CN102083746A - 用于处理海上天然气的装置和方法 - Google Patents

用于处理海上天然气的装置和方法 Download PDF

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CN102083746A
CN102083746A CN2009801260126A CN200980126012A CN102083746A CN 102083746 A CN102083746 A CN 102083746A CN 2009801260126 A CN2009801260126 A CN 2009801260126A CN 200980126012 A CN200980126012 A CN 200980126012A CN 102083746 A CN102083746 A CN 102083746A
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CN102083746B (zh
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P·J·H·卡内尔
G·袁车恩
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Johnson Matthey PLC
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Abstract

描述的是用于处理海上天然气的方法,其包括通过如下步骤在海上加工设备加工所述天然气,(i)将天然气液化和分馏以产生液化天然气料流和高级烃料流,(ii)将至少一部分的所述高级烃料流气化,(iii)使气化的高级烃料流和蒸汽在蒸汽重整催化剂上通过以产生包含甲烷、蒸汽、碳氧化物和氢气的重整气体混合物,(iv)使重整气体混合物在甲烷化催化剂上通过以产生富甲烷的气体,和(v)在液化步骤之前将富甲烷的气体与天然气合并。

Description

用于处理海上天然气的装置和方法
技术领域
本发明涉及用于处理海上天然气、特别是滨海的海上天然气的方法,例如适合用于液化天然气(LNG)生产的方法,以便提高有价值产物的储存容量,发电和减少燃烧。
背景技术
包含甲烷和高级烃类如乙烷、丙烷和丁烷的海上天然气经常采用与海底的井源相连的固定或浮动平台直接采收,或者作为产油的伴生气采收。一般可能的情况下,将采收的天然气经由管道供给陆上的气体加工设备,在那里可以进行诸如纯化之类的步骤。然而对于相当大比例的采收天然气,用管道输送至陆上设备是不可能的。在这样的情况下,期望采收并液化天然气以便海上输送至陆上设备。液化方法典型地包括将天然气冷却至非常低的温度的步骤,该温度容许乙烷、丙烷、丁烷和其它高级烃类中的至少一些与甲烷分离。液化产物具有不同的商业价值,但是在诸如裂化之类的进一步加工不可行的海上,典型地乙烷具有最低的价值,因此部分经常在液化设备中用于发电,多余部分燃烧掉。或者,可以回收多余的乙烷并随LNG一起输送至陆上设备。然而,将乙烷代替更有价值的液体输送的经济性不那么有吸引力。在不断增长的使采收烃类的利用最大化的压力加上减少在环境上不安全的燃烧的需要下,存在对改进的用于处理海上天然气的方法的需要。
最初由British Gas开发并由Davy Process Technology Ltd许可的CRG方法利用蒸汽重整、甲烷化和CO2脱除的组合以从LPG或石脑油产生合成天然气。作为选择,CRG蒸汽重整已被用作使指定去往管道供给的源自LNG的天然气的热值降低的手段。
我们已经认识到可以将CRG方法改造并且在海上使用以克服前述天然气处理方法的问题。
发明内容
因此,本发明提供用于处理海上天然气的方法,其包括通过如下步骤在海上加工设备加工所述天然气,
(i)将天然气液化和分馏以产生液化天然气料流和高级烃料流,
(ii)将至少一部分的所述高级烃料流气化,
(iii)使气化的高级烃料流和蒸汽在蒸汽重整催化剂上通过以产生包含甲烷、蒸汽、碳氧化物和氢气的重整气体混合物,
(iv)使重整气体混合物在甲烷化催化剂上通过以产生富甲烷的气体,和
(v)在液化步骤之前将富甲烷的气体与天然气合并。
本发明在于在海上气体加工设备中采用适当改造的CRG技术以克服燃烧和/或储存及输送高级烃类的问题。此外具有相对高熔点的高级烃类、特别是C5+在液化设备中的加工会是困难的,因为它们会冻结并因此在装置中造成阻塞。此外重质烃类是起泡的原因以及是酸性气体脱除单元的遗留物。减少C5+烃类克服这一问题。
本发明因此进一步提供用于处理海上天然气的装置,其包括海上天然气加工设备,该设备上安装有:
(i)包括分馏装置的天然气液化单元,其配置用于产生液化天然气料流和高级烃料流,
(ii)气化装置,其操作性地连接至所述液化单元并且配置用于将至少一部分的所述高级烃料流气化,
(iii)用于向气化的高级烃料流中添加蒸汽的装置,
(iv)操作性地连接至气化装置的重整容器,含有重整催化剂的所述重整容器经配置以使得气化的高级烃料流和蒸汽在催化剂上通过以产生包含甲烷、蒸汽、碳氧化物和氢气的重整气体混合物,
(v)操作性地连接至重整容器的甲烷化容器,含有甲烷化催化剂的所述甲烷化容器经配置以使得重整气体混合物在催化剂上通过以产生富甲烷的气体,和
(vi)混合装置,其用于将富甲烷的气体与供给天然气液化单元的天然气混合。
在第一步中,使用常规采收技术和管道设备采收天然气并提供至海上天然气加工设备。可以在海上天然气采收单元或在单独的海上加工单元中加工天然气。优选地该海上天然气加工设备为固定的海上设备或浮动的海上设备如浮动的生产、储存和卸载(FPSO)设备。
在天然气含汞的情况下,期望所述方法包括在液化和分馏步骤上游纯化天然气以除汞的步骤,以便保护经常是由铝制造的换热装置免于汞的腐蚀影响。因而,优选所述方法具有包含适合除汞的纯化材料的纯化单元,所述单元在液化步骤上游安装。合适的纯化材料是与各种聚集体形式的载体材料混合的过渡金属硫化物、特别是硫化铜。这些材料可从Johnson Matthey PLC购得,例如作为PURASPECJM TM1163。或者可以将过渡金属化合物例如羟基碳酸铜以合适的形式提供至该单元并且通过天然气中存在的硫化合物原位硫化。除汞步骤优选在100℃以下和至多约150bar abs、例如10-150bar abs的压力下操作。
在天然气含有硫化合物的情况下,期望所述方法包括在重整步骤的上游纯化天然气或高级烃料流以除去硫化合物的步骤,以便保护重整催化剂免于硫的中毒影响。所述除硫可以对液化和分馏步骤上游的天然气进行,或者可以对气化的高级烃料流进行,或者二者都进行。因而,优选地所述方法包括含有一种或多种适合脱除硫化合物的纯化材料的纯化单元,所述单元在液化装置和/或重整容器的上游安装。所述硫化合物可以包括硫化氢(H2S)、硫化羰(COS)、硫醇和噻吩中的一种或多种。在硫化合物主要是硫化氢的情况下,这可以在液化装置上游用合适的膜或采用物理洗涤溶剂如冷冻甲醇、乙二醇或碳酸亚丙酯或含水胺的酸性气体洗涤与CO2一起脱除。或者可以简单地用一个或多个诸如金属促进的、如Cu促进的ZnO/氧化铝组合物或ZnO组合物之类的硫吸收剂的床层吸收H2S。在硫化氢之外的硫化合物以高浓度存在的情况下,可能期望包括加氢脱硫的第一步,其继之以硫化氢吸收的步骤。在该实施方案中,纯化材料包括在硫化氢吸收剂床层上游设置的加氢脱硫催化剂床层。在加氢脱硫中,使天然气和少量氢气在Ni基和/或Co基催化剂上通过,该催化剂将有机硫化合物转化成硫化氢。典型的催化剂为氧化铝担载的Ni/Mo、Co/Mo、Ni/W和Co/W催化剂。上述催化剂可购得。除天然气中自然存在的任何硫化氢之外,如此生成的硫化氢可以接着由合适的硫化氢吸收剂如ZnO材料吸收。再一次地上述吸收剂材料可购得。加氢脱硫和硫化氢吸收优选在重整容器上游进行,因为接下来仅有达到重整器的有机硫化合物需要进行加氢脱硫,其顾及较小的容器、较少的氢气需求和较少的催化剂。在有机硫化合物包括硫醇的情况下,这些可能存在于乙烷、丙烷和丁烷级分中。加氢脱硫催化剂还可能有效用于氢化烯烃以及将胺类转化成氨。加氢脱硫催化剂和硫化氢吸收剂可以处于相同或不同的容器中。加氢脱硫和H2S吸收优选在150℃以上、更优选200℃以上、以及至多约50bar abs的压力下操作。加氢脱硫所需的氢气可以由储罐、单独的氢气发生装置、或者优选地通过再循环一部分重整气体混合物提供。
在一种优选实施方案中,来自甲烷化步骤的热量用于在使用加氢脱硫催化剂和/或硫化氢吸收剂的除硫步骤之前预热天然气流。因此所述装置优选包括换热装置,其传递来自甲烷化容器的热量以在将天然气或高级烃供给含加氢脱硫催化剂和/或硫化氢吸收剂的纯化单元之前将它预热。
在液化之前,可以使天然气流经历初步分离阶段,其中采用将轻质(小)的烃与重质(较大)的烃分离的膜,从而产生气态富含高级烃的料流。例如可以使用膜以5-20%的甲烷选择性由天然气生成C3+料流(参见Ind.Eng.Chem.Res.,第47卷,第7期,2008,第2109-2121页,以及其中的参考文献)。通过以这种方式部分脱除高级烃,可以减小液化单元的负担,减少冻结的C5+烃所造成的阻塞的风险,以及克服酸性气体脱除单元中的起泡问题。此外,如此分离的气态高级烃料流可以在由液化单元得到的液体高级烃料流的气化中使用。
在纯化步骤和任何初步分离阶段之后,将天然气液化并分馏以产生液化天然气料流和高级烃料流。“高级烃类”包括乙烷、丙烷、丁烷和任何C5+链烷烃、环烷烃如环己烷、以及芳烃如苯中的一种或多种。尽管重整步骤可以将所有这些高级烃转化成甲烷,可能期望的是在使剩余部分经历重整步骤之前进一步分馏高级烃料流以采收商业上更有价值的组分。因而在一种优选的方法中,液化和分馏步骤将天然气分成富甲烷料流(即液化天然气)、乙烷料流、LPG料流(含丙烷和丁烷)以及重质料流。
因而所述装置包括天然气液化单元和一座或多座分馏塔。优选处理天然气以脱除任何CO2并且干燥,之后供给至液化单元,在那里于供给至使重质烃与富甲烷料流分离的第一分馏塔之前首先将其冷却至-20到-40℃。来自塔顶的轻质级分进一步冷却并且分离冷凝的液体。因而使高级烃液化。对于来自第一座塔的轻质和重质级分可以采用一座或多座进一步的塔以获得富含甲烷、乙烷、丙烷、丁烷和其它烃的级分。以这种方式处理液化天然气料流的方法例如在US 6564579中得到描述。供给重整步骤的高级烃料流优选包含乙烷和/或一部分LPG和/或含C5+链烷烃的重质料流。含乙烷的料流是可得的,因此供给重整步骤的高级烃料流优选包含乙烷以及任选地一部分LPG和/或含C5+链烷烃的重质料流。最优选地供给重整步骤的高级烃的>50体积%、优选>75%、更优选>90%为乙烷。没有用于重整的乙烷、丙烷、丁烷和其它高级烃可以用于所述方法的发电,例如采用燃气轮机。
有待供给重整器的高级烃料流在气化器中进行气化,其有利地可以用来自甲烷化步骤的热量加热。
接着将气化的高级烃料流加压至10-50bar abs,在20bar abs以上的压力下加热至200℃以上、优选300℃以上、更优选300-520℃、最优选350-500℃,与蒸汽混合并通到含重整催化剂的重整容器中。可以通过直接注入或通过利用饱和器将蒸汽加入到气化的高级烃料流中。蒸汽也可以用于使高级烃料流气化。应当控制蒸汽比率以避免催化剂上的碳沉积,然而其中进料主要是乙烷的情况下,典型地是0.2-2.0、优选0.2-1.0。
蒸汽重整反应以绝热方式于蒸汽重整容器中在催化剂上发生,从而将高级烃料流转化成包含甲烷、一氧化碳、二氧化碳、氢气和蒸汽的气体混合物。蒸汽重整催化剂优选为Ni催化剂或贵金属催化剂,或它们的组合。合适的催化剂包含与氧化铝或铝酸钙结合的10-60%NiO。在使用之前用氢气或另一种还原性气流将Ni还原成其活性形式。在合适的惰性载体上的贵金属催化剂如Pt、Pd、Rh或Ru催化剂、特别是Ru催化剂能够在比Ni催化剂更高的空速、更低的蒸汽比率和更低的温度下操作,因此在供水有限的情况下可能是有利的。贵金属装载量典型地是0.1-1.0wt%。
需要的话,一部分重整气体可以在压缩下再循环至供给重整容器的预热过的高级烃料流,从而充当稀释剂以及提供一些氢气以抑制催化剂上的碳沉积。贵金属重整催化剂的一个优点在于不需要氢气再循环至重整器以防止碳沉积。另一优点在于贵金属催化剂的情况下由于它们与Ni催化剂相比的高活性,重整设备可以更紧凑。
作为选择,由于再循环的料流含有一些氢气,如果采用加氢脱硫的话,所述料流可以提供加氢脱硫所需的一些或全部的氢气。
在重整催化剂或其它方法条件如蒸汽比率容许的情况下,或者如果不采用加氢脱硫的话,可以将所有的重整气体通到甲烷化步骤。在甲烷化步骤之前,重整气体混合物或其剩余部分优选用一个或多个换热器冷却,该换热器可以有利地用于生成在重整步骤中使用的蒸汽。接着将冷却的气体通到甲烷化步骤。
甲烷化步骤可以包括一个或多个串联的甲烷化容器、优选一个或两个容器,其各自含有甲烷化催化剂。甲烷化步骤优选在10-50bar的压力和100-400℃、优选250-350℃的温度下进行。甲烷化催化剂优选为Ni催化剂或贵金属催化剂,或它们的组合。甲烷化催化剂造成“反向重整”反应发生,其中重整气体中的一氧化碳和氢气被消耗以生成甲烷。甲烷化反应放热,理想地在每个甲烷化容器之后提供换热装置以冷却富甲烷的气体混合物。如上所述,来自甲烷化步骤的热量可以有利地用于在加氢脱硫/硫化氢吸收之前预热天然气和/或使高级烃料流气化。通过仔细控制重整步骤,例如通过控制放热曲线和/或通过使用贵金属催化剂,可以使重整气体的氢气和碳氧化物含量最小化,从而减少对甲烷化反应器的需求,以至于甲烷化反应器的尺寸可以最小化。
重整步骤生成碳氧化物,其包括无法通过甲烷化除去的二氧化碳。二氧化碳在液化温度以上冻结,因此可能期望的是包括使用CO2脱除单元在将富甲烷的气流与天然气合并之前或之后从中脱除二氧化碳的步骤。优选地将天然气与富甲烷气体混合并使该混合物通过CO2脱除单元。CO2脱除、也称为酸性气体脱除,可以用膜技术(例如基于各向异性的醋酸纤维素、聚酰亚胺或全氟聚合物膜)或已知的含水胺洗涤或物理洗涤溶剂如冷的甲醇、N-甲基吡咯烷酮或乙二醇洗涤技术来实现。
此外,重整步骤使用蒸汽,蒸汽会被带入到富甲烷气体中。蒸汽会在液化装置中冷凝和冻结。此外,为了避免在气流中形成烃水合物以及为了避免可能接着造成腐蚀问题的气体在管道和方法装置中冷凝出水,从天然气中脱除水蒸汽是合意的。因此理想的是包括在将富甲烷气体与天然气合并之前或之后使用干燥单元将它干燥的步骤。优选地将天然气和富甲烷气体混合并使该混合物通过干燥单元。在包括二氧化碳脱除步骤的情况下,优选在CO2脱除单元下游进行最后的脱水步骤。可以用干燥合成气体混合物或天然气混合物的已知方法实现干燥步骤。脱水以降低天然气露点的若干方法工业上在气体加工工厂中实施。例如,可以用换热器将富甲烷气体或混合气体冷却至蒸汽露点以下,并且在一个或多个分离器中除去冷凝物。这可以在甲烷化阶段之后和任何CO2脱除阶段之前进行。作为选择或者另外地,将气体与固体干燥剂如硅胶或分子筛的床层接触,以及使用液体干燥剂化合物,可以实现干燥步骤。在后一种情况下,典型的方法包括使潮湿气流与乙二醇溶液接触以便从气流中脱除水至乙二醇溶液中。该方法被称为乙二醇脱水而且非常广泛地用于气体加工操作。在一些干燥方法中,甲醇或另一种醇可以用作乙二醇的代替物或者作为与乙二醇的混合物。为了达到液化单元的有效运行所需的非常低的水含量,优选例如含沸石的分子筛干燥器。分子筛可以通过加热周期性地再生。任何采收的水优选用于产生重整步骤的蒸汽。
因而通过将高级烃转化成与液化单元的进料合并的富甲烷气体,使否则可能燃烧或占据有价值的储存空间的乙烷和其它低价值烃类的量减少。
附图说明
参照附图进一步说明本发明,其中:
图1描绘基于FPSO气体加工单元的海上天然气处理设备一种实施方案的单元操作的布置,
图2描绘本发明方法的一种实施方案,以及
图3描绘催化重整和甲烷化方法的一种实施方案。
具体实施方式
在图1中,FPSO单元100具有在其上安装并且操作性地互相连接的除汞单元102、酸性气体脱除单元104、气体干燥单元106和液化与分馏装置108,其产生液化天然气料流110,以及任选地丙烷、丁烷和冷凝物料流,以便在储罐112中储存。FPSO进一步具有将来自液化与分馏装置108的重质烃料流116气化的气化装置114、脱硫单元118、用于向脱硫的重质烃料流中加入蒸汽120的装置、重整容器122和甲烷化容器124。来自甲烷化反应器124的产物富甲烷气流126回到除汞单元102与酸性气体脱除单元104之间的天然气进料管线。
在图2中,在低于100℃的温度和10-100bar abs、例如约10barabs的压力下使天然气进料流210通到含有粒状硫化铜基汞吸收剂214的第一纯化容器212。汞和其它重金属如砷被该吸收剂吸收。所得的气流216与富甲烷气流218混合并通过含有合适的从气流中分离CO2的膜的酸性气体脱除容器220。在一种可供替代的实施方案中,酸性气体脱除步骤采用胺洗涤单元,其通过使气体与含水胺溶液接触而除去CO2和一些H2S。在另一可供替代的实施方案中,酸性气体脱除步骤采用物理洗涤溶剂单元,其通过使气体与冷冻的甲醇、乙二醇、N-甲基吡咯烷酮或碳酸亚丙酯接触而除去CO2和一些H2S。所得的贫CO2的气流222通到干燥容器224,在那里它与充当干燥剂沸石分子筛接触以脱水。干燥过的气流接着在换热器228中冷却至-20到-40℃,这导致高级烃冷凝,将料流供给至第一分馏塔230,在那里使高级烃与富甲烷料流分离。冷凝物包括重质组分如苯、环己烷、一些丙烷和丁烷和C5+链烷烃、还有一些乙烷和溶解的甲烷。来自塔230顶部的轻质级分232在换热器234中进一步冷却并且在分离器236中分离冷凝的液体。这些液体回到塔230。从分离器236分离的气体接着在换热器238中进一步冷却以形成液化天然气240。从塔230采收的高级烃料流经由管线242供给运行以采收富乙烷料流的第二分馏塔244(脱乙烷塔)。将乙烷料流246气化并送往单元248中脱硫、重整和甲烷化,该单元由来自管线249的供给蒸汽(参见图3)。所得的富甲烷气流从单元248经由管线218通到管线216。由第二分馏塔244底部采收的混合料流250送往第三塔252(脱丙烷塔),在那里采收富丙烷料流254。由第三分馏塔252底部采收的混合料流256送往第四塔258(脱丁烷塔),在那里采收富丁烷料流260和冷凝物料流262。由脱丙烷塔252和脱丁烷塔258分别获得的丙烷254、丁烷260和冷凝物262可以送往储存。需要的话,这些料流中的一部分(由虚线表示)可以送往纯化、重整和甲烷化阶段248以便产生富甲烷气体。
在一种实施方案中,在干燥器224与换热器228之间,使纯化的贫CO2的干燥天然气流通过含有使一部分高级烃与天然气分离的膜的初步分离单元226,从而形成气态高级烃料流(由虚线表示),其接着供给高级烃气化器。
在图3中,将任选地含有丙烷、丁烷和/或冷凝物的富乙烷料流310供给换热器312,在那里使它气化。所得的气流314与含有一些氢气的循环气体316混合,该混合物在200-400℃、优选250-400℃以及10-50bar abs下供给容器318,其含有在ZnO吸收剂322床层上方的Ni/Mo加氢脱硫催化剂320床层。该混合物与加氢脱硫催化剂320接触导致有机硫化合物(例如硫醇)氢化以形成硫化氢。如此形成的硫化氢接着在ZnO吸收剂322上吸收。接着将脱硫的气体324与蒸汽326在350-400℃混合,并且在200-500℃、优选300-500℃和>20bar abs下,在绝热反应器330中的Ni或贵金属蒸汽重整催化剂328的床层上通过。发生蒸汽重整反应(连同平衡的变换反应和甲烷化反应),从而形成包含甲烷、氢气、碳氧化物和蒸汽的气体混合物332。该气体混合物在换热器334中冷却至约300℃,并且经由管线336供给含Ni或贵金属甲烷化催化剂340床层的甲烷化容器338。来自管线336的冷却的气体混合物的一部分经由管线342取出,通过冷却换热器344并在压缩机346中压缩以生成循环料流316。来自甲烷化反应器338的富甲烷气流348在换热器350以及接着在312中冷却以形成供回到天然气进料(图2中的216)的富甲烷气流352。在该实施方案中,来自甲烷化反应器338的热量用于在换热器350中增加蒸汽,然后在换热器312中加热高级烃。管线326中的蒸汽用换热器350中来自甲烷化反应器的热量、接着是换热器334中来自重整器的热量生成。
为了举例,用供给重整器和甲烷化容器的不同的高级烃混合物计算下列三种情况。本发明生成的CO2的量与燃烧C2+烃生成的CO2量形成对比。
实施例1:100MMSCFD进料中5%乙烷
  MMSCFD   发明   燃烧C2
 乙烷进料   5
 蒸汽   6.69
 产生的CO2   1.25   24011te/yr   255722te/yr
 甲烷产物   8.75
MMSCFD=百万标准立方英尺气体/天。
实施例2:100MMSCFD进料中5%乙烷、3%丙烷和1%丁烷的混合物
  MMSCFD   发明   燃烧C2、C3、C4
 乙烷进料   5
 丙烷进料   3
 丁烷进料   1
 蒸汽   14.75
 产生的CO2   3.5   67207te/yr   441486te/yr
 甲烷产物   19.5
实施例3:600MMSCFD进料中5%乙烷、3%丙烷和1%丁烷的混合物
  MMSCFD   发明   燃烧C2
 乙烷进料   30
 丙烷进料   18
 丁烷进料   6
 蒸汽   163
 产生的CO2   24   460916te/yr   1151940te/yr
 甲烷产物   126
蒸汽的量基于1.3kg/kg蒸汽与烃比率。
在每一种情况下,本发明的运用与燃烧相比显著减少CO2产量。

Claims (30)

1.用于处理海上天然气的方法,其包括通过如下步骤在海上加工设备加工所述天然气,
(i)将天然气液化和分馏以产生液化天然气料流和高级烃料流,
(ii)将至少一部分的所述高级烃料流气化,
(iii)使气化的高级烃料流和蒸汽在蒸汽重整催化剂上通过以产生包含甲烷、蒸汽、碳氧化物和氢气的重整气体混合物,
(iv)使重整气体混合物在甲烷化催化剂上通过以产生富甲烷的气体,和
(v)在液化步骤之前将富甲烷的气体与天然气合并。
2.权利要求1的方法,其中所述海上天然气加工设备为固定的海上设备或浮动的海上设备如浮动的生产、储存和卸载(FPSO)设备。
3.权利要求1或2的方法,其包括通过使天然气经过含有适合用于除汞的纯化材料的纯化单元,在液化和分馏步骤上游纯化天然气以除汞。
4.权利要求1-3任一项的方法,其包括通过使天然气或高级烃料流经过含有适合用于脱除硫化合物的纯化材料的纯化单元,在液化步骤和/或重整步骤的上游纯化天然气或高级烃料流以除去硫化合物。
5.权利要求4的方法,其中用于脱除硫化合物的纯化步骤在液化步骤和重整步骤上游设置。
6.权利要求1-5任一项的方法,其中用膜使纯化的天然气流经历初步分离阶段以产生气态高级烃料流。
7.权利要求1-6任一项的方法,其中液化和分馏步骤将天然气分成富甲烷料流、乙烷料流、LPG料流和重质料流。
8.权利要求7的方法,其中将乙烷和/或一部分LPG和/或含C5+链烷烃的重质料流供给重整步骤。
9.权利要求7或8的方法,其中供给重整步骤的高级烃料流包含>50体积%、优选>75体积%、更优选>90体积%的乙烷。
10.权利要求1-9任一项的方法,其中用来自甲烷化步骤的热量和/或通过加入蒸汽使高级烃料流气化。
11.权利要求1-10任一项的方法,其中重整步骤在10-50bar的压力和200℃以上的温度下在Ni催化剂或贵金属催化剂或它们的组合上操作。
12.权利要求1-11任一项的方法,其包括在一个或多个换热器中在重整气体混合物与水之间交换热量以产生用于重整步骤的蒸汽。
13.权利要求1-12任一项的方法,其中甲烷化步骤在10-50bar的压力和100-400℃的温度下在Ni催化剂或贵金属催化剂或它们的组合上操作。
14.权利要求1-13任一项的方法,其包括使用CO2脱除单元在将富甲烷的气流与天然气合并之前或之后从中脱除二氧化碳。
15.权利要求1-14任一项的方法,其包括使用干燥单元在将富甲烷的气流与天然气合并之前或之后将它干燥。
16.用于处理海上天然气的装置,其包括海上天然气加工设备,该设备上安装有:
(i)包括分馏装置的天然气液化单元,其配置用于产生液化天然气料流和高级烃料流,
(ii)气化装置,其操作性地连接至所述液化单元并且配置用于将至少一部分的所述高级烃料流气化,
(iii)用于向气化的高级烃料流中添加蒸汽的装置,
(iv)操作性地连接至气化装置的重整容器,含有重整催化剂的所述重整容器经配置以使得气化的高级烃料流和蒸汽在催化剂上通过以产生包含甲烷、蒸汽、碳氧化物和氢气的重整气体混合物,
(v)操作性地连接至重整容器的甲烷化容器,含有甲烷化催化剂的所述甲烷化容器经配置以使得重整气体混合物在催化剂上通过以产生富甲烷的气体,和
(vi)混合装置,其用于将富甲烷的气体与供给天然气液化单元的天然气混合。
17.权利要求16的装置,其中所述海上天然气加工设备为固定的海上设备或浮动的海上设备如浮动的生产、储存和卸载(FPSO)设备。
18.权利要求16或17的装置,其包括含有适合用于除汞的纯化材料的纯化单元,所述单元在液化单元上游安装。
19.权利要求16-18任一项的装置,其包括含有一种或多种适合用于脱除硫化合物的纯化材料的纯化单元,所述单元在液化单元和/或重整容器上游安装。
20.权利要求16-19任一项的装置,其包括含有膜的初步分离单元,所述单元在液化单元上游操作性地连接,其使一部分高级烃与天然气分离从而生成气态高级烃料流。
21.权利要求16-20任一项的装置,其中配置液化和分馏装置用于将天然气分成富甲烷料流、乙烷料流、LPG料流和重质料流。
22.权利要求16-21任一项的装置,其中配置液化和分馏装置用于将乙烷以及任选地一部分LPG和/或含C5+链烷烃的重质料流供给重整步骤。
23.权利要求16-22任一项的装置,其中用来自甲烷化步骤的热量和/或通过加入蒸汽来加热气化器。
24.权利要求16-23任一项的装置,其中借助于直接加入或通过饱和器将蒸汽加入到气化的高级烃料流中。
25.权利要求16-24任一项的装置,其中蒸汽重整器为含有Ni催化剂或贵金属催化剂、或它们的组合的绝热蒸汽重整器。
26.权利要求16-25任一项的装置,其包括一个或多个换热器,所述换热器配置用于用水冷却重整气体混合物从而产生在重整步骤中使用的蒸汽。
27.权利要求16-26任一项的装置,其中甲烷化催化剂为Ni催化剂或贵金属催化剂、或它们的组合。
28.权利要求16-27任一项的装置,其包括CO2脱除单元,安装该单元以使得它在将富甲烷的气流与天然气合并之前或之后从中脱除二氧化碳。
29.权利要求16-28任一项的装置,其包括干燥单元,安装该单元以使得它在将富甲烷的气流与天然气合并之前或之后将其干燥。
30.权利要求1-15任一项的方法或权利要求16-29任一项的装置的用途,其用于减少海上天然气加工设备的CO2排放。
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WO2010004300A1 (en) 2010-01-14
GB0812699D0 (en) 2008-08-20
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JP2011527371A (ja) 2011-10-27
US8956428B2 (en) 2015-02-17
JP5325295B2 (ja) 2013-10-23
US20110174016A1 (en) 2011-07-21
MY150434A (en) 2014-01-30
BRPI0915485A2 (pt) 2015-11-10

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