CN111479687A - Pekk用于制备具有低气体渗透率的部件的用途 - Google Patents
Pekk用于制备具有低气体渗透率的部件的用途 Download PDFInfo
- Publication number
- CN111479687A CN111479687A CN201880076705.8A CN201880076705A CN111479687A CN 111479687 A CN111479687 A CN 111479687A CN 201880076705 A CN201880076705 A CN 201880076705A CN 111479687 A CN111479687 A CN 111479687A
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- Prior art keywords
- pekk
- pipe
- layer
- permeability
- per
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
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Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F16L9/147—Compound tubes, i.e. made of materials not wholly covered by any one of the preceding groups comprising only layers of metal and plastics with or without reinforcement
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
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Abstract
本发明主要涉及PEKK用于降低旨在与石油流出物接触的部件的CO2和H2S渗透率的用途。其还涉及用于运输石油流出物的管道,其包括旨在与石油流出物接触的层,其特征在于,所述旨在与石油流出物接触的层包含PEKK并且对于1cm的厚度和1cm2的表面积以及每秒和每巴的CO2压力,在130℃下的CO2渗透率小于10‑8cm3,和/或对于1cm的厚度和1cm2的表面积以及每秒和每巴的H2S压力,在130℃下的H2S渗透率小于10‑8cm3,CO2和H2S的量分别通过GC测量。最后,本发明还涉及多种用于制备这种管道的方法。
Description
技术领域
本发明涉及聚(醚酮酮)(PEKK)作为气体阻隔层的用途,并且尤其是用于制造对气体例如CO2或H2S具有低渗透率的部件的用途。其更特别地涉及用于运输石油流体的管道。
背景技术
有许多领域要求材料具有低气体渗透率,甚至在严苛的条件下也是如此。
例如,在海上石油开采中,所提取的烃必须在远距离和极端条件下运输。这是因为所使用的管道可能长时间地经受超过100巴的压力以及大于90℃或甚至130℃的高温。在这些条件下运输石油流出物的期间,在所运输的烃中存在的某些气态酸性化合物例如H2S和CO2如果接触到金属组分的话可能会造成非常昂贵的腐蚀破坏。腐蚀带来了严重的风险,这是因为在管道上的相当大的应力,其不仅来自管道的重量而且还来自石油流出物和海上环境的高压。在高温下,迁移和腐蚀现象加剧。
有两种已知类型的用于运输石油流出物的管道结构体。
在刚性结构体中,管道可包括金属管,其由内部聚合物层保护以增强耐腐蚀性。内部聚合物层可采取例如通过粉末涂覆获得的衬里或胶粘剂涂层的形式。
柔性结构体从管道的内部到外部可包括:金属胎体(carcass),其由以短螺距螺旋卷绕以抵抗挤压的金属条组成;用作密封护套的挤出聚合物层;用以抵抗内部压力的紧固金属线的拱形物(vault);作为密封护套的第二挤出聚合物层;一个或多个由以特定角度螺旋卷绕的金属线组成的抗拉铠装(armor)层;以及最后地用于保护管道不受周围环境影响的外部聚合物护套。这些结构体被称为“粗孔”管道。
在此类管道中省略了胎体的情况下,其被称为“平滑孔”管道。在这些后者结构中,石油流出物与密封层的聚合物直接接触。
为了增强这些管道的耐温性,文献US 2006/0229395 A1提出了使用由热塑性聚合物挤出的内部涂层或导管,所述热塑性聚合物对化学产品具有高的耐受性并且具有高的软化点,例如聚(苯硫醚)(PPS)或聚芳基醚酮(PAEK)。该文献没有提及这些聚合物的气体渗透率。
文献WO 2014/199033提出了向聚合物添加碱金属或碱土金属氧化物,以通过化学反应来中和CO2和H2S。所提出的聚合物是来自偏二氟乙烯共聚物类的聚合物。然而,这种方法存在实施上的困难,并且填料的添加倾向于损害聚合物的机械性质,尤其是断裂伸长率。
此外,专利申请WO 2012/107753 A1提出了通过进行较慢且因此更均匀的聚合物的结晶,而降低其中的残余应力来降低在压力下运输流体的管道的失效风险。在所考虑的聚合物中,提及了PEKK,但是未举例说明。该文献也没有提及这些聚合物的气体渗透率。
尽管取得了这一进展,但仍需要具有低气体渗透率的管道,尤其是对于腐蚀性物质(例如,CO2和H2S)具有低气体渗透率,甚至在极端的运行条件下也是如此。原因是表现出较好渗透率性能的聚合物将允许增加管道的寿命和/或减小阻隔层的厚度从而减小管道的重量。
发明内容
本发明依赖于以下发现:聚(醚酮酮)(PEKK)表现出非常有利的气体阻隔性,尤其是与CO2和H2S相关的气体阻隔性,这些性质,更特别地,明显优于聚(醚醚酮)(PEEK)的气体阻隔性。
因此,在第一方面,本发明提供了PEKK用于降低旨在与石油流出物直接地或间接地接触的部件的CO2和H2S渗透率的用途。
术语“与石油流出物接触的部件”表示与所述流出物直接或间接接触的层。
术语“与石油流出物直接接触的部件”尤其表示管道的内层。
术语“与石油流出物间接接触的部件”尤其表示不是内层而是围绕内层放置的层,其中所述内层可为密封的或不为密封的。
PEKK优选具有大于5%的按质量计的结晶度。
PEKK有利地具有35%至100%、优选55%至85%并且更具体地60%至80%的T:I比。
对于1cm的厚度和1cm2的表面积、每秒和每巴的CO2压力,在130℃下的部件的CO2渗透率优选小于10-8cm3 CO2,渗透的CO2的量通过GC测量。
对于1cm的厚度和1cm2的表面积、每秒和每巴的H2S压力,在130℃下的部件的H2S渗透率优选小于10-8cm3,H2S的渗透的H2S量通过GC测量。
该部件优选地选自管、护套或压力层和内部涂层,尤其是旨在用于运输石油流出物。
在第二方面,本发明提供了一种管道,尤其是用于运输石油流出物的管道,其包括旨在与石油流出物接触的层,其特征在于,所述旨在与石油流出物接触的层包含PEKK并且对于1cm的厚度和1cm2的表面积、每秒和每巴的CO2压力,在130℃下的CO2渗透率小于10- 8cm3,和/或对于1cm的厚度和1cm2的表面积、每秒和每巴的H2S压力,在130℃下的H2S渗透率小于10-8cm3,渗透的CO2和H2S的量分别通过GC测量。
在一个实施方案中,所述旨在与石油流出物接触的层是围绕金属胎体的密封护套。
在另一个实施方案中,所述旨在与石油流出物接触的层不含增强纤维。
所述旨在与石油流出物接触的层优选地被至少一个机械增强层围绕。
在一个实施方案中,所述至少一个机械增强层由金属制成。
在另一个实施方案中,所述至少一个机械增强层由复合材料制成。在这种情况下,复合材料可为,例如,热塑性复合材料,其尤其基于聚酰胺,聚乙烯,尤其是PE-RT(“高温聚乙烯”的缩写),PEKK或PVDF,并且可进一步包含碳纤维,尤其是连续碳纤维、芳族聚酰胺纤维或玻璃纤维。
在一个实施方案中,本发明的管道还包含柔性金属框架(armature,加强件,衔铁)。在另一个实施方案中,管道还包含刚性金属框架。
此外,在第三方面,本发明提供了多种用于制造根据本发明的管道的方法。
当待制造、尤其是待翻新的管道是刚性管道时,本发明的方法包括以下步骤:
(a)制备适当尺寸的包含PEKK的管;和
(b)将所述管插入金属管内以形成衬里。
当待制造的管道是柔性粗孔管道时,本发明的方法包括以下步骤:
(a)提供金属胎体;
(b)通过十字头挤出在所述金属胎体周围挤出至少一个包含PEKK的组合物的层;和
(c)在所得结构体周围安装拱形物;
(d)安装一个或多个抗拉铠装层;和
(e)在所得组装体周围挤出外部聚合物护套。
当待制造的管道是柔性平滑孔管道时,本发明的方法包括以下步骤:
(a)通过十字头挤出来挤出至少一个包含PEKK的组合物的层;和
(b)在所得结构体周围安装拱形物;
(c)安装一个或多个抗拉铠装层;和
(d)在所得组装体周围挤出外部聚合物护套。
通过阅读下文给出的详细描述,将得出根据本发明的方法的其他特征和优点。
具体实施方式
根据本发明,建议使用聚(醚酮酮)(PEKK)来制造具有低气体渗透率的部件,并且特别是相对于CO2和/或H2S具有低气体渗透率。
PEKK
“PEKK”是指包含式(-Ar-X-)的单元以及式(-Ar'-Y-)的单元的PAEK聚合物,其中:
–Ar和Ar’各自表示二价芳族基团;
–Ar和Ar’可优选选自任选取代的1,3-亚苯基和1,4-亚苯基;
–X表示羰基;
–Y表示选自氧原子的基团。
聚-醚-酮-酮(PEKK)包含一系列的-(Ar1-O-Ar2-CO-Ar3-CO)n-类型的重复单元,其中Ar1、Ar2和Ar3各自独立地代表二价芳族基团,优选亚苯基。
在以上式中,正如在随后的所有式中一样,n代表整数。
在每个单元Ar1、Ar2和Ar3的任一侧上的键都可为对位或间位或邻位型(优选对位或间位型)。
在某些实施方案中,PEKK包含一系列的以下式(IA)和/或式(IB)的重复单元:
式(IA)的单元是衍生自间苯二甲酸的单元(或I单元),而式(IB)的单元是衍生自对苯二甲酸的单元(或T单元)。
在本发明中使用的PEKK中,相对于T和I单元的总和计,T单元的质量比例的范围可为0%至5%;或5%至10%;或10%至15%;或15%至20%;或15%至20%;或20%至25%;或25%至30%;或30%至35%;或35%至40%;或40%至45%;或45%至50%;或50%至55%;或55%至60%;或60%至65%;或65%至70%;或70%至75%;或75%至80%;或80%至85%;或85%至90%;或90%至95%;或95%至100%。
35%至100%、尤其是55%至85%并且甚至更特别地60%至80%的范围是特别合适的。在本专利申请中列出的所有范围中,除非另有说明,否则都包括端值。
PEKK在96%硫酸中的特性粘度优选为0.4至1.5dL/g,优选0.6至1.4dL/g,更优选0.8至1.2dL/g。
聚合物的结晶度可能影响气体渗透率性质。实际上,已经注意到,随着结晶度增加,PEKK的气体渗透率,尤其是相对于CO2和H2S的气体渗透率下降。因此,优选所使用的PEKK具有最大结晶度,其优选大于5%,特别地大于15%,并且非常特别地大于25%。在本发明中使用的PEKK中,结晶PEKK的质量比例可特别地为0%至1%;或1%至5%;或5%至10%;或10%至15%;或15%至20%;或20%至25%;或25%至30%;或30%至35%;或35%至40%;或40%至45%;或45%至50%。
对于某些应用,使用无定形PEKK可为有利的。无定形PEKK表示根据标准ISO11357-3:1999通过DSC测量的熔融焓小于10J/g的PEKK。
-波长:铜的主Kα1线(1.54埃)。
-发生器(Generator)功率:50kV–0.6mA。
-观察模式:透射
-计数时间:10分钟。
如此获得了作为衍射角的函数的散射强度的光谱。当在光谱上可见到除了无定形晕(halo)外的峰时,该光谱使得可识别晶体的存在。
在光谱中,可测量结晶峰的面积(标为AC)和无定形晕的面积(标为AH)。然后使用比率(AC)/(AC+AH)估计PEKK中的结晶PEKK的质量比例。
通常有利的是,结晶PEKK的含量相对较高,例如大于或等于5%,或大于或等于10%,或甚至大于或等于15%,以提供具有高机械性能的部件。高结晶度的另一个优点是更好的机械性质,包括在高温下的机械性质,例如在模量或屈服应力方面。
一种替代的可能性是通过将例如通过DSC测量的PEKK的熔融焓除以按质量计的结晶度为100%的PEKK的熔融焓来计算结晶度。
PEKK树脂可包含一种或多种属于或不属于PAEK类的另外的聚合物。
PEKK树脂中的PEKK的质量含量优选大于或等于50%,优选大于或等于60%,特别地大于或等于70%,优选大于或等于80%,并且更优选大于或等于90%。在某些实施方案中,PEKK树脂基本上由一种或多种PEKK组成。
树脂可包含添加剂,例如填料和功能性添加剂。相应地,树脂可包含增强填料,尤其是连续纤维,特别是碳纤维。也可省去填料和/或省去功能性添加剂。
树脂可特别地包含一种或多种磷酸酯或磷酸盐,以改进PAEK的熔体稳定性。
根据本发明,使用PEKK制造的部件具有低的气体渗透率,尤其是相对于CO2和/或H2S而言。在某些应用中,例如尤其是在水下石油开采中,需要具有耐受性的管道,并且这些管道在严苛或甚至极端的工作条件下仍保持这些性质,从而限制气态物质的迁移并限制腐蚀。这些条件典型地包括大于100℃,优选大于110℃,特别地大于120℃,并且非常特别地大于130℃的工作温度,和/或大于10巴,优选大于20巴,特别地大于30巴并且非常特别地大于40巴,或甚至大于50巴或甚至大于100巴的压力。
对于1cm的厚度和1cm2的表面积、每秒和每巴的CO2压力,部件有利地在130℃下的CO2渗透率小于10·10-8、特别是5·10-8、尤其是1·10-8、优选5·10-9并且特别地小于1·10-9cm3 CO2,CO2的量通过GC测量。
此外,对于1cm的厚度和1cm2的表面积、每秒和每巴的H2S压力,在130℃下的部件的H2S渗透率优选小于10·10-8、特别是5·10-8、尤其是1·10-8、有利地5·10-9、更优选小于1·10-9、特别地小于5·10-10并且非常特别地小于1·10-10cm3 H2S,H2S的量通过GC测量。
在一个实施方案中,该部件可包括两个或更多个层。其可特别地将至少一个包含PEKK的层与以下结合:至少一层不同材料,尤其是PVDF、聚酰胺、聚乙烯、尤其是PE-RT,或者用作用于将各层彼此组装的粘合剂的材料。
管道
在某些技术领域中,尤其是在石油开采中,寻求将耐温性和对化学产品的耐受性与低气体渗透率(尤其是相对于酸性化合物CO2和H2S而言)相结合的材料。原因是存在于石油中的这些化合物是酸性的,并且引起金属组分的腐蚀。因此,使用PEKK尤其有利于制造用于运输液态和/或气态烃(以下称为石油流出物)的部件。
因此,在第二方面,本发明涉及一种管道,其包括旨在与石油流出物接触的层,其特征在于,所述旨在与石油流出物接触的层包含PEKK并且对于1cm的厚度和1cm2的表面积、每秒和每巴的CO2压力,在130℃下的CO2渗透率小于10-8cm3 CO2,和/或对于1cm的厚度和1cm2的表面积、每秒和每巴的H2S压力,在130℃下的H2S渗透率小于10·10-8、特别是5·10-8、尤其是1·10-8、有利地5·10-9、更优选1·10-9、特别是5·10-10并且非常特别是1·10- 10cm3 H2S,CO2和H2S的量通过GC测量。
这些管道可用于提取设备中,用于运输石油流出物,或者用于在严苛的压力和/或温度条件下运输包含CO2和/或H2S的其他混合物。
特别地,提供了旨在用于运输烃的管道,尤其是包含至少一种气态酸性化合物的混合物,所述至少一种气态酸性化合物尤其是选自CO2和H2S的气体。
根据它们的特定用途和相关的应力,这些管道可具有各种结构。
因此,管道可例如是单层管道,或者可包括两个、三个、四个或甚至更多数的层。多层管道特别地能够在不与石油流出物接触的外部层处承受机械或热应力。
通常,旨在与石油流出物接触的层构成管道的内部层。然而,本发明还包括该层与石油流出物间接接触的情况。因此,在本发明的一个实施方案中,管道包括密封或不密封的内部层,例如金属胎体,其被包含PEKK的层围绕。在这种情况下,石油流出物至少部分地通过不密封的内部层,并且因此间接与包含PEKK的层接触。
在一个实施方案中,胎体被包含PEKK的薄膜围绕。在另一个实施方案中,薄膜由多个层组成,并且除了包含PEKK的层外还包括至少一个另外的层,其由不同的聚合物制成,例如PVDF、聚酰胺、聚乙烯、尤其是PE-RT,或者由用作用于将各层彼此组装的粘合剂的材料制成。
所述多层薄膜可例如包括包含PEKK的层和基于PVDF的层。PVDF是一种尤其因其柔性和其耐化学性和耐热性(最高达280℃)而受重视的材料,尽管其气体渗透率意味着其几乎不提供防腐蚀保护。有利地,PVDF层可设置成与胎体接触,并且包含PEKK的层可设置在胎体的外部上。可在形成薄膜的这两个层之间设置其他层。
构成薄膜的各层可例如通过机械紧固彼此结合,换句话说,通过在它们各自的表面上存在的粗糙度的接合(engagement)。
因此,管道可为被称为“粗孔”的类型。在这种类型的管道中,旨在与石油流出物接触的层可构成围绕金属胎体的密封护套。胎体由螺旋卷绕的金属带形成,该金属带用于增强管道相对于外部压力的抵抗力。这种管道可进一步包括:由例如紧固金属线制成的拱形物,以确保对管道内的内部压力的抵抗力,以及由以特定角度螺旋卷绕的金属线组成的抗拉铠装层,以允许管道特别地具有更好的抗拉强度。
管道可替代地为被称为“平滑孔”的类型。这种类型的管道没有金属胎体。石油流出物然后可与包含PEKK的层直接接触。在两种类型的管道中,旨在与石油流出物接触的层可或可不含有增强纤维。在任何情况下,以及低气体渗透率,尤其是相对于CO2和H2S而言,PEKK的一个优点是优异的耐磨性,尤其是与其他试剂(特别是增强纤维,尤其是碳纤维)配制时。相应地,PEKK的内部层提供了对由流出物中经常存在的固体颗粒引起的磨损的有效的耐受性。
根据本发明的管道典型地还包括——如前对于粗孔管道所说明地——至少一个机械增强层(其形成框架),以抵抗外部和内部压力。但是,也有仅由热塑性聚合物组成的柔性管道,例如由Airborne销售的那些。在这些管道中,增强层和任选的金属框架被由热塑性复合材料组成的增强材料代替。
所述至少一个机械增强层可由金属制成。在这种情况下,其可为金属管,或者为了更大的柔性,可为金属线或金属织物的线圈(winding)。
机械增强层可替代地由复合材料制成。该复合材料优选由用增强填料增强的聚合物组成。该聚合物优选是高性能热塑性聚合物,例如来自聚酰胺、聚乙烯、尤其是PE-RT、PVDF、PAEK类的聚合物,尤其选自PEKK和/或PEEK。在复合材料中,聚合物用增强填料,尤其是纤维、尤其是碳纤维或芳族聚酰胺纤维或玻璃纤维增强。此外,在适当情况下,包含PEKK的这种机械增强层可代替金属胎体和拱形物两者,以提供柔性的平滑孔管道。
在一个实施方案中,管道还包含柔性外部框架。在另一个实施方案中,管道还包含刚性外部框架。
旨在与石油流出物接触的层可尤其以管、护套或压力层或内部涂层的形式存在。内部涂层可特别地为旨在插入到管道、尤其是金属管道中以对其进行翻新的衬里。
在第三方面,本发明提供了用于制造如上所述的管道的方法。
特别地,当旨在与石油流出物接触的层采取管或护套的形式时,其可例如通过挤出或共挤出获得。当该层为内部涂层的形式时,其可例如通过粉末涂覆获得。
如上所述,由多个层组成的部件也可通过护套挤出或通过卷绕条带并随后焊接而获得。在这种情况下,旨在与石油流出物接触的层也称为压力层或护套。
更具体地,当待制造或翻新的管道是刚性管道时,本发明的方法包括以下步骤:
(a)制备适当尺寸的包含PEKK的管;和
(b)将所述管插入金属管内以形成衬里。
在一个实施方案中,包含PEKK的管可进一步包括一个或多个另外的层,例如PVDF、聚酰胺、PE-RT或者用作用于将各层彼此组装的粘合剂的材料的层。
当待制造的管道是柔性粗孔管道时,本发明的方法包括以下步骤:
(a)提供金属胎体;
(b)通过十字头挤出在所述金属胎体周围挤出至少一个包含PEKK的组合物的层;和
(c)在所得结构体周围安装拱形物;
(d)安装一个或多个抗拉铠装层;和
(e)在所得组装体周围挤出外部聚合物护套。
在步骤(b)之前,可在金属胎体上挤出一个或多个其他层,尤其是基于PVDF、基于聚酰胺、基于聚乙烯、尤其是基于PE-RT的层,或者基于用作用于将各层彼此组装的粘合剂的材料的层。
当待制造的管道是柔性平滑孔管道时,本发明的方法包括以下步骤:
a)通过十字头挤出来挤出至少一个包含PEKK的组合物的层;和
b)在所得结构体周围安装拱形物;
c)安装一个或多个抗拉铠装层;和
d)在所得组装体周围挤出外部聚合物护套。
在步骤(a)期间,可挤出一个或多个其他层,尤其是基于PVDF、基于聚酰胺、基于聚乙烯、尤其是基于PE-RT,或者基于用作用于将各层彼此组装的粘合剂的材料。
在以下非限制性实施例中将更详细地描述本发明。
[实施例]
实施例1 PEKK的渗透率
PEKK对气体、并且尤其是对CO2和H2S的渗透率在石油应用中起着特别重要的作用,并且相应地通过注射模塑来制备尺寸为100mm x 100mm x 2mm的PEKK(7002,由ARKEMA France销售,比率T:I=70:30)的板。还通过条带挤出随后机械加工至期望的尺寸来制备尺寸为100mm x 100mm x 2mm的8002PEKK(由ARKEMA France销售,比率T:I=80:20)的板。
通过用差示扫描量热法(DSC)测量熔融焓来表征注射模塑板中的PEKK的结晶度。对于挤出板也如此进行。由此,通过与100%结晶的理论焓进行比较,可获得注射模塑板和挤出板中的PEKK的结晶度。
然后通过将直径为90mm的由板而机械加工的盘放入到加热的渗透池(T=130℃)中来评估在严苛条件下的注射模塑板的CO2渗透率。在直径70mm的盘上对挤出板进行相同的测试。
向渗透池供应气体(当前为CO2),该气体在规定的压力下进入并且与测试材料的板的一个面接触。气体的进入压力(当前为40巴)可通过压缩机系统控制。在板的另一侧上,载体气体(当前为氮气)将渗透通过板的气体运载至检测器(当前为气相色谱仪(GC)),在其中对其进行量化。考虑板的表面积、渗透气体中的分压差、测量时间和板的厚度,使用所测量的渗透的气体的量来计算渗透率。
在瞬时状态之后的稳定状态下计算渗透率,这反映了渗透气体分子扩散通过板所需的时间。当以24h间隔的两次采样之间的测量的CO2的流量增加不超过1%时,认为已达到稳定状态。例如,在所研究的板的情况下,总共需要10天来进行渗透率测量。
结果归纳在以下表1中。
结果归纳在以下表2中。
此外,由7002PEKK(由ARKEMA France销售,比率T:I=70:30)通过挤出压延来制备厚度为50μm的无定形膜。这些膜通过在烘箱中在210℃下热处理40分钟进行结晶。面积50cm2的盘从这两个膜(无定形和结晶的)中被取出,并且用于测量对CO2、O2、N2和CH4气体的渗透率。如上所述地那样在渗透池中进行测量,但是在环境温度和大气压下进行。
结果归纳在以下表3中。
实施例2(对比)PEEK的渗透率
为了比较PEKK与PEEK的性质,重复实施例1,这次使用厚度为2mm的PEEK注射模塑板(450G,由VICTREX销售)。
如上对于CO2所述的那样,对H2S渗透率进行评估,但使用厚度为0.5mm的PEEK的注射模塑板(450G,由VICTREX销售)(随后机械加工成70mm的盘的形式),并且在15巴的压力下。
结果归纳在以下表1和2中。
此外,直径70mm的盘从通过挤出压延实现的450G PEEK的50μm膜(无定形挤出物以及在205℃下结晶大于1h的时间的挤出物)中被取出,并且用于测量对CO2、O2、N2和CH4气体的渗透率。如上所述的那样在渗透池中进行测量,但是在环境温度和大气压下进行。
结果归纳在以下表3中。
结果表明,在严苛的温度和压力条件下,PEKK的CO2渗透率明显优于PEEK的CO2渗透率。该观察更加出人意料,因为PEEK的结晶度高于PEKK。原因在于PEEK板的熔融焓大于PEKK板的熔融焓。
表1:CO2渗透率
对于H2S的渗透率,通过与PEEK相比,以相同的方式发现了PEKK明显的优越性,因为观察到PEKK的渗透率比PEEK的渗透率小2.8倍(2.8倍小)。
表2:H2S渗透率
*在0.5mm厚的板上测量
还发现,与结晶的PEEK膜相比,由结晶的PEKK制成的膜在对所有测试气体的阻隔性质方面都明显更好。类似地,与无定形PEEK膜相比,无定形PEKK膜在阻隔性质方面更好。
测试还揭示,PEKK,即使呈无定形形式的PEKK显示出比结晶的PEEK更好的对CO2、O2、N2和CH4气体的阻隔性能。
表3:PEKK和PEEK膜的渗透率
这些结果表明,在相同厚度下,在用于运输石油流出物的管道中使用PEKK允许更好地保护金属组件免受由气体(例如CO2和H2S)的迁移带来的腐蚀。而且,为了达到目标渗透率,可通过使用PEKK来减小护套的厚度,从而减小管道的重量。
Claims (17)
1.PEKK用于降低旨在与石油流出物接触的部件的CO2和H2S渗透率的用途。
2.如权利要求1所述的用途,其中PEKK具有大于5%的按质量计的结晶度。
3.如权利要求1或2所述的用途,其中PEKK具有35%至100%、优选55%至85%并且更具体地60%至80%的T:I比。
4.如前述权利要求中的一项所述的用途,其中对于1cm的厚度和1cm2的表面积、每秒和每巴的CO2压力,在130℃下的CO2渗透率小于10·10-9cm3CO2,和/或对于1cm的厚度和1cm2的表面积、每秒和每巴的H2S压力,在130℃下的H2S渗透率小于10-8cm3,CO2和H2S的量分别通过GC测量。
5.如前述权利要求中的一项所述的用途,其中所述部件选自管、护套或压力层和内部涂层,尤其是旨在用于运输石油流出物。
6.用于运输石油流出物的管道,其包括旨在与石油流出物接触的层,其特征在于,所述旨在与石油流出物接触的层包含PEKK并且对于1cm的厚度和1cm2的表面积、每秒和每巴的CO2压力,在130℃下的CO2渗透率小于10·10-9cm3CO2,和/或对于1cm的厚度和1cm2的表面积、每秒和每巴的H2S压力,在130℃下的H2S渗透率小于10-8cm3,CO2和H2S的量分别通过GC测量。
7.如权利要求6所述的管道,其中所述旨在与石油流出物接触的层是围绕金属胎体的密封护套。
8.如权利要求6或7所述的管道,其中所述旨在与石油流出物接触的层不含增强纤维。
9.如权利要求6至8中的一项所述的管道,其中所述旨在与石油流出物接触的层被至少一个机械增强层围绕。
10.如权利要求9所述的管道,其中所述至少一个机械增强层由金属制成。
11.如权利要求9所述的管道,其中所述至少一个机械增强层由复合材料制成。
12.如权利要求11所述的管道,其中复合材料包括PEKK和碳纤维。
13.如权利要求6至12中的一项所述的管道,其还包括刚性金属框架。
14.如权利要求6至13中的一项所述的管道,其还包括柔性金属框架。
15.用于制造或翻新如权利要求13所述的管道的方法,其包括以下步骤:
a.制备适当尺寸的包含PEKK的管;和
b.将所述管插入金属管内以形成衬里。
16.用于制造如权利要求14所述的管道的方法,其包括以下步骤:
a.提供金属胎体;
b.通过十字头挤出在所述金属胎体周围挤出至少一个包含PEKK的组合物的层;和
c.在所得结构体周围安装拱形物;
d.安装一个或多个抗拉铠装层;和
e.在所得组装体周围挤出外部聚合物护套。
17.用于制造如权利要求14所述的管道的方法,本发明的方法包括以下步骤:
a.通过十字头挤出来挤出至少一个包含PEKK的组合物的层;和
b.在所得结构体周围安装拱形物;
c.安装一个或多个抗拉铠装层;和
d.在所得组装体周围挤出外部聚合物护套。
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PCT/FR2018/053001 WO2019102165A1 (fr) | 2017-11-27 | 2018-11-27 | Utilisation de pekk pour la fabrication de pieces a faible permeabilite gazeuse |
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CH705381A1 (de) * | 2011-08-15 | 2013-02-15 | Moeller Medical Gmbh | Rohr beinhaltend Metallmantel mit Kunststoff-Inlay zur Verwendung bei Nieder- und Hochdruckanwendungen, insbesondere als HPLC-Säule. |
US20160069503A1 (en) * | 2013-04-29 | 2016-03-10 | Solvay Specialty Polymers Italy S.P.A. | Process for lining metal pipelines |
WO2016034181A1 (en) * | 2014-09-02 | 2016-03-10 | National Oilwell Varco Denmark I/S | An unbonded flexible pipe |
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- 2018-11-27 EP EP18827191.0A patent/EP3717237B1/fr active Active
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Publication number | Priority date | Publication date | Assignee | Title |
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US20060229395A1 (en) * | 2002-08-19 | 2006-10-12 | Tim Hsu | High temperature liner |
US20070036925A1 (en) * | 2003-09-19 | 2007-02-15 | Braad Poul E | Flexible unbonded pipe and a method for producing such pipe |
US20130112308A1 (en) * | 2010-07-14 | 2013-05-09 | National Oilwell Varco Denmark I/S | Unbonded flexible pipe |
FR3007033A1 (fr) * | 2013-06-13 | 2014-12-19 | IFP Energies Nouvelles | Composition de materiau composite pour neutraliser des composes acides et conduite comprenant une gaine realisee avec une telle composition |
CN107001787A (zh) * | 2014-10-22 | 2017-08-01 | 阿科玛法国公司 | 具有改善的性质的基于聚(亚芳基醚酮)的组合物 |
FR3046208A1 (fr) * | 2016-12-22 | 2017-06-30 | Ifp Energies Now | Conduite flexible de transport de fluide petrolier comprenant une barriere contre la diffusion |
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FR3074184B1 (fr) | 2020-07-24 |
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US11377520B2 (en) | 2022-07-05 |
EP3717237C0 (fr) | 2023-11-29 |
RU2020119943A3 (zh) | 2021-12-29 |
WO2019102165A1 (fr) | 2019-05-31 |
BR112020010299A2 (pt) | 2020-11-17 |
KR20200088420A (ko) | 2020-07-22 |
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JP2021504559A (ja) | 2021-02-15 |
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