷基并且n是0至20。
可以在制备一元酯中使用的典型羧酸的非限制性实例包括甲酸、乙酸、戊酸、辛酸、月桂酸、花生酸。可以在制备二元酯中使用的典型羧酸的非限制性实例包括草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、邻苯二甲酸、杜鹃花酸等。可以在制备三元酯中使用的典型羧酸的非限制性实例包括柠檬酸、乌头酸(aconitric acid)、均苯三酸、丙烷-1,2,3-三元羧酸等。
可用于形成本发明的酯的醇包括含有1至30个碳原子的单羟基醇并且可以是直链醇、支链醇、或格尔伯特(Guerbet)醇(通常描述为2-烷基-1-醇)。适合的醇的非限制性实例包括甲醇、乙醇、丙醇、丁醇、己醇、辛醇、癸醇、2-丁基-1-辛醇、2-丙基-1-庚醇、2-乙基-1-己醇等。
如指出的,除了上述酯之外,可用于形成本发明的组合物的表面活性剂可以包括各种各样的烷氧基化醇。通常,可用于本发明的烷氧基化醇将会具有以下通式:
CH3(CxH2x)-O-(CnH2nO)y-(C2H4O)z-H IV
其中x是3至30
n是2-4,
y是0至6,并且
z是3至20。
尤其是,优选的烷氧基化醇是乙氧基化醇,其中
x是5至29,
y是0,
z是3至12。
可以在制备表面活性剂中使用的醇的非限制性实例是异十三烷醇、异癸醇、2-丙基庚醇、2-乙基己醇、月桂醇等。
除了以上列出的组分以外,本发明的组合物可以包含通常本质上为烃的助溶剂。还重要的是提到,早前描述的醚可以同时充当溶剂和助溶剂二者。通常,助溶剂具有高含量的环烷烃和或高度支链的链烷烃。一般来说,助溶剂可以含有约20%至约90%以上的环烷烃、异链烷烃、或它们的混合物。尤其是,具有这样的组成的助溶剂将会含有在约C8至约C30范围内的烃。以下表1列出了可以在本发明的组合物中使用的各种各样的助溶剂的非限制性实例。
表1
如可以在表1中看到的,助溶剂可以包含具有约10%至约35%的异链
烷烃、约30%至约73%的环烷烃并且具有约C8至约C30的碳链长度的液体烃。如还可以从表1中看到的,一些助溶剂可以包含大量直链烷烃,而其他助溶剂可以含有少量含氧物(oxygenate)如醇、酯等。如根据表1还应当显而易见的,一些助溶剂可以含有烯烃,而其他助溶剂例如柴油可以含有大量芳族化合物。通常,表1说明,在本发明的组合物中,任选的助溶剂可以有利地使用各种各样的烃,尽管在某些情况中可以存在其他化合物。还将会理解的是,尽管可以使用柴油,其不优选作为助溶剂,这主要是因为其较高的芳族化合物含量使得其在生态上是较不理想的。
本发明的井眼清洗组合物的醚含量通常将会以总配制物的约40至约90重量%的量存在。当再使用润湿表面活性剂时,其将会占总组合物的约0.01至约5重量%。当使用助溶剂时,助溶剂将会占总组合物的约10至约90重量%。
可以使用本发明的组合物配制酸化组合物并且醚可以以总组合物(即醚、一种或多种表面活性剂和酯、任选一种助溶剂、包括任何腐蚀抑制剂在内的酸化剂)的约多至95重量%的量存在。
如本领域技术人员公知的,增产是在油气井中用于增加或恢复采集的过程。例如,在一些情况中,首先钻的井展现出低渗透性并且增产用于开始从储层中采集。其他时候,增产用于进一步促进渗透性和来自己经变得处于采集中的已经存在的井的流动。酸化是典型的增产处理,其通常为了恢复储层岩石的自然渗透性而在低于储层断裂压力进行。如本领域技术人员公知的,通过将酸泵送至井中以溶解储层岩石的沉淀物颗粒之间的石灰石、白云石、和方解石来实现酸化。通常,存在两种类型的酸化,基岩酸化和压裂酸化。
基岩酸化在将酸泵送至井中并且泵送至储层岩石的孔中时进行。在这种类型的酸化中,酸将抑制岩石渗透性的沉淀物和泥浆固体溶解,扩大了储层的自然孔,从而促进烃的流动。基岩酸化通常在足够低的压力下进行以防止储层岩石压裂,而压裂酸化包括将高度加压的酸泵送至井中,使储层岩石物理压裂并且将抑制渗透性的沉淀物溶解。在后一种情况中,形成了烃可以经过其流动的通道。尽管可以在酸化组合物中使用多种酸,但盐酸是最常用的之一并且可以与氢氟酸组合从而具有溶解来自储层岩石的石英、砂和粘土的能力。在高温应用中,有机酸如甲酸或乙酸可以用于影响更慢的反应以及因此的更深的增产。因此,在本发明的组合物的情况中,酸化组合物可以包含醚、一种或多种表面活性剂、任选一种助溶剂和选择的酸。还将会认识到,典型的酸化配制物可以含有其他组分如抑制剂添加剂以保护酸免于将井中的钢套管降解。另外,可以加入多价螯合剂以阻止铁的凝胶或沉淀剂的形成,它们可能会在酸化工作期间阻塞储层孔。
在井增产操作中,如酸化中使用的有机溶剂通常具有高贝壳松脂丁醇(kauri-butanol,KB)值,其表示它对油状残留物或有机污染物的高溶解能力或溶解力。当与d-柠檬烯相比时,在本发明中使用的己基醚溶剂具有良好的溶解力和高闪点(参见表2)。
表2
溶剂 | 闪点(°F) | 贝壳松脂丁醇值 |
甲苯 | 43 | 102 |
二甲苯 | 77 | 98 |
LPA 142 | 142 | 34 |
HF1000 | 178 | 18 |
D-柠檬烯 | 110 | 67 |
己基醚 | 207 | 95 |
表2清楚地显示,二己基醚溶剂具有与二甲苯相同的溶解力,但比d-柠檬烯高的溶解力和闪点。由于较低的用溶剂处理的风险和火灾事故的可能性,在油田操作中需要高闪点溶剂。
本发明的组合物可以用于溶解/减少来自井眼表面的油状残留物,使得这样的表面通过润湿表面活性剂被水润湿。在点滴试验方法中,使用汉克门规(Hegman gauge)评价醚溶剂、醚/表面活性剂、醚/酯和醚/酯/表面活性剂组合物从不锈钢表面移除或减少油状残留物的能力。在这种方法中,在60秒的时间段内将1mL的溶剂和/或表面活性剂、酯组合物逐滴施加至均匀涂抹在以45度角倾斜的汉克门不锈钢规上的油上。所使用的表面活性剂是由Sasol North America,Inc.制造的Ethoxylate(TDA-7)。TDA-7衍生自乙氧基化为7摩尔氧化乙烯的平均值的异十三烷醇。图1示出了在溶剂和/或溶剂/表面活性剂系统运行之前(空白)和刚运行之后在汉克门规上剩余的油的数字图像。
在使用本发明的组合物的具体方法中,在使用反相乳液钻井液钻井之后,需要从井眼表面移除油状残留物和其他有机污染物并且将井眼和套管表面水润湿,目的是进行进一步操作如固井,如本领域技术人员已知的,其用于提供套管和井眼表面之间的良好结合。当在不明显减少或移除油状残留物或滤饼的情况下完成砾石充填时,出现类似的结合问题。本发明包含以有效移除或减少井眼中的油状残留物的量存在的醚组合物和润湿表面活性剂。醚本身将会移除或减少油状残留物,但是将不会使井眼表面水润湿。包含润湿表面活性剂如TDA-7将会使地层润湿性从油润湿改变为水润湿。如在图1中看到的,醚与表面活性剂的组合似乎提高了井眼清洗液体系统的溶解力。将500ppm的润湿表面活性剂(TDA-7)加入至d-柠檬烯中还增加了油状残留物由于增加的溶解力而从不锈钢表面移除。
在井眼的钻进期间,通常在井中使用多种液体用于各种功能。液体可以通过钻管和钻头循环至井眼中,并且随后通过井眼向上流动至表面。在该循环期间,钻井液可以用于:移除钻屑,当中断循环时使钻屑和加重材料悬浮,控制地表下压力,维持井眼的完整性直到将井段下套管并且注水泥,通过提供足够静水压力来将液体从地层分离以防止地层液体进入井眼中,将钻柱和钻头冷却和润滑,和/或使透过率最大化。
保护地层的一种方式是通过在地下地层的表面上形成滤饼。当悬浮在井眼液中的粒子包覆并且堵塞地下地层中的孔时,形成滤饼,从而滤饼防止或降低流体向地层中的损失和在地层中存在的流体的流入。大量形成滤饼的方式是在本领域中已知的,包括使用桥堵粒子、由钻井过程形成的钻屑、聚合物添加剂等。在已经完成完井操作之后,移除在钻井和/或完井期间产生的、在井眼的侧壁上残留的滤饼的可能会是必需的。尽管滤饼形成和滤失小段塞的使用在钻井和完井操作中是必需的,但是,例如,如果岩石地层仍然被屏障(barrier)堵塞,屏障可能会是对来自井的烃或其他液体的采集的明显阻碍。因为滤饼是致密的,其通常强粘附至地层壁并且不能通过单独的流体作用从地层中方便或完全地冲洗出来。
在所有井中,并且尤其是在裸眼水平井完井中,高效的井清洗和完井的问题是明显的问题。井的生产率或多或少地取决于有效且高效率地移除滤饼,同时使水阻断、堵塞或破坏地层的自然流动以及完井组件的那些的可能性最小化。
因此,对于有效清洗井眼并且在井投产后不抑制地层采油或采气的能力的破碎剂流体系统,存在持续的需求。因为这种大的溶解能力、高闪蒸溶剂组成、和它们可以被配制为特定地层所需的确切规格这一事实,本发明的组合物理想的是适合的破碎剂流体和顶替流体配制物。
本发明的组合物通常显示出优异的移除/减少油状残留物和将套管/地层表面水润湿的能力(图II)。进行滤饼清洗/移除实验以确定二己基醚相对于其他溶剂的清洗效率。操作包括在API压滤机多单元装置上由非水性钻井泥浆制作滤饼。将滤饼预称重,放置在含有待测试液体的烧杯中。流变计向下放入液体中,以300RPM测试速度旋转10分钟并且将滤饼移除并再次称重。数据清楚地显示,在12磅/加仑GTL基础柴油钻井液中二己基醚表现比二甲苯好得多。如在表3中看到的,二甲苯一直是用于从油井的井眼移除油状残留物的易于实现的有机溶剂。也已经发现,取决于成分的具体选择,本发明的组合物有效移除与不同的合成油系泥浆一起形成的油状残留物。
表3
溶剂 | 滤饼移除(wt%) |
二辛基醚 | 5.9 |
二甲苯 | 8.3 |
HF1000 | 12.8 |
LPA 142 | 15.5 |
ODC-15 | 19.2 |
二己基醚 | 23.3 |
二己基醚+表面活性剂 | 24.9 |
根据本发明的组合物所处的用途,可以通过通常与井眼处理操作结合使用的多种方法将它们引入至井眼中。例如,在使用组合物作为破碎剂流体以移除滤饼的情况中,可以将采用本发明的组合物的破碎剂流体泵送至井眼中,之后将井封闭所需的时间段以将滤饼破碎,之后可以将破碎剂流体移除。在使用本发明的组合物对井进行清除、即移除油状残留物等的情况中,可以再次将含有本发明的组合物的清洗配制物注入至井中并且将井封闭所需的时间段。备选地,预期了会使清除液体在井眼/套管中循环,直到减少/移除所有残留物。
根据以上将会显而易见的是,本发明的多种组合物可以用于多种井处理包括,但不限于,井清洗、滤饼移除和酸化。结合那些井维护操作,所选择的特定组合物的量将会取决于在其中钻井的地层的性质、井下条件例如温度等。因此,基于以上所述,例如井下条件,可以使用并且选择带有酸化剂、生物杀灭剂、腐蚀抑制剂等的本发明的组合物。仅作为实例,如果酸化是所选择的井处理,可以仅与酸化剂和任选的助溶剂结合使用本发明的醚。对于滤饼移除和其他操作来说,类似的情况是可行的。
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 (15)
1.一种用于油气井中的井下操作的组合物,所述组合物包含:
A.具有以下通式的醚:
R-O-R1 I
其中R和R1各自为可以彼此独立为直链或支链的含有约1至约29个碳原子的烷基;和
B.至少一种选自由下列各项组成的组的附加组分:
(i)以下式的酯:
其中R2-R5是具有1至30个碳原子的直链或支链烷基并且n是0至20;
(ii)具有以下通式的烷氧基化醇:
CH3(CxH2x)-O-(CnH2nO)y-(C2H4O)z-H IV
其中x是3至30,n是2至4,y是0至6并且z是3至20;和
(iii)(i)和(ii)的混合物;
(iv)酸化剂;和
(v)(i)、(ii)和(iv)的混合物。
2.权利要求1所述的组合物,所述组合物还包含助溶剂,所述助溶剂包含含有约6至约30个碳原子的液体烃。
3.权利要求2所述的组合物,其中所述助溶剂含有约20至约90重量%以上的环烷烃、异链烷烃或它们的混合物。
4.权利要求2所述的组合物,其中所述助溶剂包含约10至约35重量%的异链烷烃和约30至约73重量%的环烷烃,其全部含有约8至约30个碳原子。
5.权利要求1所述的组合物,其中所述醚以约40至约90重量%的量存在,酯和烷氧基化醇的组合量以约0.01至约5重量%的量存在。
6.权利要求5所述的组合物,其中所述助溶剂以约10至约90重量%的量存在。
7.权利要求1所述的组合物,其中所述组合物含有多至约95重量%的醚。
8.权利要求1所述的组合物,其中每个R和R1含有5至7个碳原子。
9.一种处理井眼的方法,所述方法包括:
I.提供包含下列各项中的一种的组合物;
配制物A,其包含具有以下通式的醚
R-O-R1 I
其中R和R1各自为可以彼此独立为直链或支链的含有约1至约29个碳原子的烷基;和
配制物B,其包含配制物A和至少一种选自由下列各项组成的组的附加组分:
(i)以下式的酯:
其中R2-R5是具有1至30个碳原子的直链或支链烷基并且n是0至20;
(ii)具有以下通式的烷氧基化醇:
CH3(CxH2x)-O-(CnH2nO)y-(C2H4O)z-H IV
其中x是3至30,n是2至4,y是0至6并且z是3至20;和
(iii)(i)和(ii)的混合物
配制物C,其包含配制物A和烃助溶剂;
配制物D,其包含配制物B和烃助溶剂;
配制物E,其包含配制物A和酸化剂;
配制物F,其包含配制物B和酸化剂;
配制物G,其包含配制物C和酸化剂;
配制物H,其包含配制物B和烃助溶剂;
配制物I,其包含配制物F和烃助溶剂;
II.将配制物A-I中的至少一种引入至井眼中;以及
III.进行包括下列各项中的一种的操作:
(i)井眼清洗;
(ii)滤饼移除;
(iii)酸化。
10.权利要求9所述的方法,其中所述助溶剂包含含有6至约30个碳原子的液体烃。
11.权利要求10所述的组合物,其中所述助溶剂含有约20至约90重量%以上的环烷烃、异链烷烃或其混合物。
12.权利要求10所述的组合物,此时所述助溶剂包含约10至约35重量%的异链烷烃和约30至约73重量%的环烷烃,其全部含有约8至30个碳原子。
13.权利要求9所述的方法,其中所述醚以约40至约90重量%的量存在,酯和烷氧基化醇的组合量以约0.01至约5重量%的量存在。
14.权利要求9所述的方法,其中所述酸化剂选自由下列各项组成的组:盐酸、氢氟酸、过甲酸和乙酸以及它们的混合物。
15.权利要求9所述的方法,其中R和R1中的每一个含有5至7个碳原子。
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PCT/US2015/040362 WO2016011015A1 (en) | 2014-07-15 | 2015-07-14 | Compositions and methods for treating oil and gas wells |
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BR (1) | BR112017000819B1 (zh) |
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AU2015289868B2 (en) * | 2014-07-15 | 2019-07-11 | Sasol Performance Chemicals Gmbh | Compositions and methods for treating oil and gas wells |
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CO2017001390A2 (es) | 2017-05-19 |
ZA201700284B (en) | 2018-04-25 |
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US20190233710A1 (en) | 2019-08-01 |
WO2016011015A1 (en) | 2016-01-21 |
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AU2015289868B2 (en) | 2019-07-11 |
US11084968B2 (en) | 2021-08-10 |
MX2017000647A (es) | 2017-04-27 |
RU2017103460A (ru) | 2018-08-15 |
BR112017000819A2 (pt) | 2017-12-05 |
US20170158943A1 (en) | 2017-06-08 |
CA2955193C (en) | 2023-03-14 |
EP3169747A1 (en) | 2017-05-24 |
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