CN102448720B - 用于油田、气田、勘探、炼油和石化应用的结构部件 - Google Patents
用于油田、气田、勘探、炼油和石化应用的结构部件 Download PDFInfo
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- CN102448720B CN102448720B CN201080023752.XA CN201080023752A CN102448720B CN 102448720 B CN102448720 B CN 102448720B CN 201080023752 A CN201080023752 A CN 201080023752A CN 102448720 B CN102448720 B CN 102448720B
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- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
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- ZBZHVBPVQIHFJN-UHFFFAOYSA-N trimethylalumane Chemical compound C[Al](C)C.C[Al](C)C ZBZHVBPVQIHFJN-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
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- B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
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Abstract
提供了用于油田、气田、勘探、炼油和石化应用的结构部件。该结构部件包含多个层,即含有复合材料的结构层;用于接触腐蚀性石油产品的耐腐蚀层,该耐腐蚀层含有选自非晶态金属、陶瓷材料和热塑性材料和它们的组合的材料;热传导率小于0.4W/m℃的耐火层。在一个实施方案中,该结构部件具有大于5分钟的烧穿时间。在另一个实施方案中,该结构部件满足根据IMO A 18/Res.753火灾试验规程的II级耐火标准。在一个实施方案中,该结构部件为具有含热塑性材料的耐腐蚀层的管道系统形式。在一个实施方案中该管道系统的特征在于具有熔化接合的管节。还提供了改善用于油田、气田、勘探、炼油和石化应用的结构部件的耐腐蚀、耐磨损和耐火性能的方法。该方法包括提供具有多个层的结构部件,所述多个层包括耐腐蚀层和耐火层。
Description
相关申请的交叉引用
本申请按照35USC 119要求申请日为2009年4月16日的美国临时专利申请No.61/170,080的权益。本申请要求前述的优先权和权益,通过引用将其公开内容并入本文。
技术领域
本发明总体上涉及先进材料例如复合物、陶瓷金属衬里、非晶态金属、耐腐蚀材料、耐热涂层等在油气勘探、炼油和石化应用中的用途。
背景技术
已知石油产品即气体和液体烃产品含有或随同它们伴有腐蚀性物质例如二氧化碳、硫化氢和氯化物等。水性流体例如用于钻井和完井的那些可产生(contribute)盐类、胺类、酸类或其它污染物,从而致使所述流体呈腐蚀性。具有高有机酸含量的原油(crude)例如含环烷酸的那些对用于采出、输送和加工该油的设备呈腐蚀性。气体例如氯化氢、二氧化碳和硫化氢在金属表面对其变得暴露的水性条件存在下产生高度酸性环境。此外,天然气和合成气通过吸收酸性气体如二氧化碳和硫化氢的处理进行调整。吸收剂和酸性组分的降解以及副产物的产生导致金属表面的侵蚀。
除侵蚀问题外,在石油产品的处理中还存在泄漏风险以及附带的防火和耐火问题。配管系统任意部分中的密封度的损失可以导致高温、高热通量、高速度的火焰(经常称作“喷射火”)。当存在喷射火时,取决于火的性质,可以随高温一起产生极高的热通量密度。对于涉及固体燃料燃烧的火(在大多数烃加工操作中不大可能),火的温度不断升高并且可在60分钟后达到900℃,在120分钟后达到约1050℃,和在240分钟后高达1150℃。热通量密度可达到高至100kW/m2。与烃类池火相比,温度上升会更快并且可在20分钟后达到1150℃的温度且具有225kW/m2的热通量密度。对于当天然气和不同凝析物在高压下燃烧时的喷射火,温度可在几秒内升至1300-1400℃,热通量密度上升达到500kW/m2。
在油气工业中使用各种控制腐蚀的方法,所述方法包括设备的定期监控和有计划更换,腐蚀抑制剂,以及设备材料升级。操作者选择适当的方法或方法组合,这取决于腐蚀的性质、复杂性和可预见性,设备失效的可能性和后果,以及监控和抑制侵蚀的能力。每种方法具有风险和缺陷。通常不可能以高度确定性监控和规划设备的经济性更换方案。抑制剂的使用可具有不期望的副作用,例如使腐蚀移动至工艺的其它部分或这可能引起一些环境顾虑。当不确知侵蚀原因、或腐蚀原因众多、或腐蚀随工艺改变而变化时,耐受性材料的选择是困难的并且几乎总是非常昂贵的。
昂贵的钢和合金,例如不锈钢、镍基高合金等材料,已用于油气工业中。已知热循环或热剧增(thermal excursion)在高温油气应用中影响包含金属的结构部件。耐腐蚀含氟聚合物塑料例如TeflonTM可用作金属配管系统中的内衬。然而,加内衬的金属管道系统会由于内衬和金属管道的物理性能(例如由热循环引起的粘弹性能)的差异而失效。在宽的温度范围内TeflonTM含氟聚合物塑料具有是碳钢10倍的热膨胀系数,但是在70°F下其为75倍。与具有190,000MPa-210,000MPa的弹性模量的碳钢相比,TeflonTM含氟聚合物塑料具有58-80MPa的弹性模量。
因为复合非金属材料提供改善的耐腐蚀性和降低的维护要求,所以使用它们作为昂贵的钢和合金的替代品。然而,当通过来自附近火焰的热传递将包含非金属复合材料的结构部件加热到它们的引燃温度或支承体燃烧温度时,所述材料发生引燃和/或支承体发生燃烧,失去结构完整性,并且在燃烧时放出大量的烟。此外,非金属材料必须不仅耐受油气应用中遇到的温度和压力,而且它们还几乎必须经受住溶剂、脆化和工艺料流中所含烃和污染物的其它潜在劣化性能。
仍存在对用于处理石油产品的具有耐腐蚀性和耐火性能的改进结构部件的需要。本发明涉及用于油气应用的具有复合物、耐腐蚀材料和热保护涂层的组合性能的结构部件,例如配管系统。
发明概述
在一方面,提供了用于容纳(contain)腐蚀性石油产品的结构部件。该结构部件包含:含有复合材料的结构层;用于接触腐蚀性石油产品的耐腐蚀层,该耐腐蚀层含有非晶态金属;热传导率小于0.4W/m℃的耐火层;其中该结构部件具有大于5分钟的烧穿时间。在一个实施方案中,非晶态金属合金是块体凝固(bulk solidifying)非晶态合金。在另一个实施方案中,非晶态金属选自非晶态金属氧化物、非晶态金属碳化物、非晶态金属碳化物-氮化物、非晶态氮化硅和它们的组合。在又一个实施方案中,所述结构部件满足根据IMO A 18/Res.753火灾试验规程的II级耐火标准。
在一方面,提供了用于容纳腐蚀性石油产品的结构部件。该结构部件包含:含有复合材料的结构层;用于接触腐蚀性石油产品的耐腐蚀层,该耐腐蚀层含有陶瓷材料;热传导率小于0.4W/m℃的耐火层;其中该结构部件具有大于5分钟的烧穿时间。在一个实施方案中,所述复合物层具有小于9,000,000psi的挠曲模量。在另一个实施方案中,所述结构部件具有大于15分钟的烧穿时间。
在一方面,提供了给结构部件提供耐腐蚀和耐火保护的方法。所述结构部件用于容纳腐蚀性石油产品,包含具有第一表面和与该第一表面相对的第二表面的结构层。所述方法包括:向第一表面施加选自陶瓷、非晶态金属和它们的组合的材料,从而形成与腐蚀性石油产品接触的耐腐蚀层;以及向第二表面施加足够量的热传导率小于0.4w/m.℃的耐火材料用以获得具有足够厚度的耐火涂层从而使结构部件满足根据IMO A 18/Res.753火灾试验规程的II级耐火标准。在另一个实施方案中,在1996年的喷射火试验程序OTI 95634中所述结构部件具有的保护比没有耐火层涂层的结构部件所获得的保护长30%。
在一方面,提供了用于容纳腐蚀性石油产品的管道系统。所述系统包含至少两个管节,其中每个管节包含:含有复合材料的结构层;用于接触腐蚀性石油产品的耐腐蚀层,该耐腐蚀层含有热塑性材料;和热传导率小于0.4W/m℃的耐火层,其中至少两个管节熔化接合在一起形成管道系统。在一个实施方案中,管道系统的特征在于满足根据IMO A 18/Res.753火灾试验规程的II级耐火标准。
在第二方面,提供了用于容纳腐蚀性石油产品的管道系统,其中所述管道系统具有至少两个熔化接合在一起的不同管节,其中每个管节包含:热传导率小于0.24BTU-ft/hr-ft2-°F的结构层;用于接触腐蚀性石油产品的耐腐蚀层,该耐腐蚀层含有热塑性材料;和热传导率小于0.4W/m℃的耐火层。
在一方面,本发明涉及将用于容纳腐蚀性石油产品的管道系统中的管节进行接合的方法,该方法包括:将两个不同管节定位成彼此接邻,其中每个管节包含含有复合材料的结构层和用于接触腐蚀性石油产品的耐腐蚀层、以及耐火层;施加能量以将所述第一和第二管节的耐腐蚀层接合在一起从而形成接合部;围绕所述第一和第二管节的接合部施加外部包裹物;以及通过化学固化和热处理中的至少一种将该外部包裹物结合到所述接合部和所述复合物结构层。
在另一方面,本发明涉及将用于容纳腐蚀性石油产品的管道系统中的管节进行接合的又一种方法。所述方法包括:在两个不同管节的腐蚀层边缘处施加能量从而一起形成接合部;围绕该接合部施加外部包裹物;通过化学固化和热处理中的至少一种将该外部包裹物结合到所述接合部和所述复合结构层;以及将足够量的耐火材料施加到所述外部包裹物和管道结构层上以使管道系统满足根据IMO A 18/Res.753火灾试验规程的II级耐火标准。
附图简要描述
图1是包含复合物层和外部膨胀型涂层的结构部件的实施方案的横截面侧视图。
图2是具有多个层即复合物层、中间陶瓷层和膨胀型涂层的结构部件的第二实施方案的横截面侧视图。
图3是具有多个层即内部陶瓷层和/或非晶态金属层、中间复合物层和外部膨胀型涂层的结构部件的第三实施方案的横截面侧视图。
图4是具有多个层即复合物层、中间金属层和外部膨胀型涂层的结构部件的第四实施方案的横截面侧视图。
图5是结构部件的实施方案的侧正视图,其中在施加膨胀型层(intumescent layer)之前使用增强网状层(mesh layer)。
图6是具有多个层的结构部件的第五实施方案的横截面侧视图,所述多个层包括陶瓷层和/或非晶态金属层、复合物层、金属层和膨胀型层(施加到未显示的增强网状层上)。
图7是具有多个层的结构部件的第六实施方案的横截面侧视图,所述多个层包括耐腐蚀热塑性内衬、复合物层和耐火绝缘层。
图8是结构部件的第七实施方案的横截面侧视图,其中膨胀型层作为另外的耐火涂层施涂到图7的结构部件上。
图9是管段的两个节段之间的接合部的实施方案的侧剖平面视图,其中不同段的耐腐蚀层是熔化接合。
图10是图9的接合部的外部的示意性横截面,其中外部纤维包裹物将两个管节的复合物层接合。
图11是绘制出管道内部温度变化作为外径上强制温度的时间的函数的坐标图。
图12是显示另一个管道在暴露于外径上强制温度后的温度变化作为半径(从ID到OD)函数的的坐标图。
图13是显示图12的管道的内部温度变化作为时间函数的坐标图。
详述
以下术语将用于通篇本说明书中并且除非另外指明外将具有以下含义。
如本文所使用的,术语“石油产品”是指天然气;天然和合成的液体烃产品(包括但不限于生物降解油,原油,包括汽油、其它燃料和溶剂的炼油产物);以及半固体/固体烃产物(包括但不限于焦油砂、沥青等)。
如本文所使用的,术语“结构部件”是指管线、管材、容器、反应器、处理设备(包括但不限于用于油气和石化工业的蒸馏塔、换热器等)。在一个实施方案中,结构部件用于容纳石油产品。
如本文所使用的,术语“结构层”是指为结构部件产生或提供结构支承的层。
如本文所使用的,术语“耐腐蚀层”是指与石油产品接触的结构部件层。腐蚀层用来降低和/或减轻通过内部容纳的石油产品所致的全面腐蚀和侵蚀腐蚀。
如本文所使用的,术语“耐火层”或“抗火层”是指在发生火灾时保护结构部件达规定时间段的层。
如本文所使用的,术语“容纳”(或者容纳(动词),或者容纳(名词))是指用于其中使用石油产品或与石油产品接触的环境,其包括石油产品的输送、加工、处理、储存、运送和容留,而无论是基于连续基础、附带基础或间歇基础。
如本文所使用的,“厚度”是指横跨(across)基材表面的材料层的平均厚度,所述材料层施加在所述基材表面上。
如本文所使用的,术语“陶瓷”是指包含陶瓷材料,或具有陶瓷材料的性能的材料,例如具有同时类似于陶瓷和金属的性能的铝化物。
如本文所使用的,“复合”材料是指由两种或更多种具有不同物理或化学性能的组成材料制得的工程材料,并且其在成品结构内于宏观层面上保持分离和相异。在一个实施方案中,复合物层包含在基质中的纤维材料,例如纤维增强的陶瓷基质复合材料,或在金属基质中具有增强纤维的金属基质复合物,或在玻璃陶瓷复合物中的玻璃纤维材料,等等。
如本文所使用的,术语“非晶态金属”是指具有无序原子尺度结构的金属材料。对于在超过1mm的厚层中具有非晶态结构的非晶态金属,该术语可有时与“金属玻璃”或“玻璃状金属”或“块体金属玻璃”互换使用。
如本文所使用的,术语“膨胀型”或“膨胀剂(intumescents)”是指材料在暴露于升高的温度时经历热降解,这生成热稳定的、发泡的多孔室(multi-cellular)残余物(称作“膨胀炭”)。
如本文所使用的,“熔化焊接”或“熔化结合”或“熔化接合”是指用于将结构部件的不同节段例如管节接合在一起而不需要机械地将它们接合在一起(如在现有技术中)例如将带凸缘的节段栓固的方法。
如此处所使用的,术语“腐蚀性石油产品”是指在油气工业中于腐蚀性或材料劣化环境下应用,或腐蚀性材料的容纳,包括但不限于:含有硫、亚硫酸(sulfurous)、硫化氢、硫酸(sulfuric)、氟化氢或氯化氢或有机酸(例如乙酸、甲酸和高分子量有机酸)、二氧化碳蒸气和冷凝物、碳酸盐和碳酸氢盐、氨、胺、咪唑(imidiazole)与它们的盐和衍生物、以及氯化物和氟化物盐和酸;油气环境中的高度酸性至高度碱性溶液;在油气环境中含有这些物质的在酸性和碱范围内且为各种形式例如H2S(酸性水)的水;包括低和高API比重的原油的烃;经处理或炼制的油例如石脑油、瓦斯油、渣油和运输燃料(例如汽油、柴油、喷气燃料)。
在一个实施方案中,结构部件的特征在于具有多层结构,其中最内层包含提供腐蚀、磨损和/或侵蚀保护的材料,最外层包含耐火层,例如膨胀型材料,其能够经受住烃火焰达限定时间量。耐腐蚀层包含至少一种选自热塑性材料、陶瓷材料、金属陶瓷、非晶态金属和块体金属玻璃/金属复合物的材料。结构层包含复合材料。耐火层包含膨胀型涂层、绝缘层或它们的组合中的至少一种。
结构层:在一个实施方案中,结构层包含复合材料。复合物层用作包括耐火层和/或耐腐蚀层在内的其它附加层的基材或支承层。
复合物层的厚度随着许多因素而变化,所述因素包括但不限于:a)应用类型,例如工艺/输送管道、容器、换热器系统、容器中的内构件例如蒸馏塔板,等等;b)结构部件的尺寸,12”或48”标称直径管道,直径为8ft.的容器,等等;c)操作环境,例如内部爆破压力,等等;和d)在结构部件上的位置,例如接合部可能比壁更厚。例如,对于25cm标称直径管道,复合物层可以具有7mm的厚度,相比而言对于具有48”直径的管道,复合物层可以具有3-5”的厚度。
复合物层可由一层(ply)或多层形成,其中每个层具有一种或多种置于基质内的纤维,例如聚合物、树脂、陶瓷材料或热塑性材料。复合物层可由一个或多个复合材料层形成,其中所述层可以是相同或不同的复合材料。
在一个实施方案中,复合物层的基质材料是选自酚醛树脂和环氧树脂的树脂材料。在另一个实施方案中,基质材料是具有优异耐火特性的特种化学品,选自氰酸酯、酚醛树脂(phenolic)/聚酯共混物、硅树脂(silicone)和苯二甲腈(phthalonitrile)。在第三实施方案中,树脂基质是选自硅氧烷改性的酚醛树脂、呋喃树脂和它们的混合物的材料。在第四实施方案中,树脂材料是乙烯基酯。
在一个实施方案中,可将炭黑加入到树脂材料中以使复合物层具有108ohms/cm的电阻率。炭黑添加剂有助于提供静态放电,该静态放电可有利地防止容纳在结构部件内的易燃石油产品的引燃。在另一个实施方案中,可使用阻燃添加剂,例如三水合氧化铝(“ATH”),商业非溴化阻燃添加剂如Avtec的TSWB来改善复合物层的阻燃性能。
可对一个或多个复合物层中的纤维材料和取向进行选择以给结构部件提供所需的机械特性。在一个实施方案中,结构复合物层包含基于该复合物总重量计约55-85wt.%的增强纤维。适合用作结构部件的增强纤维的材料包括但不限于玻璃、碳、陶瓷材料、聚合物材料、金属和金属合金。实例包括但不限于碳、玻璃、聚酰胺、聚酯、铍、碳化铍、氧化铍、钢、石英、钽、钛、氧化铝、硅酸铝(aluminum silica)、铝、钨、碳化钨等。
在一个实施方案中,复合材料是在金属基质中的金属纤维增强复合物,所述纤维由奥氏体或沉淀硬化的不锈钢或镍基合金构成。同样,可使用金属合金,所述金属合金具有比复合材料强度更大的强度并且在高达600℃的温度下不会被热机械处理永久性损伤。纤维可以例如是Ti、TiAl、FeAl、NiAl或Co丝线。这种金属纤维增强的复合材料包含以夹层(sandwich)结构交替设置的金属层(作为基质)和增强金属层。金属纤维以松散结构形式置于金属层之间,夹层结构通过热机械方法进行结合。
在一个实施方案中,增强纤维包含结构纤维和/或柔性纱。结构纤维可以由碳、尼龙、聚酯、芳纶(aramid),热塑性材料、玻璃、凯芙拉(Kevlar)纤维或其它合适的纤维材料形成。在一个实施方案中,增强纤维包含由尼龙、聚酯、芳纶、热塑性材料、玻璃或其它合适的纤维材料形成的柔性纱(编织纤维)。在一个实施方案中,复合材料是细丝缠绕(filament wound)玻璃增强的乙烯基酯。
在一个实施方案中,复合材料包含作为增强纤维的陶瓷材料。在一个实施方案中,陶瓷纤维包含选自非晶态硼、碳化硼、氮化硼、无定形碳、类金刚石碳(DLC)、金属硼化物、碳化物、氮化物、氧化物、难熔金属、硅化物、碳化硅、硫化物、钨和碳化钨、以及它们的混合物的材料。在一个实施方案中,复合材料包含在钛合金基质中的硅、硼和碳化硅纤维。
在一个实施方案中,复合材料是商购陶瓷纤维例如NicalonTM和/或NextelTM纤维在陶瓷基质中的连续纤维陶瓷复合物(CFCC)。在另一个实施方案中,复合材料包含在玻璃-陶瓷基质中的陶瓷纤维,例如锂铝硅酸盐复合物。在又一个实施方案中,复合材料包含在环氧基质中的陶瓷纤维,例如在环氧树脂中的高模量多晶氧化铝陶瓷纤维的细丝。
在一个实施方案中,复合物层中的增强纤维可以织造、编织(braided)、针织(knitted)、缝合(stitched)、周向缠绕(circumferentially wound)或螺旋缠绕(helically wound)。在一个实施方案中,纤维可以双轴或三轴编织。复合物层可以通过拉挤方法、编织方法或连续细丝缠绕方法形成。在又一个实施方案中,可通过以下方法中的任意一种将纤维纳入基质中形成复合物:树脂浸渍、拉挤、细丝缠绕和树脂输送模制。
在其中复合物层包含热固化基质的一个实施方案中,所述基质具有至少180°F(82℃)的玻璃化转变温度。在其中使用热塑性基质的情形中,所述基质具有至少250°F(121℃)的熔化温度。
在一个实施方案中,复合材料还包含至少一种使该复合物具有有效阻燃程度的阻燃添加剂。在一个实施方案中,当将复合物暴露于约50kW/m2的辐射热源时,该复合材料具有大于150秒的ASTM E-1345易燃性。
在一个实施方案中,复合材料具有50-90MPa的层间剪切强度,和在一个实施方案中具有750-1500MPa的挠曲强度,以及在另一个实施方案中具有800-1300MPa的挠曲强度。在一个实施方案中,对于其中部件可遭受高的内压的应用,复合物层具有超过100,000psi(689MPa)的轴向弹性模量。在一个实施方案中,复合物层具有至少100,000psi(689MPa)的拉伸模量。在另一个实施方案中,所述层具有至少250,000psi(1724MPa)的拉伸模量。
在结构部件包含+/-55程度(degree)细丝缠绕玻璃增强乙烯基酯的一个实施方案中,复合物层的特征在于具有约1.14*10^6psi的轴向挠曲模量和拉伸模量,1.89*10^6psi的环箍(hoop)挠曲模量和拉伸模量,1.16*10^6psi的剪切模量,和19.94*10^-6in/in/°F的轴向线性热膨胀系数(CLTE)。层合结合部的特征在于具有约1.5*10^6psi的轴向挠曲模量和拉伸模量,1.5*10^6psi的环箍挠曲模量和拉伸模量,以及12*10^-6in/in/°F的CLTE。在没有任何玻璃增强的情况下乙烯基酯树脂相比而言(comparable)的挠曲模量和拉伸模量为5.1*10^5psi。
耐腐蚀层:结构部件包含至少一个与容纳在其内的石油产品接触的耐腐蚀层。耐腐蚀层包含热塑性材料、非晶态金属、陶瓷材料或它们的组合中的至少一种。在一个实施方案中,耐腐蚀层直接位于结构复合物层上。
在一个实施方案中,在耐腐蚀层和结构复合物层之间提供多个通气孔,从而有助于释放可能受困在层间的任何压力。在另一个实施方案中,在结构层中提供多个通气孔用以释放积累压力。
取决于所使用的材料,耐腐蚀层厚度发生变化。当热塑性材料用作耐腐蚀层时,该层在一个实施方案中具有0.5-25mm的厚度;在第二实施方案中具有1-15mm的厚度;和在第三实施方案中具有2-10mm的厚度。在一个实施方案中,当陶瓷材料用作耐腐蚀层时,该层在一个实施方案中具有0.01-10mm的厚度;在第二实施方案中具有0.015-5mm的厚度;在第三实施方案中具有0.75-3mm的厚度;和在第四实施方案中具有0.1-2mm的厚度。当使用非晶态金属时,耐腐蚀层在一个实施方案中具有0.010-5mm的厚度;在第二实施方案中具有0.015-3mm的厚度;在第三实施方案中具有0.75-2mm的厚度;和在第四实施方案中具有0.5-1mm的厚度。
热塑性内衬作为耐腐蚀层:在一个实施方案中,结构部件包含至少一个热塑性内衬(层)作为与石油产品接触的内涂层,用以保护不受容纳在其中的石油产品的腐蚀/侵蚀。在一个实施方案中,将热塑性内衬直接结合在复合物层上。热塑性内衬可由任何合适的热塑性材料形成,所述热塑性材料包括但不限于例如聚氯乙烯、聚丙烯、高密度聚乙烯、聚偏氟乙烯(KynarTM)、乙烯-氯三氟-乙烯(HalarTM)、聚四氟乙烯(TeflonTM)、聚苯硫醚(PPS或RytonTM)、全氟烷氧基氟碳、离聚物和三元离聚物(SurlynTM)组合物,和热塑性弹性橡胶。在一个实施方案中,热塑性内衬可包括玻璃垫衬背。在另一个实施方案中,可对其进行化学处理或蚀刻以改善对结构层的附着。在一个实施方案中,热塑性材料是聚四氟乙烯。在另一个实施方案中,该材料是聚苯硫醚。
在一个实施方案中,耐腐蚀层包含多个热塑性内衬,所述内衬由相同或不同的材料构成。在一个实施方案中,可以在施加外部结构复合物层之前将粘合剂施涂到多个耐腐蚀层和/或可以将粘合剂在其施涂到耐腐蚀内衬之后施涂到结构复合物层。在另一个实施方案中,可以加热耐腐蚀层的外表面以增强附着力和/或将所述层嵌入结构复合物层中。
在耐腐蚀层包含PPS的一个实施方案中,内衬的特征在于具有500,000psi的拉伸模量,575,000psi的挠曲模量,以及在低于185°F的温度下28*10^-6in/in/°F的CTLE和在高于185°F的温度下64*10^-6in/in/°F的CTLE。对于包含全氟烷氧基氟碳的对比耐腐蚀层,拉伸模量为39,000-51,000psi;挠曲模量为90,000-97,000psi,和CTLE为约77.8*10^-6in/in/°F。
陶瓷层作为耐腐蚀层:在一个实施方案中,结构部件包含至少一个陶瓷层作为耐腐蚀层。在一个实施方案中,陶瓷层是与容纳在其中的腐蚀性材料接触的腐蚀层。在另一个实施方案中,陶瓷层位于复合物层和直接与腐蚀性材料接触的金属箔层之间。
在腐蚀性以及侵蚀应用的一个实施方案中,例如在流化催化裂化单元(FCCU)中,使用陶瓷层作为与石油产品接触的涂层。在FCUU工作条件下,结构部件暴露于侵蚀性的石油流体以及硬固体颗粒例如催化剂颗粒。在其中将结构部件用于侵蚀性油气勘探应用和其中将结构部件暴露于磨蚀性材料例如砂子的一个实施方案中,使用陶瓷层作为与烃产品接触的腐蚀涂层。
在一个实施方案中,陶瓷层包含至少一种金属氧化物例如二氧化钛(TiO2)、氧化锆(ZrO2)、五氧化二钽(Ta2O5)、氧化铝(Al2O3)、二氧化铪(HFO2)、氧化铈(CeO2),相稳定的氧化锆例如氧化钇稳定的氧化锆、氧化钙稳定的氧化锆、氧化钪稳定的氧化锆、氧化镁稳定的氧化锆、由任意稀土氧化物稳定的氧化锆,或类似氧化物,或它们的组合例如与氧化锆共混的钇氧化物。在一个实施方案中,首先施加陶瓷层作为金属层,即Ti、Zr、Ta、Al、Hf、Ce等,以最终被氧化。在又一个实施方案中,陶瓷层包含金属碳化物例如碳化硅、碳化铝、碳化硼和碳化锆;金属氮化物例如氮化硅、氮化硼和氮化铝;金属硅酸盐例如硅酸铝、堇青石、锆石和滑石;以及金属硼化物例如四硼化硅、硼化钨和硼化锆中的至少一种。
在一个实施方案中,陶瓷层包含陶瓷金属材料,即具有陶瓷相和金属粘合剂相的陶瓷-金属复合物。陶瓷金属通常比本领域中已知的耐高温材料更加耐侵蚀。在一个实施方案中,陶瓷相是碳化物、硼化物、碳氮化物、氧化物、氮化物陶瓷或这些陶瓷的混合物。在一个实施方案中,金属相是选自钴、镍、铁、钼、钛、锆、铝和它们的混合物的金属。在一个实施方案中,陶瓷层包含氮化铬,或纳米结晶金属碳化物/非晶态烃复合物(MC/aC:H)。在另一个实施方案中,陶瓷层包含TiC/非晶态烃纳米复合物。在又一个实施方案中,陶瓷层包含碳化铬或氧化铬-镍铬涂料。
在一个实施方案中,陶瓷层包括约30-95vol.%陶瓷相,和金属粘合剂相。在一个实施方案中,金属粘合剂相包含至少30wt.%的选自Fe、Ni、Co、Mn和它们的混合物的金属,以及至少一种选自Cr、Al、Si和Y的元素。
在一个实施方案中,陶瓷层包含铝化镍、铝化铁、铝化钽、铝化钛例如γ铝化钛或它们的混合物中的至少一种。在又一个实施方案中,所述层包含具有优异的抗氧化和硫化性的铝化铁-陶瓷复合物。在另一个实施方案中,所述层是表面处硅浓度为约1-10wt.%的硅改性的扩散铝化物层。在另一个实施方案中,所述层包含硅改性的铝化物或钇改性的铝化物,其作为10-100μm厚的薄涂层进行施加。在又一个实施方案中,陶瓷层是在高达900℃的温度下具有优异耐热腐蚀性的铂改性的铝化物涂层。
在一个实施方案中,陶瓷材料还包括作为颗粒或纤维或这二者的耐高温填料。在一个实施方案中,填料包含任意的玻璃、石墨或陶瓷纤维和颗粒。在另一个实施方案中,陶瓷层是包含10-25wt.%硅酸钠、15-30wt.%水,12-25wt.%粘土和15-35wt.%云母的耐火材料。
在一个实施方案中,除陶瓷涂层外,还使用另外金属箔来提供具有二(duplex)或双(dual)组成部分涂层的复合物层从而进一步给结构部件提供抗磨损性和耐腐蚀性。在一个实施方案中,另外涂层是金属或金属合金的薄(例如小于约3μm)层,例如Ni或Ni合金层,其施加在陶瓷涂层例如氮化铬或MC/aC:H层的顶部。在一个实施方案中,复合物层通过本领域已知的方法,例如离子注入如等离子体渗氮、等离子体浸没离子注入或典型(classical)离子注入等进行表面处理以为其提供另外涂层。
在一个实施方案中,将陶瓷层作为涂层直接施加到复合物层上。在另一个实施方案中,将陶瓷层夹在复合物层和另一个层例如热塑性耐腐蚀内衬、金属片层(sheeting layer)或膨胀型涂层之间。在热塑性材料作为与石油产品接触的耐腐蚀层的实施方案中,陶瓷层用作绝缘涂层,从而使得下面的复合物层在由于火和/或热而破坏掉之前经受住较高的温度和/或较长的时间。
在一个实施方案中,陶瓷层还用作渗透层,发挥抑制/减轻流体向结构部件内层中渗透的作用。在一个实施方案中,陶瓷层具有每seccm2-bar小于0.01cm3/cm的渗透率。
在一个实施方案中,陶瓷层具有从0.1微米至小于10mm的厚度。在第二实施方案中,陶瓷层具有约1-约200密耳(1密耳=.001英寸)的厚度。在另一个实施方案中,保护性陶瓷层是具有0.1-5微米厚度的氧化物层。在第三实施方案中,陶瓷层具有从0.5mm至小于5mm的厚度。在第四实施方案中,陶瓷层小于2.5mm。陶瓷层的厚度取决于许多因素,这些因素包括但不限于所使用的涂覆方法、容纳在其中的石油产品和是否使用陶瓷层作为中间层或涂层。
在一个实施方案中,陶瓷层的特征在于具有优异的侵蚀和断裂韧性性能。在一个实施方案中,陶瓷层具有按照Hot Erosion/AttritionTesting方法(HEAT)测量的至少5.0的HEAT耐侵蚀指数,其是在经受热和磨蚀颗粒物质时材料性能的量度,并且是依照美国专利公开No.US2008/0003125中所描述。HEAT耐侵蚀指数越高,材料的耐侵蚀性能越好。在这种HEAT试验中,所述指数通过测量试验材料在给定持续时间内损失的体积来确定。试验模拟器的速度范围是10-300ft/sec(3.05-91.4m/sec),其涵盖流化催化裂化单元(FCCU)的速度范围。试验温度是可变的并且可以为至多1450°F(788℃)。冲击(impingement)试验角为1-90度。质量流量可以为1.10-4.41lbm/分钟。
在一个实施方案中,通过使用以下方法将陶瓷层施加到复合物层(或相邻层例如金属箔或热塑性材料层)上:化学气相沉积(CVD),用等离子体进行热喷涂,高速氧燃料(HVOF)或高速空气燃料(HVAF)喷涂,线电弧(wire arc),物理气相沉积(PVD),RF(射频)溅射和电镀,漆料喷射,喷涂,浸涂,用刷子或轧辊施涂,粉末涂覆,气相沉积,或上述的组合。
非晶态金属层作为耐腐蚀层:在一个实施方案中,结构部件至少包含非晶态金属层作为与石油产品接触的内涂层,用以保护不受容纳在其中的石油产品的腐蚀/侵蚀。在一个实施方案中,将非晶态金属作为涂层直接施加在复合物层上。在另一个实施方案中,将非晶态金属涂覆到沉积在复合物层上的金属片层上面。在第三实施方案中,将非晶态金属涂覆到紧贴复合物层的陶瓷层上。
应理解的是,非晶态涂层可包括可以无规填充在合金基质例如颗粒或纳米颗粒内的结构连接件(association)或单元,所述颗粒或纳米颗粒具有10-100埃;10-150nm;和15-1000nm中任意的尺寸。其实例包括直径为1-100nm的纳米晶体。
在一个实施方案中,非晶态金属层的厚度为0.1-500μm。在第二实施方案中为5-2,500μm。在第三实施方案中为厚度10-100μm。在第四实施方案中小于50μm。在第五实施方案中为20-100μm。在第六实施方案中,非晶态层具有约0.5-约100密耳的厚度。
在一个实施方案中,非晶态金属是商购的铁基合金,例如Superhard Steel AlloysTM。在另一个实施方案中,非晶态金属是以商标名VITROLOY(基于Ti、Zr、B、Ni)销售的商购材料。
在一个实施方案中,非晶态金属包含至少50%铁,可选的铬,一种或多种选自硼和磷的元素,钼和钨中的一种或这两种;以及Ga、Ge、Au、Zr、Hf、Nb、Ta、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、N、S和O中的至少一者。在第三实施方案中,金属玻璃包含(Fe0.8Cr0.2)79B17W2C2。
在另一个实施方案中,非晶态金属层包含非晶态金属氧化物(a-Me1-xCx),非晶态金属碳化物(a-Me1-yCy),非晶态金属碳化物-氮化物(a-Me(C,N)),或非晶态氮化硅(a-Si1-zNz),其中x为0.3-0.7,y为0.25-0.9,z为0.3-0.8,和Me(金属)主要是过渡金属例如Cr、Al、Ti、Zr或者其它化学元素例如硅(Si)中的一种。
在另一个实施方案中,非晶态金属层包含如美国专利公开No.US2009/0014096(通过引用以其全文并入本文)中所公开的具有改善耐腐蚀性能的块体凝固非晶态合金(BMG)。在一个实施方案中,所述层包含与CoCrMo的耐腐蚀性相当(match)的Zr-Ti基BMG,其具有分子式:(ZraTib)1-z(BecXd)z,其中X是选自Y、Co、Fe、Cr、Mo、Mg、Al、Hf、Ta、Nb和V的添加材料;z为20-50at%;c和d之和等于z,c为至少约25at%;以及电负性大于1.9的元素仅以痕量存在。
在一个实施方案中,通过热沉积或喷涂技术将非晶态金属层施加到相邻层上。喷涂技术的实例包括火焰喷射、冷喷涂、等离子体喷射、丝电弧、爆炸喷枪、冷喷射和高速氧燃料(HVOF)。在一个实施方案中,使用热喷涂,其中熔融或半熔融的金属被喷射到结构部件的支承层上。在另一个实施方案中,将硬颗粒涂料基质系统施加到结构部件的基材层例如陶瓷层或复合物层上。
在施加非晶态金属层作为涂层后,在一个实施方案中通过热处理方法使涂层至少部分玻璃化。玻璃化可以致使形成纳米级或接近纳米级大小的晶粒。
在一个实施方案中,通过形成多个玻璃层的连续积层来形成非晶态金属层。在另一个实施方案中,非晶态金属层通过在预定温度和控制速率下金属玻璃层的不同加热/冷却循环来形成,用以产生不同的显微组织和最佳的耐腐蚀性。在又一个实施方案中,将非晶态金属层形成为梯度涂层,所述梯度涂层通过在冷或热喷涂操作期间将一种非晶态金属粉末变换为另一种非晶态金属粉末来完成。在第四实施方案中,梯度层可以是金属(或陶瓷)材料,所述材料包含与非晶态金属层、与第一非晶态金属、与具有更多合金化元素的第二不同非晶态金属等相邻的层。梯度结合产生熔合(fuse)界面使得在金属材料和基材之间存在至少部分金属结合(metallic bonding)。
在一个实施方案中,非晶态金属层具有至少约5GPa的硬度。在另一个实施方案中,包含Superhard Steel AlloysTM的非晶态涂层具有至少约9.2GPa的硬度。在第三实施方案中,具有至少约16GPa的硬度。在一个实施方案中,将非晶态金属层与相邻层例如金属层、陶瓷层或复合结构层结合,其中结合强度为至少5,000psi。在一个实施方案中,非晶态金属层在约90℃的6.5N HCl中具有μm/年的量级的腐蚀速率。在一个实施方案中,甚至将非晶态层与12M HCl溶液接触1周也没有检测到腐蚀。在又一个实施方案中,非晶态层在0.6M NaCl中(1/3月)没有显示出质量损失(低于ICP-M的检测极限)。
可选的抗挤压层:在一个实施方案中,将复合结构层被覆到抗挤压层上,所述抗挤压层包含可有助于提高复合物层强度的材料。在一个实施方案中,所述层给复合材料提供抗挤压性或抗挤毁性。在一个实施方案中,抗挤压层可以结合或不结合到复合物内层。抗挤压层可以包含一个或多个热塑性材料层、热固化材料层或金属材料层。
在一个实施方案中,抗挤压层是金属层(箔)。在一个实施方案中,金属选自铝、铝合金、钢、碳钢、不锈钢和它们的组合。在一个实施方案中,该片材具有置于与复合材料接触的外表面上的粘附结合层。
在一个实施方案中,在复合物层制造期间围绕复合物层包裹金属箔,或在制造中共同形成金属箔。或者,可使用涂覆方法例如沉积;用等离子体热喷涂或HVOF喷射、HVAF喷射或丝电弧喷射;物理气相沉积;RF溅射;电镀;粉末喷涂,和它们的组合将金属箔施加到复合物层上。在又一个实施方案中,金属箔包含具有低熔化温度的易熔金属,使得允许该金属以液体或半液体状态施加到复合物层(或陶瓷层,或另一个中间层)上。
可选的能量吸收层:在一个实施方案中,结构部件还包含置于复合物层表面上(在远离与石油产品接触的表面的表面上)的能量吸收层。在一个实施方案中,能量吸收层具有约0.6-3毫米的厚度。能量吸收层包含能够在温度低于结构壁的劣化温度即低于复合物层的劣化温度下通过相转变以例如产生气体来吸收能量的材料。通过这种相转变形成的气体在复合结构内产生绝热空气套(pocket)。
在一个实施方案中,能量吸收层包含选自以下的材料:聚乙烯、水合硫酸钙(石膏)、氢氧化铝和其它能够在低于约300℃气化或产生气体组分的水合化合物物或含氢氧化物的化合物。在其中聚乙烯用作能量吸收材料的一个实施方案中,可将其以片材形式施加到复合物层上,从而形成所需的层数目或层厚度。当能量吸收材料是除聚乙烯外时,可将其以片材形式、喷涂物形式或构造成配合起来包裹复合物层的实心半片形式施加。
耐火层:结构部件还包含用作被动防火的耐受层作为最外层或内部保护涂层。该耐受层的特征在于具有低的热传导率以在发生火灾时保护设备和其内容物。耐火层的益处之一是其能够吸收在热事故(例如在与结构部件相邻的区域中的火)期间产生的一些热能,从而防止或延迟内部的层暴露于可以导致设备失效的热失控。随着作为另外燃料的烃泄漏到火灾中,设备失效可具有灾难性后果。
在一个实施方案中,耐受层具有0.03-0.20W/m.K(在70℃下)的热传导率。在第二实施方案中,该层具有0.04-0.08W/m.K(在70℃下)的热传导率。在耐受层包含在提高的温度下膨胀的膨胀型材料的第三实施方案中,耐受层在200-800℃的温度范围具有0.1-0.4w/m.℃的热传导率。在耐受层包含膨胀型材料的第四实施方案中,所述层在室温至800℃的温度范围中(在不同火情下的热模型中)的热传导率值为0.005-0.4W/m℃。
在一个实施方案中,耐火层配设有多个通气孔。在正常操作期间,通气孔有助于释放可能在设备中积累的过量的热。在一个实施方案中,可以将吹风机/风扇装配到通气孔中用于获得有效通风循环。
膨胀型材料作为耐火层:在一个实施方案中,耐火层包含膨胀型层。在一个实施方案中,膨胀型层在达到该材料的活化温度(例如暴露于火)时膨胀约15-30体积倍。在热失控事故(例如火灾)中,膨胀型层通过吸热反应吸收过量的热。一旦达到活化温度(或“开始膨胀温度”或SET)时,所述层开始胀大(swell)或膨胀。随着膨胀型层胀大,它在火焰和结构部件之间提供了绝缘阻挡层。在膨胀之后,该材料产生炭层或灰状层。在一个实施方案中,不燃性炭层防止或至少阻止热传递至下面的复合物层基材材料。
在一个实施方案中,在施加膨胀型层之前,首先将增强网状物施加到结构系统,例如复合物层或中间层如金属金属片。当暴露于火灾的升高的温度时,所述网状物有助于膨胀型材料保持它们的绝缘层或炭层。在一个实施方案中网状物是松散织造材料,其可以是或可以不是首先充满膨胀型层,然后围绕结构部件进行包裹。或者,网状物可首先围绕结构部件进行包裹,然后将膨胀型材料施加到该网状物上。
在一个实施方案中,膨胀型层包含插入在片状剥落和/或可膨胀无机材料(选自可膨胀石墨和可膨胀云母)的网格层之间的防火化合物。在一个实施方案中,可膨胀无机材料以膨胀型层的5-50wt.%的量存在。
在一个实施方案中,膨胀型层包含可膨胀石墨插层化合物,其通过将石墨颗粒分散在溶液中而产生,其含有氧化剂和带插入的客体(guest)化合物。在一个实施方案中,氧化剂选自硝酸、氯酸钾、铬酸、高锰酸钾、过氧化氢、磷酸、多聚磷酸等。
在一个实施方案中,膨胀型层是如美国专利公开No.US2004/0054035中所公开的适合于预安装或后安装到结构部件的柔性层,包含由如下构成的含水分散体:20-70wt.%的成膜聚合物,20-70wt.%的阻燃剂组合物,1-10wt.%的平均颗粒尺寸为40-150微米的玻璃或陶瓷材料,5-30wt.%的可膨胀薄片石墨,和可选的1-10wt.%的磷基阻燃剂,其中所有wt.%加起来等于100%。
可将膨胀型化学物质纳入各种涂层系统中,包括环氧化物、脲醛、酚醛(novolac),聚偏二氯乙烯、聚氯乙烯、聚丙烯腈、聚脲、有机基聚硅氧烷、不饱和聚酯及其共聚物、聚氨酯、乳胶、水基物质(water-borne)和溶剂基物质(solvent-borne)。在一个实施方案中,膨胀型涂层含有在选自以下的载体材料中的片状剥落石墨:丙烯腈丁二烯苯乙烯(ABS)、聚邻苯二甲酰胺(PPA)、结晶聚合物、聚苯乙烯、硅橡胶、胶乳、丙烯酸系聚合物或共聚物、茂金属聚合物、聚乙烯、聚丙烯、聚乙烯-聚丙烯共聚物、丙烯酸系聚合物、聚碳酸酯以及它们的混合物。在一个实施方案中,膨胀型涂层包含5-50wt.%片状剥落石墨。
在一个实施方案中,膨胀型涂层是商购涂料产品,例如水基树脂、环氧基树脂、基于聚氨酯的树脂、基于脲醛的树脂。商购膨胀型涂层材料的实例包括Houston,Tex.的Flame Seal Products,Inc.的FX-100TM;Melbourne,Fla.的Hy-Tech Thermal Solutions,Inc.的CKC-F-268TM;Lancashire,United Kingdom的Interex International,Ltd.的PycotexTM;MM Systems Corporation of Pendergrass,GA的PyroflexTM;Kent,United Kingdom的Firetherm Intumescent andInsulation Supplies,Ltd.的FiresteelTM;Bay of Plenty,New Zealand的Altex Coatings,Ltd.的Firetex TM;Ontario,Canada的AD FireProtection Systems,Ltd.的A/D FirefilmTM;Osaka,Japan的NipponPaint Company的TaikalittTM;St.Louis,MO的Carboline的Thermo-lagTM;来自International Paint of Akzo Nobel的CHARTEKTM;和Eagle Specialized Coatings and ProtectedEnvironments,即DW Pearce Enterprises,Ltd.of British Columbia,Canada的一个部门的SafecoatTM产品,以及其它。
在一个实施方案中,膨胀型层还包含1-20wt.%的量的陶瓷(或玻璃)中空微球。在一个实施方案中,所述微球具有40-150微米的平均颗粒尺寸。在一个实施方案中,所述微球的颜色为白色。陶瓷微球在纳入环氧(或类似聚合物)树脂粘合剂中形成涂层时,提高涂层反射红外辐照的能力从而使少很多的热吸被收到涂层中并且该涂层在开始破坏掉或膨胀之前经受住较高的温度。所述微球还极大地提高膨胀型层的绝热性能。
在一个实施方案中,膨胀型层还包含导电材料以防止电荷积累。在一个实施方案中,导电材料由较大的导电颗粒例如本体直径(bulkdiameter)为1/32”至1/2”和长度为1/32”至1”的短纤维。在另一个实施方案中,导电颗粒是本体直径为1/4”至1/2”和长度为1”至4”的纤维、薄片、球等形式。
在一个实施方案中,膨胀型层包含开始膨胀温度(SET)为150-200℃的材料。SET是膨胀型层由于例如与结构部件相邻区域中的火所致而开始膨胀时的温度。在另一个实施方案中,所述层包含SET为至少200℃的材料。在第三实施方案中,包含SET为至少250℃的材料。在第四实施方案中,包含SET为至少约300℃的材料。
在一个实施方案中,包含膨胀型材料的耐受层在达到其SET点时膨胀小于25%。在另一个实施方案中,膨胀小于50%。在第三实施方案中,膨胀小于100%。
在一个实施方案中,耐火层包含至少两个具有不同材料特性的不同层,其中外层比内层具有较高的热容量。在结构部件外部发生火灾时,外层快速吸收过量的热能并且有助于在防止设备上形成热点。具有较高SET的外层延迟了传递到内层的热能,从而提供了对热失控向较内的膨胀型层和/或包含不同材料如硅酸钙的耐受层蔓延的抵制。
可使用本领域已知的方法将膨胀型层施加到结构部件上,所述方法分一次或多次施加产生所需的涂层厚度,包括但不限于等离子体喷射,漆料喷射,喷涂,浸涂,用刷子或辊施涂,粉末涂覆,气相沉积,刀口涂覆或刮片涂覆,或上述的组合,接着按具体膨胀型材料所需在室温或提高的温度下进行干燥,以形成附着性耐久涂层。非平面的表面可以通过模涂(die-coating)、喷涂、刷涂、浸涂等进行涂覆,并且类似地进行干燥。在一个实施方案中,膨胀型层是以可围绕(或捆裹)结构部件的基材进行包裹直到该基材覆盖有至少一个膨胀型层的“包裹物”形式。
在使用膨胀型层作为耐火层的一个实施方案中,膨胀型层的干燥厚度为100微米-100mm,这取决于所需的防火水平。在第二实施方案中,膨胀型层具有0.5-5mm的厚度。在第三实施方案中,膨胀型层具有3-10mm的厚度。在第四实施方案中,厚度为至少15mm以上。在第五实施方案中,层厚度为至少50mm。在第六实施方案中,厚度小于20mm。膨胀型涂层可作为单一层或多个层进行施加。对于溶剂基或水基膨胀型产品,可通过施加多个涂层获得较高的干燥膜厚度。当用作耐火层时,膨胀型涂层的热传导率在提高的温度下发生变动。在一个研究中,显示在初始加热阶段,膨胀型层的有效热传导率降低直到表面和内层例如复合物层保持大约不变,然后热传导率收敛于恒定值。
绝缘材料作为耐火层:在一个实施方案中,作为膨胀型涂层的替代或补充,结构部件包含绝缘材料作为耐火层。在一个实施方案中,绝缘层是内部耐火层,进一步受保护于或涂覆有作为最外层的膨胀型层。在另一个实施方案中,绝缘材料仅充当耐火层。在又一个实施方案中,将绝缘层是在外部施加的绝热系统或最外耐火层。
在一个实施方案中,耐火层包含厚度为1-10”的绝缘层,包裹在绝缘体周围用以将绝缘保持在适当位置的网状物,和保持绝缘体干燥的外套(或耐候阻挡层)。在另一个实施方案中,绝缘层为2-4”厚。
在一个实施方案中,耐火层包含选自以下的嵌入网状层中的绝缘材料:硅酸钙(ASTM C 533I型或II型),蜂窝状玻璃(ASTM C 552I型),膨胀珍珠岩(ASTM C 610),矿棉(ASTM C 547分类3或ASTMC 612 4B型2类),或它们的混合物。在一个实施方案中,网状层包含金属丝网。在另一个实施方案中,网状层包含18规格(0.047英寸直径)或16规格(0.063英寸直径)类型的绑丝、304不锈钢。
在一个实施方案中,耐火层是最大使用温度为1200°F和最大密度为14lbs/ft3或22lbs/ft3的I型绝缘材料。在另一个实施方案中,它是最大使用温度为1700°F和最大密度为22lbs/ft3的II型材料。在一个实施方案中,耐火层是在暴露于最大使用温度后最大线性收缩为2%,和热传导率为0.040-0.075W/m.°K的硅酸钙。
可选的中间容纳结构:在一个实施方案中,结构部件还包含与复合物层外表面结合的第二容纳结构。在一个实施方案中,容纳结构包含覆盖复合物层表面的多层织物,其中该多层织物具有与复合物层外表面结合的第一层和包含固化树脂涂料的至少第二层。在一个实施方案中,固化树脂的特征在于抵抗以化学方式引起的腐蚀、冲击和磨损。
可选的外套:在一个实施方案中,耐火层还包覆有0.01-0.125英寸厚的ASTM A 240 304或316型不锈钢外套。在一个实施方案中,外套还层合有1密耳聚乙烯水汽阻挡层。在另一个实施方案中,热密封的水汽阻挡层是3密耳SurlynTM和聚乙烯的共挤出物。在一个实施方案中,所有配件例如箍带、铆钉、螺丝、T形管、端帽等都由不锈钢材料制成以进一步密封隔绝水汽。
可选的粘合剂层:在一个实施方案中,在各个层之间,例如在复合物层和耐火层之间、在复合物层和抗挤压层如金属箔之间、或者在金属箔和耐火层之间、或者在金属箔和陶瓷层之间等使用至少一个可选的粘合剂层。粘合剂层的材料可以包括任意聚合物或者适合于以化学、机械和/或其它方式结合的其它材料。合适的材料可以包括例如接触型粘合剂或液体树脂型粘合剂,金属涂覆的聚合物,填充聚合物,热塑性弹性体,热固性材料,热塑性材料,填充聚合物或它们的组合。
粘合剂层是可选的。在某些实施方案中,粘合剂层可以并非是必要或所需的。例如,在对于施加膨胀型涂层作为耐火层而使用网状物的一个实施方案中,可以不需要粘合剂层来结合膨胀型涂层。
描述实施方案的附图:将参照附图进一步描述本发明的实施方案。附图以举例方式且不以限制方式,即不将结构部件限制为具有所描述横截面区域的管道的方式,来描述本发明。结构部件可以具有其它配置,例如容器等。结构部件还可以具有附图中未加描述的不同多层配置,例如具有用腐蚀/侵蚀涂层处理的复合物层表面和带外部绝缘层的膨胀型层。
参考所示的图1,结构部件10由两个层(未显示最内的耐腐蚀层)构成,所述两个层即用于结构支承的复合物层11和所涂覆有的用以获得阻燃性的外部膨胀型涂层12。在图2中,除复合物层11和耐火层12外,结构部件10还包含耐腐蚀层例如非晶态金属层、热塑性内衬或陶瓷层13。在一个实施方案(未示出)中,结构部件还包含能量吸收层。
在图3中,结构部件的最内层(与腐蚀性产品接触)是涂覆到复合物层11上的陶瓷层13。耐火层包含膨胀型涂层12。在一个实施方案(未示出)中,最内层包含作为陶瓷层的替代或补充的非晶态金属用于耐腐蚀/耐磨蚀。在图4中,结构部件10的多层结构由涂覆有热塑性内衬(未示出)作为与腐蚀性产品接触的层的复合物层11、中间金属层14和外部膨胀型涂层12组成。图5是结构部件10的实施方案的侧正视图图,其中增强网状层15在最终涂覆膨胀型层12之前施加到复合物层11上。
在图6中,结构部件10具有多个层,即陶瓷(或非晶态金属)耐腐蚀层13、复合物层11、金属层14和直接施加到金属层14上的膨胀型层12。在一个实施方案中,在金属层14和复合物层11之间,或者在金属层14和膨胀型层12之间具有增强网状层(未示出)。
图7描述了结构部件例如管节的另一个实施方案的横截面。管道具有多个层,包括与容纳于其内的石油产品接触的热塑性耐腐蚀层16、含有复合材料的结构层11和含有绝缘材料的耐火层17。在一个实施方案(未示出)中,所述管节还可以包含用于容纳耐火层17的金属涂层例如不锈钢箔。
图8是图7中所描述实施方案的变型,其中所述管节还配设有另一个不同的耐火层,例如用于进一步防火的膨胀型涂层12。
应用:多层构造适合用作油气生产、运输和工艺应用中容纳腐蚀性石油产品的结构部件。结构部件的实例包括但不限于石化工艺设备和管线、工艺容器、输送管线和工艺管道、换热器、旋风分离器和蒸馏塔。具有多层构造的结构部件的特征在于具有优异的腐蚀/侵蚀性能、耐火性能,以及由于结构支承体的复合材料而轻且坚固。
本文所述的油生产、运输和工艺应用包括但不限于:油气勘探过程,包括烃提取和油/水/盐水/气体分离的生产过程,原料或成品烃产物的管送、船运、货车运输,包括涉及胺、碳酸盐的气体脱硫(sweeten)的生产和炼油工艺,或除去二氧化碳和/或硫化氢或其它气体的其它过程,原油蒸馏单元,流化催化裂化单元,催化重整单元,热裂解单元,加氢处理单元,硫酸或氟化氢烷基化单元,异构化单元,酸性水处理单元,和支持功用(supporting utility)单元例如冷却水、锅炉水,以及流出物处理单元。
在一个实施方案中,多层结构部件适合用于容纳具有从低ppm至高百分数水平的H2S浓度的硫(包括单质硫)含量的腐蚀性石油产品。在一个实施方案中,H2S具有50-100ppm的低浓度。在涉及酸性气体的应用的另一个实施方案中,例如,H2S浓度为20,000ppm-50,000ppm或更大(2-5%)。
在一个实施方案中,所述部件用于与总酸值(TAN)为至少0.01mgKOH/g的腐蚀性石油产品一起使用。在一个实施方案中,石油产品具有至少0.50mg KOH/g的TAN。在另一个实施方案中,石油产品具有0.50-10mg KOH/g油的TAN。TAN典型地通过ASTM方法D-664-01进行测量并且以毫克KOH/克油的单位表示。TAN值低于0.5的油通常认为呈非腐蚀性,0.5-1.0认为呈中度腐蚀性,而高于3.0认为呈腐蚀性。在一个实施方案中,结构部件用于容纳具有高的环烷属酸含量,即具有至少为3的较高TAN的高TAN原油或高酸性原油,。
在一个实施方案中,所述部件用于与盐水平为至少3lbs/bbl(原油的桶)的腐蚀性石油产品一起使用。在一个实施方案中,盐是约3-200pounds/bbl的量的氯化物盐例如氯化镁、氯化钠和氯化钙。在一个实施方案中,结构部件是用于容纳或运输具有高浓度氯化物的石油例如催化重整汽油、催化重整气体等。
在一个实施方案中,结构部件是内径为12”-18”的工艺/输送管道的形式,用于在至少300°F的连续工作温度和至少200psi的内压下使用。在另一个实施方案中,结构部件是直径为至多48”的工艺/输送管道的形式。在一个实施方案中,多层结构部件还包含2”-10”厚的绝缘层,或具有高温环境(高于500°F,特别为800°F或以上)所要求厚度的绝缘层。
应注意的是,结构部件不限于运送和/或容纳腐蚀性石油产品。在一个实施方案中,使用结构部件作为适合于海上石油平台、油轮等中喷淋系统等的耐腐蚀和耐火管道系统,用于容纳大体积海水和与石化环境有关的火灾。
在其中与石油产品接触的结构部件表面涂覆有陶瓷层的一个实施方案中,结构部件特别合适用于流化催化转化单元、流体焦化器以及炼厂灵活焦化单元和石化单元的领域。
形成方法:多层结构的各个层可在在安装前或在工作现场施加。
在用热塑性材料作为耐腐蚀层的前安装形成方法的一个实施方案中,在初始按所需形状或外形(profile)挤出内衬。然后将所述外形材与增强纤维和树脂接触以形成结构层。随后可使用本领域已知的方法将后续的层例如耐火层形成到或涂覆到结构层上。
在后安装的一个实施方案中,还可以在前安装的涂层上应用如先前所述产生涂层的任何涂覆方法,以提高涂层厚度,或修补在安装期间操作引起的损坏区域。
在一个实施方案中,结构部件由现有的装置或已构造的设备(例如由已具有一些耐腐蚀/耐侵蚀性能的复合材料构造的设备)构成。可将保护涂层/耐火膨胀型涂层施加在现有设备的表面上以提供所需的耐火性能。在又一个实施方案中,可将保护涂层施加在结构部件的内表面(与石油产品接触)上,以便填充孔穴和孔隙并给与石油产品接触的表面提供耐腐蚀和/或侵蚀耐保护。
可使用本领域已知的方法,包括刷涂、热喷涂、漆料喷射、喷涂、浸涂、用刷子或辊施涂、或它们的组合将涂层例如陶瓷层/非晶态涂层/膨胀型层或金属箔层施加在现有设备上,从而给结构部件提供共形表面处理。
在使用至少一个金属箔层、金属丝网或非晶态涂层的实施方案中,结构部件具有足够的导电性。在例如具有陶瓷涂层、作为基材的复合物层、和膨胀型涂层的多层结构部件的其它实施方案中,该结构部件可能不具有足够导电性从而导致静电电荷(ESC)积累。在减少电荷积累的一个实施方案中,可将涂层或层或静电消散(ESD)涂料施加在膨胀型层的顶部上,所述涂料提供足够高的电导率并同时保持所需的耐火性能。高电导率将电荷在积累时进行消散,最终将电荷传导至地面。
在使用复合材料作为结构层和塑料材料例如聚四氟乙烯用作耐腐蚀层的工艺/输送管道的一个实施方案中,可将工艺管节熔合或接合在一起(“熔合焊接”或“熔化焊接”)。
在一个实施方案中,使用本领域已知的施加能量的方法首先将热塑性腐蚀内衬适当地熔合或接合(或焊接),所述方法包括但不限于激光焊接,红外焊接;微波焊接,熔化焊接,超声波焊接,摩擦焊接等。
图9是将管段的两个节段接合的实施方案的侧剖平面视图,其中将两个管节101和201的耐腐蚀层16熔化结合。所述管段各自包含最内耐腐蚀层16、复合物结构层11、耐火层17和最外金属箔层12。在一个实施方案中,将两根管101和201的第一端在接合线160处对准并熔合在一起之前进行削剪(cut back)(除去复合物层)。在接合线160处将分别管节的耐腐蚀层接合之后,接下来接合分别节段的结构层11。
在一个实施方案中,在接合线160处熔合热塑性侵蚀内衬之后,修整削剪区域并且用接合带、织物或纤维包裹物将其沿周向包裹。在一个实施方案中,在用接合带包裹前之前首先加热修整区域(使耐腐蚀层暴露)。在另一个实施方案中,可以在包裹接合区域之前将接合带牵拉通过树脂浴。在一个实施方案中,接合带累积达到厚度为复合结构层厚度的1.10-2倍。
在一个实施方案中,可将预浸材料卷绕在接合区域160上并然后进行化学固化。在一个实施方案中,使用套管或环绕层形式的纤维覆盖接合段,然后将纤维和树脂化学接合在一起。在另一个实施方案中,使用粘合剂将纤维与接合段化学结合。在又一个实施方案中,还应用加热来加速和/或改善纤维套管和复合物管节之间的化学结合。
图10是图9接合部160的外部的示意性横截面,其中将外部玻璃纤维包裹物110将两个管节的复合物层接合。在一个实施方案中,包裹物110包含多种用热固性树脂润湿且相对于管道沿周向包裹的包裹体,其中包裹物在沿管节101和201纵向的边缘处逐渐变细。虽然未示出,管道系统还可通过以下进行构建:首先将具有耐腐蚀内衬的复合管道的节段熔化结合,然后将耐火材料层(和其它层或材料)施加到管段的接合部和其余部分从而在火灾发生时保护该系统。
在使用热塑性材料作为复合物层的基质的一个实施方案中,如果随后需要接近管道内部则可以通过熔化除去纤维套管。在一个实施方案中,施加热还有助于改善热塑性腐蚀层对结构层中织造玻璃纤维的粘合。
结构部件的性能:在一个实施方案中,包含至少复合物层和膨胀型层的多个层的结构部件,具有足够的厚度用于使该结构部件在喷射火试验程序OTI 95634中获得的保护比仅包含复合物层的部件获得的保护长至少30%。在一个实施方案中,结构部件获得长50%的保护。在第三实施方案中,长100%的保护。在1996年的喷射火试验程序OTI 95634中,对于约1100℃的温度和约300kW/m2的热通量,0.3kg/s丙烷蒸气在1米远以声速撞击1.5m2靶。足够的厚度取决于许多因素,包括结构部件的大小(例如直径、尺寸等),复合物层的厚度,复合物层构成材料(例如玻璃、陶瓷、热固化基质等),包含在其中的石油产品的类型等。在一个实施方案中,足够的厚度为至少10mm厚。在另一个实施方案中,为至少15mm厚。在第三实施方案中,为至少30mm厚。
在一个实施方案中,在烧穿试验中,具有至少复合物层和膨胀型层的多层结构部件显示出优异的耐火性和阻燃性,即至少5分钟。在第二实施方案中,结构部件具有大于15分钟的烧穿时间。在第三实施方案中,烧穿时间大于30分钟。在第四实施方案中,为至少45分钟。在一个实施方案中,在烧穿试验中,具有至少复合物层和厚度为0.5-2cm的膨胀型层的多层结构部件具有至少15分钟的阻燃性。
在一个实施方案中,具有至少复合物层和膨胀型层的多层结构部件证明了与厚度为至少0.07”厚的碳钢相等的烧穿耐受性。在另一个实施方案中,多层结构部件证明了与厚度为至少0.10”厚的碳钢相等的烧穿耐受性。在第三实施方案中,烧穿耐受性与0.15”厚的碳钢相等。
在烧穿试验(基于美国海军试验MIL-STD-2031)中,将试样放置在500,000BTU/小时丙烷火的前面。通过直接火焰,例如在烃火中于试样表面处产生1100℃(约2000°F)的温度。所述样品是24”乘24”乘1/4”厚的节段。监测基材的未暴露侧的阻燃性并且测量材料烧穿的时间。
在一个实施方案中,管道系统形式的多层结构部件的特征在于满足根据国际海事协会(IMO A753,1993年11月4日采用)规定的试验方法的II级耐火标准,即管道可长持续时间地耐受完全着起来的烃火而不丧失在干燥条件下的完整性。根据国际海事协会(IMO A 753,1993年11月4日采用)规定的试验方法,在外径上约1100℃的强制温度下,满足II级标准的持续时间的最小值是30分钟。满足I级标准的持续时间较高,最小值是1小时。
在一个实施方案中,在IMO A753试验条件下在管道内径(内部管道表面)达到190℃之前需要至少45分钟。在另一个实施方案中,在管道内径达到190℃之前需要至少1小时。在另一个实施方案中,在管道内径达到190℃之前需要至少11/2小时。
在一个实施方案中,具有至少复合物层和膨胀型层的多层结构部件显示出优异的挠曲强度,即使在暴露于辐射热通量之后。期望在暴露于25kW/m2的辐射热通量后于20分钟之后,具有至少复合物层和耐火层的多层结构部件的剩余挠曲强度是由复合物层材料制造的现有技术结构部件的挠曲强度的至少2倍(按照ASTM D-790)。在第二实施方案中,该多层结构部件在暴露于辐射热后具有的剩余挠曲强度是现有技术复合物部件(没有耐火层)的挠曲强度的至少3倍。
在其中结构部件是工艺/输送管道的一个实施方案中,该结构部件具有203mm-1016mm(8”-40”)的标称直径,工作压力提升至10,000psi,并且爆裂压力是工作压力的2.5倍。在一个实施方案中,爆裂压力为827-1034bar(12,000-15,000psi)。在一个实施方案中,管道具有2-5%的线性弯曲应变。在另一个实施方案中,工艺管道形式的结构部件具有3%的最大线性弯曲应变。
在一个实施方案中,使用热塑性侵蚀内衬的配管系统需要比现有技术中使用带有栓固凸缘的碳钢的类似配管系统少至少20%的维护(当用于容纳石油产品时)。这是因为需要最少(如果有的话)的栓固凸缘来接合节段。对于热塑性材料层而言复合物更加相容,特别是在高温和/或频繁热循环下操作。复合材料即纤维增强塑料或FRP,具有与碳钢相比低得多的挠曲模量。取决于碳的量,在一个实施方案中碳钢具有189-210GPa或27,000,000-30,000,000psi的挠曲模量。复合材料具有的挠曲模量是金属材料的挠曲模量的约1/10-1/30,典型地为1,000,000-2,000,000psi。在一个实施方案中,挠曲模量为75,000-2,000,000psi。在第三实施方案中,挠曲模量为500,000-1,500,000psi。在复合物包含碳环氧材料(carbon epoxy)和/或硼环氧材料的第四实施方案中,挠曲模量可以高很多,但是仍比挠曲模量小于9,000,000psi的碳钢小得多。在使用碳环氧材料的一个实施方案中,复合物具有约54GPa(7,800,000psi)的挠曲模量。
取决于所选择的热塑性材料,在一个实施方案中,耐腐蚀层具有75,000-1,000,000psi的挠曲模量(对于1∶1-26∶1的复合物/热塑性材料挠曲模量比)。在另一个实施方案中,耐腐蚀层的挠曲模量为90,000-750,000psi。在第三实施方案中,腐蚀内衬的挠曲模量为100,000-600,000psi。对于较低的挠曲模量,就受冲击的结构部件而言,可变形恢复,这与可永久变形的现有技术中使用碳钢的结构部件相反。
除挠曲模量的相容性外,复合材料就热膨胀而言还较好地匹配用作与石油产品接触的耐腐蚀层的热塑性材料。复合材料的热膨胀系数比碳钢的热膨胀系数高。复合物层的热膨胀速率取决于该层中纤维的量和纤维的取向。在一个实施方案中,复合物层具有0.9-2*10^-5in/in/°F的CTLE。与此相比之下碳钢具有0.6-0.65×10^-5in/in/°F的CTLE。作为常用耐腐蚀层材料的PTFE具有7.5*10^-6in/in/°F的CTLE。
对于就结构层使用复合材料,在一个实施方案中,结构部件的特征在于具有的压力膨胀在一个实施方案中是碳钢的至少10倍,在第二实施方案中是20倍,以及是使用碳钢的结构部件高达25倍。
关于热传导率,使用复合材料作为结构层的结构部件的特征在于具有总体较低的热传导率,这特别适合于具有热失控或热点的情形。这是因为复合物层的热传导率低得多。在一个实施方案中,复合物层热传导率是碳钢热传导率的100-300分之一。与碳钢的25-50BTU-ft/hr-ft2-°F热传导率,和PTFE(可用于耐腐蚀层的典型的热塑性材料)的1.70BTU-ft/hr-ft2-°F相比,复合物层的热传导率在一个实施方案中为0.1-0.24BTU-ft/hr-ft2-°F。
最后,在一个实施方案中,结构部件的特征在于具有优异的耐火性能,这是因为用作结构层的复合材料的高熔点。在一个实施方案中,复合物层具有远高于2900°F的熔点,具有经受住温度高达1800°F的烃火30分钟的能力。碳钢典型地具有2600-2800°F的熔点。
实施例:以下说明性实施例旨在是非限制性的。
使用有限元分析(FEA)或预测模型对结构部件例如管道的实施方案进行建模。所使用的预测模型是来自Solidworks的通用专业套件。所建模的管道是8”ID管道,包含用于结构复合物层的玻璃增强环氧热固性材料,用于耐腐蚀层的热塑性材料,和包含硅酸钙的耐火层。在热建模中,不考虑耐腐蚀层,这是因为热数据与结构层和耐火层的热数据相比是不重要的。
在实施例1中,8”ID管道具有厚度为0.43”的结构层和包含2”厚硅酸钙的耐火层。根据国际海事协会(IMO A 753,1993年11月4日采用)规定的试验方法,图11以外径上约1100℃强制温度的时间的函数绘制出了管道内部温度(ID)作为。管道内径在1小时后达到191℃。
在实施例2中,所建模的管道具有为8”的相同ID,但是具有0.83”的厚得多的结构复合物层。图12描述了在暴露于外径上约1100℃的强制温度4680秒(78分钟)后,管道温度作为半径(从ID到OD、再到包括耐火层的外壁)的函数。图13描述了管道(ID)内部温度作为时间的函数,其在至少5400秒(或11/2小时)内没有达到192℃。
出于本说明书和附属权利要求书的目的,除非有其他说明,用于本说明书和权利要求书中表示数量、百分数或比例、以及其他数值的所有数,在任何情况下都应理解为由术语“约”修饰。因此,除非有相反说明,在下列说明书和附属权利要求书中提出的数值参数是可随本发明所试图获得的期望性质而变化的大约值。应注意,如本说明书和附属权利要求书中所使用的,单数形式“一个”、“一种”和“所述”包括多个提及物,除非明确且清楚地限制为一个提及物。如本文中所使用的,术语“包括”及其语法变体旨在是非限制性的,使得列表中各项的描述不会排除其他类似项,所述类似项能够代替列出的项或添加至所列出项中。
此处书写的说明书使用实施例来公开本发明,包括最佳实施方式,另外还使得本领域所有技术人员能够实施和使用本发明。专利范围由权利要求书限定,且包括本领域技术人员所能想到的其他实施例。如果这些其他实施例的结构元素与权利要求书的文字语言并无差异,或者,如果它们包括与权利要求书的文字语言无本质不同的等价结构元素,则这些其他实施例也在权利要求书的范围内。此处通过参考将所有的引用明确地并入到本文中。
Claims (24)
1.一种用于容纳腐蚀性石油产品的结构部件,该结构部件包含:
含有复合材料的结构层;
用于接触腐蚀性石油产品的耐腐蚀层,该耐腐蚀层含有非晶态金属;
热传导率小于0.4W/m℃的耐火层;
其中该结构部件具有大于5分钟的烧穿时间;和
其中所述腐蚀性石油产品包含以下中的至少一种:酸性水、含有H2S的石油产品、TAN为至少0.50mg KOH/g的石油产品和盐水平为至少3lbs./bbl的石油产品,和其中该结构部件为工艺容器、输送管线、工艺管道、换热器、旋风分离器或塔的形式。
2.一种用于容纳腐蚀性石油产品的结构部件,该结构部件包含:
含有复合材料的结构层;
用于接触腐蚀性石油产品的耐腐蚀层,该耐腐蚀层含有非晶态金属;
热传导率小于0.4W/m℃的耐火层;
其中该结构部件满足根据IMO A 18/Res.753火灾试验规程的II级耐火标准;和
其中所述腐蚀性石油产品包含以下中的至少一种:酸性水、含有H2S的石油产品、TAN为至少0.50mg KOH/g的石油产品和盐水平为至少3lbs./bbl的石油产品,和其中该结构部件为工艺容器、输送管线、工艺管道、换热器、旋风分离器或塔的形式。
3.一种用于容纳腐蚀性石油产品的结构部件,该结构部件包含:
含有复合材料的结构层;
用于接触腐蚀性石油产品的耐腐蚀层,该耐腐蚀层含有非晶态金属;
热传导率小于0.4W/m℃的耐火层;
其中在1996年的喷射火试验程序OTI 95634中该结构部件获得的保护比没有耐火层的结构部件所获得的保护长至少30%;和
其中所述腐蚀性石油产品包含以下中的至少一种:酸性水、含有H2S的石油产品、TAN为至少0.50mg KOH/g的石油产品和盐水平为至少3lbs./bbl的石油产品,和其中该结构部件为工艺容器、输送管线、工艺管道、换热器、旋风分离器或塔的形式。
4.权利要求1-3中任一项的结构部件,其中所述复合物具有小于0.24BTU-ft/hr-ft2-°F的热传导率。
5.权利要求1-3中任一项的结构部件,其中所述耐腐蚀层具有0.010mm-10mm的厚度。
6.权利要求1-3中任一项的结构部件,其中所述复合材料具有小于9,000,000psi的挠曲模量。
7.权利要求1-3中任一项的结构部件,其中该结构部件具有大于15分钟的烧穿时间。
8.权利要求1-3中任一项的结构部件,其中在根据IMO A18/Res.753火灾试验规程的试验中,耐腐蚀层上的内表面达到190℃需要至少90分钟。
9.权利要求1-3中任一项的结构部件,其中所述复合材料包含在基质材料中的增强纤维,其中所述增强纤维含有选自玻璃、碳、陶瓷材料、聚合物材料、金属和金属合金的材料;并且其中所述基质包含选自酚醛树脂、硅氧烷改性的酚醛树脂、乙烯基酯、环氧树脂、氰酸酯、酚醛树脂/聚酯共混物、硅树脂、苯二甲腈、呋喃树脂和它们的混合物的材料。
10.权利要求1-3中任一项的结构部件,其中所述耐火层包含硅酸钙。
11.权利要求1-3中任一项的结构部件,其中所述复合材料具有0.9-2*10^5in/in/°F的热线性膨胀系数,并且其中所述耐火层是在载体材料中包含可膨胀无机材料的膨胀型材料。
12.权利要求1-3中任一项的结构部件,其中按照ASTM D-790该结构部件在暴露于25kW/m2的辐射热通量后于20分钟之后,具有的剩余挠曲强度是没有耐火层的结构部件的挠曲强度的至少2倍。
13.权利要求1-3中任一项的结构部件,其中所述耐腐蚀层以至少5000psi的结合强度与所述结构层结合。
14.权利要求1-3中任一项的结构部件,其中所述耐腐蚀层包含HEAT侵蚀指数为至少5的陶瓷材料。
15.权利要求1-3中任一项的结构部件,其中所述耐腐蚀层包含陶瓷材料,并且其中所述陶瓷材料通过沉积、热喷涂、物理气相沉积、RF溅射、电镀、粉末涂覆和它们的组合中的任意一种施加到结构层上以形成耐腐蚀层。
16.一种将权利要求1-3中任一项的用于容纳腐蚀性石油产品的结构部件中的管节进行接合的方法,所述结构部件包含至少两个不同的管节,即第一管节和第二管节,所述方法包括:
将第一管节定位成与第二管节接邻,每个管节包含含有复合材料的结构层和用于接触腐蚀性石油产品的耐腐蚀层、以及耐火层;
施加能量以将所述第一和第二管节的耐腐蚀层进行接合在一起从而形成接合部;
围绕所述第一和第二管节的接合部施加外部包裹物;以及
通过化学固化和热处理中的至少一种将该外部包裹物结合到所述接合部和复合物结构层。
17.权利要求16的方法,其中围绕接合部和至少部分复合物结构层施加所述外部包裹物。
18.权利要求16-17中任一项的方法,其中通过化学固化和热处理中的至少一种将所述外部包裹物结合到所述接合部和所述复合物结构层。
19.权利要求16-17中任一项的方法,其中围绕接合部以及第一和第二管节的至少部分复合物结构层沿周向包裹所述外部包裹物。
20.权利要求16-17中任一项的方法,在施加能量以接合耐腐蚀层之前,该方法还包括除去第一和第二管节的至少部分结构层和至少部分耐火层以暴露接近所述第一和第二管节的接合部的耐腐蚀层。
21.一种给权利要求1-3中任一项的用于容纳腐蚀性石油产品的结构部件提供耐腐蚀和耐火保护的方法,所述结构部件包含具有第一表面和与该第一表面相对的第二表面的结构层,所述方法包括:
向第一表面施加非晶态金属,从而形成与腐蚀性石油产品接触的耐腐蚀层;
向第二表面施加足够量的热传导率小于0.4W/m.℃的耐火材料以获得具有足够厚度的耐火涂层从而使所述结构部件满足根据IMO A18/Res.753火灾试验规程的II级耐火标准。
22.权利要求21的方法,其中施加足够量的耐火材料以使结构部件具有至少15分钟的烧穿时间。
23.权利要求21-22中任一项的方法,其中施加足够量的耐火材料用以在1996年的喷射火试验程序OTI 95634中使所述结构部件具有的保护比没有耐火层涂层的结构部件所获得的保护长30%。
24.权利要求21-22中任一项的方法,该方法还包括在施加耐火涂层之前将增强网状物施加到结构层上。
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CN102448720A (zh) | 2012-05-09 |
CA2758971A1 (en) | 2010-10-21 |
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RU2011146336A (ru) | 2013-05-27 |
WO2010121143A2 (en) | 2010-10-21 |
AU2010236259A1 (en) | 2011-11-03 |
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