CN103189594A - 用表面化合作用抑制水合物沉积 - Google Patents
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Abstract
一种用于生产和输送原油的系统,该系统包括:用于生产原油的井;用于处理原油的处理设施;和穿过井和处理设施之间至少一部分距离的管线,其中至少一部分管线在温度低于20℃的大气中穿行,其中管线包括在管线内表面上的涂层,和其中原油包含表面活性剂添加剂。
Description
技术领域
本发明涉及经管线输送流体以将水合物累积降至最低。
背景技术
通常通过用一个或多个井穿透地层和泵送或允许油和气流过这些井来从地下地层采收油和气。在从深水井生产油和气的过程中,海底温度低和流体压力高会导致形成气体水合物。气体水合物会达到使井筒和输送气体的地面管线发生堵塞的程度。该气体水合物和/或其它沉淀物造成的阻塞会影响油和气流向地面分站。
美国专利申请公开2006/0186023公开了一种经管线输送产出流体同时限制在所需的管线内壁位置上产生沉积的方法,该方法包括提供所述所需的管线内壁位置处的内表面粗糙度Ra小于2.5微米的管线,强制所述产出流体经过该管线,其中所述产出流体在所述所需的管线内壁位置处每平方厘米的壁剪切应力为至少1达因。美国专利申请公开2006/0186023在这里全文引入作为参考。
共同待审的PCT专利申请PCT/US2010/020420公开了一种不粘装置,该装置包括包含第一材料的液体储存或运输制品;在制品的内表面上包含第二材料的涂层;其中第二材料的临界表面张力值小于75mN/m和以莫氏标度(Moh's scale)计硬度值小于5。PCT专利申请PCT/US2010/020420在这里全文引入作为参考。
发明内容
本发明的一个方面提供一种用于生产和输送原油的系统,该系统包括:用于生产原油的井;用于处理原油的处理设施;和穿过井和处理设施之间至少一部分距离的管线,其中至少一部分管线在温度低于20℃的大气中穿行,其中管线包括在管线内表面上的涂层,和其中原油包含表面活性剂添加剂。
附图说明
图1显示了海上生产井。
图2是液体与固体表面接触角的示意图。
图3是在固体表面上前进和后退接触角的示意图。
具体实施方式
一方面,这里公开的实施方案涉及用表面化合作用抑制在钻探管壁上水合物沉积的系统和方法。更特别地,这里公开的实施方案涉及通过将壁涂层和向产出物流添加表面活性剂组合起来抑制在钻探管壁上水合物沉积物的系统和方法。
将油和气井钻入地下地层以生产蕴藏在这些地下地层中的天然气。深水钻探操作实现了烃的勘探和生产。天然气中可能存在二氧化碳、硫化氢和多种水合物形成烃如甲烷、乙烷、丙烷和丁烷。水也可以以不同的量与这些水合物形成烃和其它石油成分一起存在。在低海底温度和高流体压力下,当烃、石油成分和其它水合物形成物质与水混合时,可形成笼状水合物。笼状水合物是含水晶体,它围绕客体分子如水合物形成烃形成笼状结构。气体水合物是一类笼状水合物,和在石油工业中受到特别关注。水合物的聚集导致天然气和其它石油流体的生产和/或输送期间发生管线堵塞。因此,阻止或最小化这种由水合物引起的堵塞的发生是流动保证的首要目标。
图1:
参照图1,包括井10的系统100连接到海上钻井平台11。在升高的压力下在包含天然气、油或它们的组合的地下地层12中完成了井10。井10由具有通向地下地层12的孔14的套管13加套。生产管15悬吊在套管13中,它具有与地下地层12和生产管15流体连通的环隙16。生产管15从井10经上升管17向上延伸到平台11。封隔器密封元件18将油井的上部与地下地层12的生产区隔开。
气体和其它石油流体经环隙16从地下地层12进入生产管15,流向平台11。从地下地层流出过程中,气、油或它们的组合温度降低。这可能是由于井自身温度低或由于流到地表时气体中的压力降低大。该温度降低会导致形成不希望的水合物和/或可能形成其它固体。沉积物的持续需要沉积物与壁的粘合力足以将沉积物保持在壁上。
本公开的实施方案提供了阻止堵塞发生或将堵塞发生频率最小化的新方法。这里公开的实施方案比传统方法使用的化学品少,因此更加环境友好。这里公开的实施方案涉及抑制在生产和/或输送装置的内表面上形成水合物和发生沉积的系统和方法,该方法包括:(a)沉积涂层和(b)向产出物流添加表面活性剂以1)减少沉淀的固体或沉淀固体的材料与生产和/或输送装置内表面的接触,和2)减小水合物沉积物与生产和/或输送装置内表面的粘合作用。
可通过将表面涂层与添加表面活性剂组合起来以增大产出流体物流的接触角(θ)来实现减少沉淀的固体或沉淀固体的材料与生产和/或输送装置内表面的接触。接触角(θ)是液体在固体上铺展或者固体被液体润湿的定量量度。因此,如果水滴在平坦固体表面上的接触角小于90°,则固体表面被称为“水润湿”,而如果水滴在平坦固体表面上的接触角大于90°,则不能水润湿。可使用接触角测量法间接测量固体的表面能。
图2:
大体上,参照图2,作为接触角通常意义上的解释,将液滴21置于固体表面20上。几何学上,将接触角定义为在液体21、蒸气22和固体20接触的三相边界处由液体形成的角。接触角与固体20、液体21和蒸气22三相间界面能之间的关系由杨氏方程定义:
Cosθ=(γSV-γSL)/γLV
其中γSV、γSL和γLV分别代表固体/蒸气、固体/液体和液体/蒸气界面处的界面张力。表面能通过如下关系式涉及到γSV:
γSV=γS-πe
其中γS是固体的真实表面能,πe是平衡铺展压力,它是通过蒸气22吸附到固体20表面上释放出的能量的量度。当固体的表面能高和液体的表面张力低时,只有平衡铺展压力是重要的。
可以静态或动态测量接触角。静态接触角由θstatic表示,它反映了处于平衡的系统。通常使用测角术测量θstatic。液体的固着或自由液滴21在固体表面20上的接触角由固体20与液体液滴21在表面上的切线之间形成的角来确定。
动态接触角反映了固体/液体/蒸气相处于运动状态的系统。动态接触角可以是前进的即θadv,和后退的即θrec。参照图3a,当使用毛细吸管32添加液体时测量前进的接触角θadv。当添加液滴时,液滴31的弯液面移向未润湿的固体表面30。参照图3b,当使用毛细吸管32移除液体时测量后退的接触角θrec。当移除液体时,液滴31的弯液面从已经润湿的固体表面30退回。θadv提供了关于固体表面的疏水或低表面能性质的信息,而θrec反映了固体表面的亲水或高表面能性质。滞后θΔ是前进的和后退的接触角之间的差值(θΔ=θadv-θrec)。
对于本公开来说,有几个接触角需要关注。特别地,在产出的流体物流的连续流体中,存在盐水在导管上的接触角αb和沉淀的水合物在导管上的接触角αh。如上面所解释的,沉淀水合物的盐水在导管上的表面能可以称为β,而沉淀的水合物的粘合作用可以称为γ。
减少沉淀固体与导管接触的一种途径是选择涂覆-添加表面活性剂组合的导管表面,该组合增大产出的流体物流的连续流体中产出的流体物流沉淀的水合物在导管表面上的接触角αh或者沉淀水合物的盐水在导管表面上的接触角αb。所形成的接触角越大,与壁的接触就越少,因此会更少发生堵塞。实现该结果的第二种途径是选择涂覆的导管表面-添加的表面活性剂组合,该组合减少在连续流体中盐水在导管表面上的表面能β。如果实现了该方法,则与具有表面能β的未经处理的导管相比,与导管表面接触的盐水更可能在形成水合物沉积物之前即被去除。
本发明的实施方案不是具有减小的接触力,而是替代地争取减小水合物沉积物在壁上的粘合作用。实现该目标的一种方法是选择壁涂层-化学品(抗聚结化学品)组合,该组合减小连续流体中沉淀的固体在导管上的粘合力γ。粘合力越低,沉积物就越不可能附着在导管表面。
因此,本公开的实施方案涉及一种组合的系统,该系统使用具有增大接触角的化学添加剂的涂覆导管,或使用了降低粘合作用的化学添加剂的涂覆导管,或者它们的组合。
根据本公开,涂层可包括非金属涂层(如硅涂层、陶瓷涂层)和由硅氧烷、氟硅氧烷和含氟聚合物制备的最小粘合聚合物涂层,这是因为它们的表面能低,这会减小极性和与周围水分子的氢键相互作用,因此减小粘合能量。在本公开的另一个实施方案中,涂层可以包括金属涂层。
根据本公开,涂层可以包括可使用这里公开的那些技术施用的任何涂层。例如,在本公开的一个实施方案中,可通过使生产和/或输送装置的内表面亲水化并随后接枝低表面能聚合物链来施加涂层,由此使接触角较高。在本公开的另一个实施方案中,可通过施用交联聚合材料如硅氧烷、氟硅氧烷和含氟聚合物来形成涂层。在本公开的又一个实施方案中,可通过自组装来形成涂层。
根据本公开,涂层可以包括可以是“基本均匀的涂层”的任何涂层。这里使用的“基本均匀的涂层”是指可以被所需厚度的涂层完全覆盖的生产和/或输送装置的内表面。例如,在一个实施方案中,根据涂层类型和施用方法,涂层厚度可以是至少约0.5μm。在另一个实施方案中,根据涂层类型和施用方法,涂层厚度可以是约1μm或更多。在又一个实施方案中,根据涂层类型和施用方法,涂层厚度可以是约10μm或更多。
如上所述,可通过将表面涂层与向产出的物流中添加表面活性剂组合起来以实现减少沉淀的固体或沉淀固体的材料与生产和/或输送装置内表面的接触。这里使用的表面活性剂是指通常对于在可渗透材料如地下储层内置换油有效和对于改变基体岩石润湿性有效的表面活性剂。可注入地下地层或流动管线的表面活性剂的例子可包括:水性阴离子表面活性剂,如芳香醚聚磺酸酯和烷氧基醇硫酸酯的混合物;有机磺酸酯表面活性剂,如可以以商品名如“Bryton Chemical F467”、“Witco Chemical TRS-10”和“American Cynamid Aerosol OT”广泛商购的那些;非离子表面活性剂,如聚乙氧基化烷基酚、聚乙氧基化脂肪醇、羧酸酯、羧酸酰胺和聚氧乙烯脂肪酸酰胺;阴离子和非离子表面活性剂的组合;和其它许多。
根据本公开,可通过将表面活性剂溶液注入注入井和/或生产井来添加用于处理的表面活性剂。
根据本公开,可添加抗聚集剂以大体上阻止较小的水合物聚集成较大的水合物晶体,由此较小的水合物可泵送通过生产和/或输送装置内表面。可涂覆到生产和/或输送装置内表面的抗聚集剂分子的例子可包括溴化三丁基十六烷基、溴化三丁基十六烷基铵和其它烷基化的铵、或锍化合物、两性离子化合物如R(CH3)2N+-(CH2)4-SO3 31。
有利地,本公开的实施方案可以最小化或甚至消除可形成于生产和/或输送系统内表面的水合物形成。此外,本公开的实施方案还可以使增加用来最小化或消除气体水合物形成的化学品剂量的需要减少。
示例性实施方案:
在一个实施方案中,公开了一种用于生产和输送原油的系统,该系统包括:用于生产原油的井;用于处理原油的处理设施;和穿过井和处理设施之间至少一部分距离的管线,其中至少一部分管线在温度低于20℃的大气中穿行,其中管线包括在管线内表面上的涂层,和其中原油包含表面活性剂添加剂。在一些实施方案中,大气温度低于15℃。在一些实施方案中,大气温度低于10℃。在一些实施方案中,涂层包含聚合物。在一些实施方案中,涂层包含硅氧烷和/或PTFE(聚四氟乙烯)。在一些实施方案中,表面活性剂包括阴离子表面活性剂。
在一个实施方案中,公开了一种生产和输送原油的方法,该方法包括:从井中提取原油;将原油置于管线中以输送原油离井;用非金属表面涂覆管线的至少一部分内表面;在将原油置于管线中之前向原油中添加表面活性剂;其中至少一部分管线在环境温度低于20℃的大气中穿行。在一些实施方案中,大气温度低于15℃。在一些实施方案中,大气温度低于10℃。在一些实施方案中,涂层包含选自特氟隆和硅氧烷的材料。在一些实施方案中,管线包括第一材料,其中涂层包含第二材料,和其中第二材料的电导率比第一材料低。在一些实施方案中,具有涂层的管线中原油的粘合作用比没有涂层的管线中原油的粘合作用低至少25%。在一些实施方案中,具有涂层和表面活性剂的管线中原油的接触角比没有涂层和没有表面活性剂的管线中原油的接触角大至少25%。
在一个实施方案中,公开了一种不粘装置,该装置包括:包含第一材料的液体储存或运输制品;在制品的内表面上包含第二材料的涂层;制品内包含表面活性剂添加剂的液体。在一些实施方案中,第一材料选自钢、不锈钢、铸铁、铜和塑料。在一些实施方案中,第二材料包括非金属聚合漆或涂料。在一些实施方案中,制品包括管。在一些实施方案中,制品包括槽。在一些实施方案中,表面活性剂添加剂包含亲水头和疏水尾。
本发明已就有限数量的实施方案进行了描述,但得益于本公开的本领域技术人员将会理解,可以设计不背离这里公开的本发明范围的其它实施方案。因此,本发明的范围应当只由所附的权利要求书限定。
Claims (19)
1.一种用于生产和输送原油的系统,该系统包括:
用于生产原油的井;
用于处理原油的处理设施;和
越过所述井和所述处理设施之间至少一部分距离的管线,其中至少一部分所述管线在温度低于20℃的大气中穿行,其中所述管线包括所述管线内表面上的涂层,和其中原油包含表面活性剂添加剂。
2.权利要求1的系统,其中大气温度低于15℃。
3.权利要求1-2任一项的系统,其中大气温度低于10℃。
4.权利要求1-3任一项的系统,其中所述涂层包含聚合物。
5.权利要求1-4任一项的系统,其中所述涂层包含硅氧烷和/或PTFE(聚四氟乙烯)。
6.权利要求1-5任一项的系统,其中所述表面活性剂包括阴离子表面活性剂。
7.一种生产和输送原油的方法,该方法包括:
从井中提取原油;
将原油置于管线中以输送原油离井;
用非金属表面涂覆所述管线的至少一部分内表面;
在将原油置于所述管线中之前向原油中添加表面活性剂;
其中至少一部分管线在环境温度低于20℃的大气中穿行。
8.权利要求7的方法,其中大气温度低于15℃。
9.权利要求7-8任一项的方法,其中大气温度低于10℃。
10.权利要求7-9任一项的方法,其中所述涂层包含选自特氟隆和硅氧烷的材料。
11.权利要求7-10任一项的方法,其中所述管线包含第一材料,其中所述涂层包含第二材料,和其中第二材料的电导率比第一材料低。
12.权利要求7-11任一项的方法,其中具有涂层的管线中原油的粘合作用比没有涂层的管线中原油的粘合作用低至少25%。
13.权利要求7-12任一项的方法,其中具有涂层和表面活性剂的管线中原油的接触角比没有涂层和没有表面活性剂的管线中原油的接触角大至少25%。
14.一种不粘装置,该装置包括:
包含第一材料的液体储存或运输制品;
在所述制品的内表面上包含第二材料的涂层;
所述制品内包含表面活性剂添加剂的液体。
15.权利要求14的装置,其中第一材料选自钢、不锈钢、铸铁、铜和塑料。
16.权利要求14-15任一项的装置,其中第二材料包括非金属聚合漆或涂料。
17.权利要求14-16任一项的装置,其中所述制品包括管。
18.权利要求14-16任一项的装置,其中所述制品包括槽。
19.权利要求14-18任一项的装置,其中所述表面活性剂添加剂包含亲水头和疏水尾。
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NO20130720A1 (no) | 2013-05-23 |
BR112013009822A2 (pt) | 2016-07-26 |
WO2012058144A2 (en) | 2012-05-03 |
CN103189594B (zh) | 2018-11-16 |
GB2498472A (en) | 2013-07-17 |
WO2012058144A3 (en) | 2012-08-16 |
AU2011320622A1 (en) | 2013-05-02 |
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