CN101263211A - 作为井漏控制剂材料的水溶胀性聚合物 - Google Patents
作为井漏控制剂材料的水溶胀性聚合物 Download PDFInfo
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Abstract
本发明公开了一种包含反相乳液聚合物的封堵剂组合物,以及使用这种组合物来维护井身的方法。在一个实施方案中,公开了一种维护穿透地层的井身的方法。所述方法包括将包含反相乳液聚合物的封堵剂组合物置入井身中,以减少在井身中置入流体期间的地层中的流体损失。
Description
技术领域
本发明涉及封堵剂组合物领域,更具体而言,涉及包含反相乳液聚合物的封堵剂组合物,以及使用这种组合物来维护井身的方法。
背景技术
残留在地层或地下区域中的天然资源如天然气、石油和水经常是通过向地层下钻井、同时循环井身中的钻井液来回收的。在终止钻井液循环后,一列管子例如套管在井身中运转。然后,通常使钻井液向下循环穿过所述管子的内部和向上穿过位于管子外部与井壁之间的环带。接下来,通常进行初次注水泥,由此将水泥浆置入环带中,并使其凝固成为硬质体(例如护套),因此使管子列与井壁相连并封堵环带。随后也可以进行次级注水泥操作。次级注水泥操作的一个实例是挤压式注水泥,借此用水泥浆堵住和封掉水泥护套和/或套管中的不期望的流动通道。尽管在初次注水泥和次级注水泥操作中水泥浆是一种类型的封堵剂组合物,但是也可以使用其它不含水泥的封堵剂组合物。
例如,称为胶黏物质挤压(gunk squeeze)的方法涉及将胶黏物质堵塞物置入井漏区中以减少液漏。胶黏物质挤压涉及混合粘土如膨润土与柴油,并将混合物置入井身中,其中粘土与水接触并形成封堵剂组合物。其缺点包括井下输送问题,例如在井身中混合水与粘土。其它缺点包括胶黏物质挤压方法通常不足以用于空穴损失(vugular losses),因为所述组合物具有缓慢的反应化学性。其它方法包括使用颗粒来封堵井漏区。该方法的缺点包括操作成本(例如增加的泵送成本)。其它缺点包括对较大井漏区的不充分的堵塞。
因此,需要有一种改进的封堵剂组合物。其它需要包括足以堵塞井漏区且并容易在井下输送的封堵剂组合物。
发明内容
现有技术中的这些和其它需求提出了一个实施方案中的用于维护穿透地层的井身的方法。该方法包括将包含反相乳液聚合物的封堵剂组合物置入井身中,以降低在所述井身中置入流体期间的地层中的流体损失。
在另一个实施方案中,现有技术中的这些和其它需求提出了一种包含反相乳液聚合物的封堵剂组合物。该反相乳液聚合物包含粒度为约0.01微米-约30微米的颗粒。
在一个实施方案中,现有技术中的这些和其它需求提出了一种包含油分散的聚合物的封堵剂组合物,其中所述聚合物包含平均粒度为约0.01微米-约30微米的颗粒。
包含反相悬浮乳液聚合物的封堵剂组合物克服了现有技术中的问题。例如,所以封堵剂组合物可以容易地在井下输送。另外,所述封堵剂组合物可以减少在大的透过性区域如空穴断层中的流体损失。
前面已相当宽泛地描述了本发明的特征和技术优点,所以以下本发明详细的说明书可以得到更好的理解。本发明另外的特征和优点将在形成本发明权利要求主题的下文中进行描述。本领域技术人员应当理解,公开的概念和具体实施方式可以方便地作为改进或设计其它用于实现本发明的相同目的的其它构造的基础。本领域技术人员还应当认识到,这种等价的构造不会背离在所附权利要求中阐述的本发明的精神和保护范围。
附图说明
为详细地描述本发明的优选实施方案,现可以参考以下的附图,其中:
图1所示为FLEXPLUG井漏材料的挤出流变仪试验的轮廓曲线;
图2所示为反相乳液聚合物和NaCl的挤出流变仪试验的轮廓曲线;
图3所示为反相乳液聚合物和海水的挤出流变仪试验的轮廓曲线;
图4所示为计算的反相乳液聚合物和NaCl的混合物的Bagley系数;和
图5所示为计算的反相乳液聚合物和海水的混合物的Bagley系数。
具体实施方式
在一个实施方案中,封堵剂组合物包含反相乳液聚合物。所述封堵剂组合物是可以在流体(例如钻井液)损失的井身区中增粘的混合物。例如,所述封堵剂组合物可以在井漏区增粘,并因此而恢复循环。增粘过的混合物可以凝固成为柔韧、有弹性且刚性的材料,其可以防止在重新开始循环时的进一步流体损失。反相乳液聚合物对液体可以具有相似的特性,因此可以适合于在井身中的井下输送。
所述封堵剂组合物用于穿透地层的井身中。应当理解,“地层”包括暴露的地表之下的区域,以及由水覆盖的区域,例如由海洋或淡水覆盖的地表之下的区域。封堵剂组合物可以用于任何用途。例如,所述封堵剂组合物可以用于维护井身。在无限制下,维护井身包括将封堵剂组合物布置在井身中,以便将所述地层与部分井身分开;支撑井身中的导管;堵塞导管中的空隙或裂缝;堵塞布置在井身环带的水泥护套中的空隙或裂缝;堵塞水泥护套和导管之间的开口;防止含水或非水钻井液损失进入井漏区如空隙、空穴区或断层中;被用作注水泥操作中的水泥浆之前的流体;用于封堵井身和膨胀性管子或管子列之间的环带;以及它们的组合。
反相乳液聚合物包括油包水型乳液,水溶胀性聚合物分散在所述乳液中。该乳液包括油的连续相和水的分散相。所述油可以是与水不相混溶并适合于在钻井中使用的任何油。在无限制下,合适的油的实例包括石油润滑油、天然油、合成衍生油、矿物油、硅油、或它们的组合。在一些实施方案中,所述油可以是α烯烃、内烯烃、酯、碳酸的二酯、石蜡、煤油、柴油、矿物油、硅油、或它们的组合。水可以是任何适于形成分散相并用于钻井中的水。在无限制下,合适的水的实例包括去离子水、市政处理水、淡水、海水、天然存在的卤水、含有单价和/或多价阳离子的氯化物基、溴化物基或甲酸盐基的卤水。适宜的氯化物基的卤水的实例无限制性地包含氯化钠和氯化钙。进一步无限制下,适宜的溴化物基卤水的实例包含溴化钠、溴化钙和溴化锌。另外,甲酸盐基的卤水的实例无限制性地包括甲酸钠、甲酸钾和甲酸铯。
所述反相乳液聚合物可以包含适于分散水溶胀性聚合物且用于置入井身中的任何合适量的油和水来形成反相乳液。在一个实施方案中,所述反相乳液包含以反相乳液聚合物的总重量计约10-约80重量%的油,或约30-约50重量%的油。另外,所述反相乳液包含以反相乳液聚合物的总重量计约0-约70重量%的水,或者约30-约70重量%的水。
在一些实施方案中,所述反相乳液聚合物包含乳化剂。所述乳化剂可以是适于保持油和水在悬浮体中的任何乳化剂。在一个实施方案中,所述反相乳液聚合物包含水溶性和油溶性的乳化剂(例如乳化试剂或表面活性剂)来稳定反相乳液聚合物。在无限制下,适宜的乳化剂的实例包括多价金属皂、磷酸酯、脂肪酸、脂肪酸皂、烷基苯磺酸盐、或它们的组合。所述反相乳液聚合物可以含有任何量的适于保持油和水在悬浮体中的乳化剂。在一个实施方案中,所述反相乳液聚合物包含以反相乳液聚合物的总重量计约1-约10重量%的乳化剂,或者约1-约20重量%的乳化剂。
所述反相乳液聚合物可以含有任何需要量的有效用于目的的井身维护的水溶胀性聚合物。在一个实施方案中,反相乳液聚合物包含以反相乳液聚合物总重量计约30-约50重量%的水溶胀性聚合物,或者约30-约70重量%的水溶胀性聚合物,或者约5-约100重量%的水溶胀性聚合物。水溶胀性聚合物是指任何可以吸收水并膨胀的聚合物,即在吸收水时增加其尺寸的聚合物。在一个实施方案中,由于水溶胀性聚合物的溶胀,反相乳液聚合物形成为糊状物质体,其可有效用于堵塞流体的流动通道。在某些实施方案中,所述糊状物质体对于维护井身所用的流体具有相对较低的透过率,如对于钻井液、压裂液、水泥、酸化液、注入物等等,由此产生对这种流体的障碍。糊状物质体是指分散在液体(反相乳液)中、柔软的粘性固态物质体(例如溶胀的水溶胀性聚合物)。在备选的实施方案中,反相乳液在与泥浆混合时形成基本上硬的粘稠物质体。在无限制下,适宜的水溶胀性聚合物的实例包括合成聚合物、超吸收体、天然聚合物、或它们的组合。适宜的合成聚合物的实例包括交联的聚丙烯酰胺、聚丙烯酸盐、或它们的组合。
在一个实施方案中,水溶胀性聚合物包括超吸收体。超吸收体通常用于吸收性产品如园艺产品、擦抹或溅出控制剂、电线和电缆阻水剂、冰航运包装物、尿布、训练裤、女用卫生产品、以及多种工业用途。超吸收体是可膨胀的交联聚合物,其可以吸收并储存很多倍于其自身重量的含水液体。超吸收体保留其吸收的液体,即使在压力下也通常不会释放出已吸收的液体。超吸收体的实例包括具有三维网状分子结构的基于丙烯酸钠的聚合物。不受理论的限制,所述聚合物链通过几十万至百万个相同的丙烯酸单体的反应/连接而形成,而丙烯酸单体已基本上用氢氧化钠(苛性钠)中和。另外,不受理论的限制,交联化学品将聚合物链连接在一起而形成三维网络,这使得所述超吸收体吸收水或水基溶液至分子网络的空间中,由此形成锁定液体的凝胶。适宜的超吸收体的其它实例包括但不限于交联的聚丙烯酰胺;交联的聚丙烯酸盐;交联的水解的聚丙烯腈;羧烷基淀粉的盐如羧甲基淀粉的盐;羧烷基纤维素的盐如羧甲基纤维素的盐;任何交联的羧烷基多糖的盐;丙烯酰胺和丙烯酸盐单体的交联的共聚物;丙烯腈和丙烯酸盐单体接枝的淀粉、两种或多种烯丙基磺酸盐、2-丙烯酰胺基-2-甲基-1-丙烷磺酸、3-烯丙基氧基-2-羟基-1-丙烷磺酸盐、丙烯酰胺和丙烯酸单体、或它们的组合的交联的聚合物。在一个实施方案中,所述水溶胀聚合物包含交联的聚丙烯酰胺和/和聚丙烯酸盐。在一个实施方案中,所述超吸收体不仅吸收很多倍其重量的水,而且还由于吸收了很多倍干物质体积的水而增加其体积。在一个实施方案中,所述超吸收体增加约10-约800倍的其原始重量。
在一个实施方案中,所述水溶胀性聚合物在其吸水之前(即以其固体形式)的粒度(即粒径)为约0.01-约30微米,或者约1-约3微米。水溶胀性聚合物的膨胀时间可以是约5秒钟-约5小时,或者约1秒钟-约48小时。
不受理论的限制,微米尺寸的水溶胀性聚合物使得反相乳液聚合物表现为足以在井身中进行井下输送的液体(例如,具有与液体相似的流动特性)。而且,不受理论的限制,微米的尺寸也使得脱水形式的反相乳液聚合物(例如油分散的聚合物)表现得像液体。该反相乳液聚合物的密度为约1.1g/ml至约1.7g/ml,或者约1.0g/ml至约2.5g/ml。另外,该反相乳液聚合物的吸收容量为基于其自身重量的约10至约100倍,或者约1至约1000倍于其自身重量。
反相乳液聚合物的适宜的商业实例是可商购自Hychem,Inc.的AE 200聚合物。AE 200聚合物含有约30重量%的水溶胀性聚合物、约30重量%的矿物油、约30重量%的水和约10重量%的乳化剂。所述水溶胀性聚合物含约30重量%的聚丙烯酸和约70重量%的聚丙烯酰胺的交联聚合物。水溶胀性聚合物的粒度约1-约3微米。水溶胀性聚合物的pH为约5.0至约8.0,优选约6.0至约7.5。该反相乳液聚合物的密度为1.0g/ml-约2.5g/ml,优选约1.1g/ml-约1.7g/ml。
在一个实施方案中,将经脱水的反相乳液聚合物置于井身中。该反相乳液聚合物被恰当地脱水以除去至少一部分水和提供油分散的聚合物。在一个实施方案中,该反相乳液聚合物被脱水至形成油分散的聚合物,其包含约0-约10重量%的水,或者约0-约5重量%的水,或者约3-约5重量%的水。不受理论的限制,对反相乳液聚合物进行脱水,因为脱水提供了聚合物中更高百分比的水溶胀性聚合物。而且,不受理论的限制,对反相乳液聚合物进行脱水减少了根本改变原油基钻井液性质的可能性。反相乳液聚合物可以通过任何适宜的方法进行脱水以提供油分散的聚合物。在一个实施方案中,所述油分散的聚合物包含以油分散的聚合物总重量计约45-约50重量%的油,或约30-约70重量%的油。另外,所述油分散的聚合物包含以油分散的聚合物总重量计约45-约50重量%的水溶胀性聚合物,或者约30-约70重量%的水溶胀性聚合物。
该油分散的聚合物的密度为约1.2g/ml至约1.7g/ml,或者约1.0g/ml至约2.5g/ml。另外,该油分散的聚合物的吸收容量为其自身重量的约10至约200倍,或者其自身重量的约1至约1000倍。
在无限制下,脱水的反相乳液聚合物(例如油分散的聚合物)的商业实例是可商购自Hychem,Inc.的AD 200聚合物。AD 200聚合物是含有约1-3重量%的水和约50重量%的活性组分的交联聚合物,其包括以聚合物总重量计量为约30重量%的聚丙烯酸盐和约70重量%的聚丙烯酰胺的水溶胀性聚合物。AD200聚合物的密度为1.25g/ml(±10%)。另外,AD 200聚合的吸收容量(在蒸馏水中)为20g蒸馏水/1gAD 200聚合物,并进一步具有5g 3%的NaCl溶液/1gAD200聚合物。AD 200聚合物在150℃、16小时下的非挥发性残余物的百分数为63%(±10%)。
在一些实施方案中,封堵剂组合物包括可以适合于改进或改变其性质的添加剂。在无限制下,适宜的添加剂的实例包括颗粒材料、增粘剂、填充物、或它们的组合。填充物可以用来增加封堵剂材料的密度。在一个实施方案中,将足够量的填充物与封堵剂组合物混合,以增加向下穿过井身的组合物的密度。不受理论的限制,增加的密度可以增加封堵剂向下穿过井身中流体的速度。进而,不受理论的限制,增加的密度减少了井身爆裂的可能性。在无限制下,合适填充料的实例包括重晶石、硅石粉状物、沸石、铅颗粒、沙子、纤维、聚合物材料、或它们的组合。所述密度可以增加至任何需要的密度。在一个实施方案中,所述密度增加至密度为约10ppg至约20ppg。
在一个实施方案中,反相乳液聚合物被加入井身中,以防止含水或非水钻井液在钻探中进入井漏区如空隙、空穴区及天然或诱导断层中时的漏失。在井身处理期间,对于给定的处理,需要时可将各种组分逐次泵送工作管柱之下和/或同时在环带之下。在一个实施方案中,所述反相乳液聚合物被泵入井身中以维护井身。在所述反相乳液聚合物被泵入井身中之前,可以将隔离液泵入井身中。在一些实施方案中,所述隔离液适用于除水(即从管中)。例如所述隔离液可以含有润湿剂,例如LE SUPERMUL乳化剂。LE SUPERMUL乳化剂可商购自Halliburton Energy Services,Inc.。然后所述反相乳液聚合物被泵入井身中。在一些实施方案中,在将反相乳液聚合物泵入井身中之前将填充物如重晶石加入反相乳液聚合物中。在这种泵送之后,额外的隔离液可以被泵入井身中。所述封堵剂组合物得以形成,并在井漏区中提供相对粘稠的物质体。然后可以在合适的压力下将钻井液泵入井身中,以挤压封堵剂组合物进入井漏区中。所述封堵剂组合物也可以在井漏区中形成非流动的、完整的(intact)物质体。该物质体堵塞所述区域,并抑制随后泵送的钻井液的漏失,这使得能够进行进一步的钻探。在其中钻井液为非水性的实施方案中,处理组合物可以在反相乳液聚合物和额外的隔离剂泵入后被泵入井身中。在一个实施方案中,可以泵入足够量的处理组合物,以减少与反相乳液聚合物接触的钻井液中的钙和镁的量。在一个实施方案中,处理组合物包括苏打灰、NaHCO3、单价盐、二价盐或它们的组合。在无限制下,这种盐的实例包括Na+、K+、Ca2+、和Ma2+。不受理论的限制,减少钙和镁以防止反相乳液聚合物或油分散聚合物中的盐中毒,其可以防止需要的固体糊的形成并堵塞地层中的空隙。在这样的实施方案中,随后可以将隔离液泵入井身中,接着是钻井液。应当理解,非水钻井液可以包括柴油、矿物油、内烯烃、直链α烯烃、酯、或它们的组合。在备选的实施方案中,在反相乳液聚合物泵入井身中之前和/或之后,没有将隔离液泵入井身中。在一些实施方案中,反相乳液聚合物被脱水以形成油分散的聚合物,由此形成了封堵剂组合物。
在一个实施方案中,封堵剂组合物与水基泥浆被置入井身中。置入的方法包括将处理过且活性的钻探泥浆泵入井身中。可以将任何适宜量的钻探泥浆泵入井身中。例如,可以将包含约15-约20桶量的钻探泥浆泵入井身中。在其中可溶性钙存在于泥浆中的情况下,所述泥浆可以用处理组合物处理,以处理出至少部分钙。在一个实施方案中,对泥浆的处理在钙的存在量为大于200mg/l时进行。任何适宜量的处理组合物都可以使用。隔离剂(例如LE SUPERMUL乳化剂)在泥浆之后被泵入井身中。任何适宜量的隔离剂都可以泵入井身中。例如,可以将包含约5-约10桶量的隔离剂泵入井身中,或者可以将约6-约7桶的隔离剂泵入井身中。在隔离剂之后将反相乳液聚合物泵入井身中。可以将包含量为约15-约20桶、或约16-约17桶的反相乳液聚合物可以被泵入井身中。反相乳液聚合物可以用填充物增重。然后可以将一定量的隔离剂泵入井身中。可以包括将约5-约10桶、或者将约6-约7桶的隔离剂量的隔离剂泵入井身中。然后将适宜量的泥浆泵入井身中。在一个实施方案中,泥浆的量为20桶或更少。在泥浆被泵入井身中之后,保持轻微的挤压压力一段适宜的时间,以使封堵剂组合物在井漏区域中形成非流动性的完整的物质体。可以保持任何适宜的压力。例如,所述压力可以是约175-约225psi。应当理解的是,在一些实施方案中,将油分散的聚合物与水基泥浆置入井身中,而不是反相乳液聚合物。
在另外的实施方案中,将封堵剂组合物与非水性泥浆置入井身中。置入的方法包括将隔离剂泵入井身中。任何适宜定量的隔离剂都可以使用。例如,约1桶的隔离剂可以泵入井身中。隔离剂之后将反相乳液聚合物泵入井身中。可以将包含量为约10-约20桶,或者约16-约17桶、或者约11桶的反相乳液聚合物泵入井身中。反相乳液聚合物可以用填充物增重。在所述反相乳液聚合物之后,将一定量的隔离剂泵入井身中。在一个实施方案中,包含量为约1-约5桶、或者3-约5桶、或者约2桶的隔离剂被泵入井身中。处理组合物(例如苏打灰)在隔离剂之后被泵入井身中。例如,苏打灰可以与隔离剂、钻探泥浆或AD 200聚合物混合,并被泵入井身中。可以泵入任何适宜量的处理组合物,以防止反相乳液聚合物的盐中毒。在一些实施方案中,约30-约70桶、或者约35-约40桶、或者约50-约70桶的处理组合物被泵入井身中。在处理组合物之后一定量的隔离液被泵入井身中。在一个实施方案中,将量为约1-约5桶、或者约3-约5桶、或者约3.5桶的隔离剂泵入井身中。将适宜量的泥浆在隔离剂之后泵入井身中。在一个实施方案中,泥浆的量为20桶或更少。在泥浆被泵入井身中之后,保持轻微的挤压压力一段适宜的时间,以使封堵剂组合物在井漏区中形成非流动性的完整的物质体。可以保持任何适宜的压力。例如,所述压力可以是约175-约225psi。应当理解的是,在一些实施方案中,将油分散的聚合物与非水泥浆置入井身中,而不是反相乳液聚合物。
在一个实施方案中,包括反相乳液聚合物的封堵剂组合物可以用于完井操作中,例如初次和次级注水泥操作。在一个实施方案中,隔离液被泵送穿过钻探管。然后反相乳液聚合物被泵送穿过钻探管并形成封堵剂组合物。额外量的隔离液此时可以被泵送穿过钻探管。在备选的实施方案中,没有将隔离液在反相乳液聚合物之前和/或之后泵入钻探管中。在初次注水泥中,这种封堵剂组合物可以被置入井身的环带中,并使其凝固,以便其将地层与井身的不同部分隔离。由此封堵剂组合物形成防止该地层中的流体迁移进入其它地层中的障碍。在环带内,封堵剂组合物也起到支撑导管、例如井身中的套管的作用。在一个实施方案中,布置封堵剂组合物的井身属于多重侧向的井身构造。应当理解,多重侧向井身构造包括至少两个通过一个或多个辅助井身连接的主井身。在次级注水泥中(通常称为挤压式注水泥中),封堵剂组合物可以策略性地布置在井身中,以堵塞导管中的空隙或裂缝、堵塞残留在环带中的硬化的封堵剂(如水泥护套)中的空隙或裂缝、堵塞在硬化的封堵剂和导管之间称为微环带的小开口等等。在一些实施方案中,反相乳液聚合物被脱水至形成油分散的聚合物,由此封堵剂组合物从其中形成。可以采纳的用于在井身中使用封堵剂组合物的各种步骤描述在US 5,346,012和5,588,488中,其全部内容通过参考而结合在此。
为了进一步说明本发明的各示范性实施方案中,提供了以下实施例:
实施例1
在该实施例1中,进行了3组试验(试验1-9),对常规井漏材料FLEXPLUG井漏材料(试验1)与反相乳液聚合物AE 200聚合物(试验2-9)进行对比。可商购自Halliburton Energy Services,Inc.的FLEXPLUG井漏材料使用颗粒来防止流体损失。将不同比例的AE 200聚合物与去离子水、1%NaCl溶液或海水混合。使用挤出流变仪来测试每个混合物。
挤出流变仪的主要部件包括芯部,芯部具有开口宽度为1mm、2mm或3mm的狭缝。流变仪为2、4或6英寸长。对于每个试验,用材料(AE 200聚合物或FLEXPLUG材料)充填流变仪以供测试。施加压力以将材料推出不同尺寸芯部。观察到在相同的条件下,需要不同的力来将不同的材料推出相同的芯部。以磅计测量并记录该力。结果在下表I中列出,其中样品标记为以英寸计的流变仪的长度乘以以毫米计的流变仪的宽度(例如,2英寸长乘以1毫米宽=2INLX 1MMW)。
表I
样品标记 | FLEXPLUG材料 | AE 200聚合物∶去离子水(1∶9) | AE 200聚合物∶1%NaCl(1∶6) | AE 200聚合物∶1%NaCl(1∶3) | AE 200聚合物∶海水(1∶3) |
2INLX1MMW | N/A | N/A | N/A | Ave:209SD:2.38COV:1.1% | N/A |
4INLX1MMW | N/A | Ave:134.7SD:5.67COV:4.2% | Ave:136.3SD:5.7COV:4.2% | Ave:283SD:1.15COV:0.5% | Ave:248SD:1.16COV:0.5% |
6INLX1MMW | N/A | N/A | N/A | Ave:517SD:6.56COV:1.3% | N/A |
2INLX2MMW | N/A | Ave:46.1SD:2.61COV:5.7% | Ave:41.3SD:3.27COV:7.9% | Ave:90.6SD:1.88COV:2.1% | Ave:82.0SD:1.76COV:2.1% |
4INLX2MMW | N/A | N/A | N/A | Ave:166.8SD:2.15COV:1.3% | N/A |
6INLX2MMW | N/A | N/A | N/A | Ave:231SD:4.85COV:2.1% | N/A |
2INLX3MMW | N/A | N/A | N/A | Ave:52.6SD:3.01COV:5.7% | N/A |
4INLX3MMW | N/A | N/A | N/A | Ave:80.9SD:1.87COV:2.3% | N/A |
6INLX3MMW | Ave:526SD:69COV:13.1% | Ave:57.2SD:8.9COV:15.6% | Ave:62.1SD:1.19COV:1.9% | Ave:114.4SD:8.34COV:7.3% | Ave:108.8SD:7.82COV:7.2% |
在表I中,列出的流变仪读数以磅计。所列数值是对每个试验记录结果的平均。“SD”表示标准偏差,“COV”表示方差系数,并通过SD/XAve计算。
从表I中可以看出,AE 200反相乳液聚合物的标准偏差和COV比FLEXPLUG材料的要好得多。在各个实施方案中,反相乳液聚合物的流变仪读数SD为小于9、8、7、6、5、4、3或2,COV为小于8%、7%、6%、5%、4%、3%或2%。
图1所示为对于其初始压力的FLEXPLUG材料的轮廓曲线,其是推动FLEXPLUG材料进入空穴、多孔的地层中时所需的初始压力。从图1可以看出,FLEXPLUG材料表现出压力降。如图2和3中所示,对于AE 200聚合物样品没有这样的压力降。图1-3显示的是在x轴上以英寸计的位置,和在y轴上以磅-力计的载荷。
实施例2
将实施例1的挤出流变仪数据用于实施例2中推导每个试验的Bagley因子。为了推导Bagley因子,狭缝的宽度保持相同。通过在相同条件下变化芯部的长度而得到了不同的力,如图4中所示。
Bagley因子定义如下:Bagley因子=F0/FL2。F0定义为当X=0时的力。FL2定义为在此具体情况下使用4英寸芯部时得到的力。通常,Bagley因子在0和80%之间。对于FLEXPLUG材料,Bagley系数通常在25和80%之间,更典型为在35和55%之间。Bagley因子越小,所述材料就越容易被压力或其它材料替换。
图4和5举例说明了对于不同芯部的AE 200聚合物∶1%NaCl(1∶3)而言所计算的Bagley因子。从图4和5可以看出,所述Bagley因子比例如FLEXPLUG材料的更低。通过具有这种较低的Bagley因子,AE 200聚合物和1%NaCl的混合物可以比FLEXPLUG材料更容易被推入裂缝层中。
实施例3
对AE 200聚合物用水基泥浆(磺化木质素泥浆)进行测试。表II显示所述泥浆的配制。AQUAGEL增粘剂是一种粘度和凝胶化试剂,可商购自HalliburtonEnergy Services,Inc.。QUIK-THIN稀释剂是一种铬铁合金木质素磺酸盐,可商购自Halliburton Energy Services,Inc.。CARBONOX过滤控制剂是褐煤材料,可商购自Halliburton Energy Services,Inc.。REV-DUST添加剂是一种钙蒙脱粘土,可商购自Milwhite,Inc.。
表II磺化木质素泥浆的配制
样品,(lb/ga) | 14.0 |
淡水,bbl | 0.76 |
AQUAGEL增粘剂,lb/bbl | 20 |
QUIK-THIN稀释剂,lb/bbl | 6 |
NaOH,lb/bbl | 3(PH~11-11.5) |
CARBONOX试剂,lb/bbl | 4 |
REV-DUST添加剂,lb/bbl | 30.0 |
重晶石,lb/bbl | 271.6 |
在150°F的烘箱中热辊16小时后,对泥浆中不同浓度的AE 200聚合物进行测试,结果见表III和IV中所示。所述浓度是通过添加1.0mL的AE 200聚合物和不同量的磺化木质素泥浆(例如,试验如1X、2X或50X所要求的)至烧杯中而测试的。将混合物充分混合。记录下混合物硬化所需的时间和混合物的条件。
表III AE 200聚合物与磺化木质素泥浆的试验结果
样品 | 1∶1(v/v) | 1∶2 | 1∶10 | 1∶20 | 1∶30 | 1∶50 |
AE 200聚合物与磺化木质素泥浆(含淡水) | 在1分钟内变稠。形成疏松固体 | 在1分钟内变稠。形成粘土状固体 | 在1分钟内变稠。形成粘土状固体 | 在1分钟内变稠。形成粘土状固体。稍微湿于1∶10 | 轻微的浆体状,更像水泥状 | 浆体和水状 |
表IV AE 200聚合物与磺化木质素泥浆的试验结果
样品 | 1∶5(v/v) | 1∶10 | 1∶15 | 1∶20 |
AE 200聚合物与磺化木质素泥浆(含海水) | 在1分钟内变稠。形成橡胶状粘土 | 在1分钟内变稠。形成粘土状固体 | 首先是浆体,然后在1小时后硬化 | 首先是浆体,然后在1.5小时后硬化 |
从表III和IV可以看出,即使稀释因子为1∶30(AE 200聚合物∶泥浆),由两种组分的混合物形成的固体仍然是水泥状的浆体糊。还可以从这些表中进一步看出,当使用海水形式的磺化木质素泥浆时,稀释因子下降为10而不是20。海水中的阳离子(例如Na+、K+、Ca2+、Ma2+等)可以通过盐中毒而影响AE 200聚合物的性能。在此情况下,观察到盐中毒效果对于Ca2+比Na+更严重。为了处理出Ca2+离子,将0.2lb/bbl的苏打灰(Na2CO3)加入具有优异结果的泥浆中。观察到稀释因子又反而增加至20,而固体的质地则又更像淡水的泥浆。
实施例4
在实施例4中,考察盐度、pH和密度对AE 200聚合物性能的影响。配制不同密度、pH和密度的泥浆,如表V中所示。BARAZAN D Plus悬浮剂/增粘剂是可商购自Halliburton Energy Services,Inc.的分散增强的黄原胶。FILTER-CHECK过滤控制剂是可商购自Halliburton Energy Services,Inc.的改性淀粉。CLAY SYNC泥浆稳定剂是可商购自Halliburton Energy Services,Inc.的用于水基泥浆的粘土抑制剂。CLAY GRABBER絮凝剂是用于水基钻井液的聚合物添加剂,可商购自Halliburton Energy Services,Inc.。CLAY SEAL泥浆稳定剂是化学钻井液添加剂,可商购自Halliburton Energy Services,Inc.。
表V泥浆配制
对表V中的所有泥浆在烘箱中150°F下热辊16小时。热辊后进行pH测量。表VI中所示为与24%(w/w)NaCl混合的泥浆的密度。将表V(24%(w/w)NaCl(密度=13)的泥浆加入不同量的NaOH,以调节泥浆的pH,并确定实现相同的试验结果所需要的泥浆的量。
表VI密度和pH对AE200聚合物性能的影响
密度可对混合泥浆与AE 200聚合物后的固体质量具有重要的作用,也可以确定形成固体所需要的AE 200聚合物的量。如表VI中所示,在相同的条件下,密度越低,就有越多的AE 200聚合物可用于形成固体(4mL的AE 200聚合物对于D=10/2mL的AE 200聚合物对于D=16,即体积下降50%)。
观察到在使用密度为16的泥浆时,形成的固体显然比使用密度为10的泥浆更稠和更强。在相同的条件下,通过对比pH=7.66和11的泥浆,观察到在pH=7.66下其需要1.5分钟来形成固体,对于pH=11而言需要1分钟,这可以规因于作用于AE 200聚合物的″盐中毒″(例如,阳离子中毒效果)。pH越低,就可能有更多的游离H+离子可在溶液中,结果对AE 200聚合物就可能有更差的盐中毒作用。但是,当pH从9变化至11时,没有观察到差异。
实施例5
测试实施例4的泥浆的盐度。观察到盐度对AE 200聚合物比pH有更大的影响。表VII所示为盐度结果。
表VII盐度对AE 200聚合物性能的影响
淡水 | 10%(w/w)NaCl | 24%(w/w)NaCl | |
密度(lb/gal) | 13 | 13 | 13 |
泥浆体积(mL) | 10 | 10 | 10 |
pH | 9.03 | 9.05 | 9.06 |
AE 200聚合物(mL) | 1 | 2 | 3 |
观察结果 | 只需要1mL的AE200聚合物来形成聚合物糊/固体。所述糊的质地也是所有其它样品中最佳的。 | 固体的质地和强度介于淡水和24%(w/w)NaCl之间。 | 在24%(w/w)NaCl的泥浆中AE 200聚合物仍然有效。其只需要更多的AE 200聚合物来形成糊/固体。 |
表VII的淡水泥浆就AE 200聚合物的使用量、以及混合后形成的固体的质量而言性能最好。同时,溶液中阳离子越多,就需要更多的AE 200聚合物来形成固体。因此,从表VII中可以看出,当盐度增加时增加用量的AE 200聚合物。为了知道KCl的存在是否会影响AE 200聚合物的性能,进行了两个试验,结果见表VIII中所示。
表VIII
样品 | 10%KCl | 3%KCl+24%NaCl |
AE 200聚合物(3mL)∶盐溶液(10mL) | 形成固体 | 形成固体 |
结果显示,无论是在10%的KCl溶液中或是在含有3%KCl的24%的NaCl溶液中固体形成都没有问题,只要在混合物中有足够量的AE 200聚合物(在此情况下是3mL的AE 200聚合物)即可。
实施例6
用各种泥浆对AD 200聚合物进行测试,结果见表IX中所示。AD 200聚合物是脱水形式的AE 200聚合物。测试方法类似于以上所述的测试。在烧杯中将1mL的AD 200聚合物和20mL泥浆混合。记录下混合物硬化所需的时间。比较固体糊的质地。
表IX AD 200聚合物与各种水基泥浆
样品 | 1∶20(v/v)(AD200聚合物∶泥浆) |
HYDRO-GUARD体系 | 在1分钟内变稠并形成聚合物固体。 |
磺化木质素泥浆 | 在1分钟内变稠并形成聚合物固体。 |
含有6ppb石灰的磺化木质素泥浆 | 在1分钟内变稠并形成聚合物固体。 |
含有6ppb石灰的磺化木质素泥浆(在加入AD 200聚合物之前加入了0.5g的Na2CO3) | 在1分钟内变稠并形成聚合物固体。但是,此泥浆形成聚合物固体所需的时间比以上的时间更短。所述聚合物固体的强度和质地也比以上所得的要更好些。 |
GEM GP泥浆 | 在1分钟内变稠并形成聚合物固体。 |
HYDRO-GUARD体系是可商购自Halliburton Energy Services,Inc.的水基的泥浆。GEM GP(通用型)是可商购自Halliburton Energy Services,Inc.的二醇增强的泥浆,并且也是水基的泥浆。观察到AD 200聚合物与不同的水基泥浆之间运转非常良好。另外,观察到即使是高石灰泥浆,形成固体也没有问题。在加入AD 200聚合物之前将苏打灰加入所述高石灰泥浆中时结果甚至会更好。
实施例7
为了能够在井下安全地输送AD 200聚合物,为此使用适宜的隔离剂。表X归纳了该发现的结果。泥浆中AD 200聚合物用乳化剂(例如,LE SUPERMUL乳化剂)进行测试,该乳化剂被用作隔离剂。测试结果见表X中所示。
表X润湿剂、隔离剂、泥浆、AD 200聚合物及其相容性和稳定性
样品 | 评述 |
LE SUPERMUL乳化剂 | 润湿剂(聚胺化的脂肪酸)。 |
SF基油 | 隔离剂的主要组分。 |
在SF基油中的2%(v/v)的LE SUPERMUL乳化剂 | 隔离剂将被用于水泥浆体系中。其应当在井下输送AD 200聚合物之前和之后使用。 |
隔离剂∶AD 200聚合物(10mL∶10mL) | 稳定性或相容性没有问题。消耗了25mL水来反转乳液。 |
磺化木质素泥浆∶隔离剂∶AD 200聚合物(1∶1∶0.5) | 形成聚合物固体没有问题。 |
GEM GP泥浆∶隔离剂∶AD200聚合物(1∶1∶0.5) | 形成聚合物固体没有问题。 |
SF基油是可商购自Halliburton Energy Services,Inc.的内烯烃。观察到当AD 200聚合物用重晶石增重至19lb/gal时没有出现问题。
实施例8
用ACCOLADE钻井液测试AD 200聚合物。ACCOLADE液是不含粘土的合成系钻井液,可商购自Halliburton Energy Services,Inc.。泥浆的配制在表XI中列出。表XII所示为AD 200聚合物与ACCOLADE液不同混合的结果。ACCOLADE液按照表XI中进行配制,然后在150°F的烘箱中热辊16小时。ADAPTA过滤退粘剂是一种共聚物,其提供在非水性流体体系中的HPHT过滤控制,并可商购自Halliburton Energy Services,Inc.。BARACARB桥接剂是可商购自Halliburton Energy Services,Inc.的碳酸盐颗粒。RHEMOD L增粘剂可商购自Halliburton Energy Services,Inc.。
表XI ACCOLADE泥浆的配制
样品,(lb/gal) | (12.0lb/gal)70/30油∶水 |
水相盐度 | 250,000ppm |
ACCOLADE流体基,bbl | 0.436 |
LE SUPERMUL乳化剂,lb/bbl | 10 |
水,bbl | 0.24 |
石灰,lb/bbl | 1 |
ADAPTA HP过滤退粘剂,lb/bbl | 2 |
重晶石,lb/bbl | 188.96 |
REV-DUST添加剂,lb/bbl | 20.0 |
BARACARB 25试剂,lb/bbl | 7.5 |
BARACARB 50试剂,lb/bbl | 7.5 |
CaCl2,lb/bbl | 29.09 |
RHEMOD L悬浮剂/增粘剂,lb/bbl | 1 |
表XII AD 200聚合物和ACCOLADE泥浆的初级实验室测试结果
观察到与20mL泥浆混合的1mL AD 200聚合物能够形成固体糊的混合物。也观察到2∶1(AD 200聚合物∶泥浆)的混合比加上20mL的苏打灰溶液被用来形成如表XII中所示的固体/糊。当2mL的AD 200聚合物与1mL泥浆混合时,AD 200聚合物的浓度从50%变为33.33%(例如,33%的活性AD 200聚合物与20mL苏打灰溶液反应形成固体)。Na2CO3的用量(0.1g)根据溶液中化学计算量的Ca2+计算。使用1.0g的Na2CO3来替代0.1g,以观察过量的Na2CO3是否会影响AD 200聚合物的性能。过量的Na2CO3对AD 200聚合物的作用是盐中毒,因此所述混合物具有更困难的形成固体的时间。
观察到油性泥浆的固体的质地不如水基泥浆的好。因此,将额外的固体加入,如表XIII中所示。STEEL SEAL是可商购自Halliburton Energy Services,Inc.的石墨。
表XIII AD 200聚合物与ACCOLADE泥浆的初级实验室测试结果
观察到添加的固体提供了就质地和强度而言更好的最终糊状物。
实施例9
用AD 200聚合物(PETROFREE SF液和ENVIROMUL液)测试两种更多的油基泥浆。PETROFREE钻井液可商购自Halliburton Energy Services,Inc.。ENVIROMUL钻井液可商购自Halliburton Energy Services,Inc.。其配制见下表XIV和XV中所示。GELTONE II增粘剂和GELTONE V增粘剂是包含研磨的亲有机物粘土的凝胶化的和增粘的试剂,可商购自Halliburton Energy Services,Inc.。对两种泥浆都在150°F的烘箱中热辊16小时。ESCAID液是一种可商购自Exxon Chemical Company的油。SUSPENTONE悬浮剂是一种亲有机物的粘土,可商购自Halliburton Energy Services,Inc.。EZ MUL NT乳化剂是一种合成系的泥浆乳化剂,可商购自Halliburton Energy Services,Inc.。DURATONE HT(高温)油性泥浆过滤控制剂包括亲有机物的褐煤共混物,其可商购自HalliburtonEnergy Services,Inc.。DEEP-TREAT稀释剂是润湿剂,可商购自HalliburtonEnergy Services,Inc.,而COLDTROL稀释剂可商购自Halliburton EnergyServices,Inc.。测试包括向烧杯中加入20mL的水,接着是Na2CO3。如果需要的话,也可加入STEELSEAL添加剂、重晶石或REV-DUST添加剂。然后在烧杯中加入2mL AD 200聚合物和1mL泥浆。再将烧杯的内含物混合。记录混合物硬化所需的时间。试验结果见表XVI中所示。
表XIV PETROFREE SF泥浆的配制
样品,(lb/gal) | (12.0lb/gal)70/30油∶水 |
水相盐度 | 250,000ppm |
SF Base(IO),bbl | 0.426 |
LE SUPERMUL乳化剂,lb/bbl | 8 |
ADAPTA HP过滤退粘剂,lb/bbl | 1 |
水,bbl | 0.257 |
RHEMOD L悬浮剂/增粘剂 | 0.25 |
重晶石,lb/bbl | 208.1 |
CaCl2,lb/bbl | 29.11 |
REV-DUST添加剂,lb/bbl | 10.0 |
BARACARB 5试剂,lb/bbl | 10.0 |
GELTONE II增粘剂,lb/bbl | 4.0 |
表XV ENVIROMUL泥浆的配制
样品,(lb/gal) | (12.0lb/gal)70/30油∶水 |
水相盐度 | 250,000ppm |
ESCAID液110,bbl | 0.524 |
水,bbl | 0.233 |
GELTONE V增粘剂,lb/bbl | 12.0 |
SUSPENTONE试剂,lb/bbl | 4.0 |
EZ MUL NT乳化剂,lb/bbl | 5.0 |
INVERMUL NT乳化剂,lb/bbl | 4.0 |
石灰,lb/bbl | 2 |
DURATONE HT过滤控制剂 | 8.0 |
DEEP-TREAT稀释剂,lb/bbl | 5.0 |
COLDTROL稀释剂,lb/bbl | 2.5 |
CaCl2,lb/bbl | 28.4 |
重晶石,lb/bbl | 209.8 |
表XVI AD 200聚合物与PETROFREE SF和ENVIROMUL泥浆的试验结果
*该表中的所有试验都是用20mL水进行的。
从实施例8和9可以看出,含有PETROFREE SF和ENVIROMUL泥浆的AD 200聚合物与含有ACCOLADE泥浆的试验结果相似。
尽管已显示和描述了本发明的优选实施方案,但是在不背离本发明的精神和教导下,本领域技术人员可以对其进行改进。这里描述的实施方案仅是示范性的,不应看成是限制性的。本发明这里公开的很多变化和改进都是可能的,并且在本发明的保护范围内。其中在表述数范围或限制时,这种表述范围或限制应当理解为包括落入表述范围或限制内的相同数量(例如从约1至约10包括2、3、4,等等;大于0.10包括0.11、0.12、0.13等等)的重复(iterative)范围和限制。权利要求任何部分所用的术语“任选”意指主题元素是需要的,或者是不需要的。两种备选方式都在权利要求的范围之内。更宽泛使用的术语例如包含、包括、具有等应理解为对更窄的术语例如“由...组成、基本由...组成、基本上由...构成等等”提供支持。
因此,保护范围不是由以上所阐述的说明书限定,而是仅由其后的权利要求限定,并且所述范围包括权利要求主题所有的等价物。每一个和每项权利要求都被结合到说明书中作为本发明的实施方案。因此,权利要求是进一步的说明,并且是本发明优选实施方案的补充。发明背景技术中的参考文献的讨论不应将其认为是本发明的现有技术,尤其是具有在本申请优先权日之后的出版日的任何参考文献。文中引用的所有专利、专利申请、出版物的公开内容都通过引用结合在此,以至于它们为这里所描述的提供示范性的、程序上的、或其它细节上的补充。
Claims (23)
1、一种维护穿透地层的井身的方法,其包括:
将包含反相乳液聚合物的封堵剂组合物置入井身中,以降低在所述井身中置入流体期间的地层中的流体损失。
2、权利要求1的方法,其中所述反相乳液聚合物包含石油润滑油、天然油、合成衍生油、矿物油、硅油、或它们的组合。
3、权利要求1的方法,其中所述反相乳液聚合物包含以该反相乳液聚合物的总重量计约10-约80重量%的油。
4、权利要求1的方法,其中所述反相乳液聚合物包含以该反相乳液聚合物的总重量计约0-约70重量%的水。
5、权利要求1的方法,其中所述反相乳液聚合物包含水溶胀性聚合物。
6、权利要求5的方法,其中所述反相乳液聚合物包含以该反相乳液聚合物的总重量计约5-约100重量%的水溶胀性聚合物。
7、权利要求5的方法,其中所述水溶胀性聚合物包含合成聚合物、超吸收体、天然聚合物、或它们的组合。
8、权利要求5的方法,其中所述水溶胀性聚合物包含粒度为约0.01微米-约30微米的颗粒。
9、权利要求1的方法,其中所述反相乳液聚合物在置入井身中之前被脱水。
10、权利要求9的方法,其中所述反相乳液聚合物被脱水至含约0-约10重量%的水。
11、权利要求1的方法,其还包括在将所述反相乳液聚合物置入井身中之前添加填充物至所述反相乳液聚合物中。
12、权利要求1的方法,其还包括在置入所述封堵剂组合物之前向井身中置入隔离液。
13、权利要求1的方法,其还包括在井身中置入所述封堵剂组合物之后向井身中置入钻井液。
14、权利要求1的方法,其中所述流体包括水基钻井液或非水钻井液。
15、权利要求1的方法,其还包括在井身中置入所述封堵剂组合物之后在井身中置入处理组合物。
16、一种包含反相乳液聚合物的封堵剂组合物,其中所述反相乳液聚合物包含粒度为约0.01微米-约30微米的颗粒。
17、权利要求16的封堵剂组合物,其中所述反相乳液聚合物包含水溶胀性聚合物。
18、权利要求17的封堵剂组合物,其中所述反相乳液聚合物包含以该反相乳液聚合物的总重量计约5-约100重量%的水溶胀性聚合物。
19、权利要求17的封堵剂组合物,其中所述水溶胀性聚合物包含合成聚合物、超吸收体、天然聚合物、或它们的组合。
20、一种包含油分散的聚合物的封堵剂组合物,其中所述聚合物包含粒度为约0.01微米-约30微米的颗粒。
21、权利要求20的封堵剂组合物,其中所述油分散的聚合物包含石油润滑油、天然油、合成衍生油、矿物油、硅油、或它们的组合。
22、权利要求20的封堵剂组合物,其中所述油分散的聚合物包含约0-约10重量%的水。
23、权利要求20的封堵剂组合物,其中所述油分散的聚合物包含水溶胀性聚合物。
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CN102676141A (zh) * | 2012-04-20 | 2012-09-19 | 中国海洋石油总公司 | 一种钻井液用可变形封堵防塌剂 |
CN102676141B (zh) * | 2012-04-20 | 2014-05-14 | 中国海洋石油总公司 | 一种钻井液用可变形封堵防塌剂 |
CN104388067A (zh) * | 2014-10-31 | 2015-03-04 | 中国石油化工集团公司 | 一种油基钻井液用复合防漏剂 |
CN104388067B (zh) * | 2014-10-31 | 2020-01-14 | 中国石油化工集团公司 | 一种油基钻井液用复合防漏剂 |
CN106543983A (zh) * | 2015-09-23 | 2017-03-29 | 中国石油天然气股份有限公司 | 阻止井喷的辅助剂及其应用 |
CN106543983B (zh) * | 2015-09-23 | 2020-08-07 | 中国石油天然气股份有限公司 | 阻止井喷的辅助剂及其应用 |
CN108485633A (zh) * | 2018-03-31 | 2018-09-04 | 青岛大学 | 一种新型网状聚季胺油气井页岩防膨剂的制备方法 |
CN108485633B (zh) * | 2018-03-31 | 2021-10-08 | 青岛大学 | 一种网状聚季胺油气井页岩防膨剂的制备方法 |
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DK1902115T3 (da) | 2014-05-26 |
EP1902115B1 (en) | 2014-03-19 |
US20070012447A1 (en) | 2007-01-18 |
MX2008000432A (es) | 2008-03-10 |
US7870903B2 (en) | 2011-01-18 |
WO2007007118A1 (en) | 2007-01-18 |
CN101263211B (zh) | 2015-04-15 |
CA2614272C (en) | 2011-09-13 |
US8703657B2 (en) | 2014-04-22 |
US20110118381A1 (en) | 2011-05-19 |
CA2614272A1 (en) | 2007-01-18 |
RU2008105311A (ru) | 2009-08-20 |
AR091303A2 (es) | 2015-01-28 |
RU2436946C2 (ru) | 2011-12-20 |
AR056670A1 (es) | 2007-10-17 |
AU2006268023B2 (en) | 2011-12-01 |
EP1902115A1 (en) | 2008-03-26 |
AU2012200222B2 (en) | 2012-06-28 |
AU2006268023A1 (en) | 2007-01-18 |
AU2012200222A1 (en) | 2012-02-02 |
NO20080203L (no) | 2008-04-14 |
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