CN116096672A - 提高富co2流的纯度 - Google Patents
提高富co2流的纯度 Download PDFInfo
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- CN116096672A CN116096672A CN202180053869.0A CN202180053869A CN116096672A CN 116096672 A CN116096672 A CN 116096672A CN 202180053869 A CN202180053869 A CN 202180053869A CN 116096672 A CN116096672 A CN 116096672A
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- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 58
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 37
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
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- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
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- 230000003750 conditioning effect Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- QVGXLLKOCUKJST-BJUDXGSMSA-N oxygen-15 atom Chemical compound [15O] QVGXLLKOCUKJST-BJUDXGSMSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
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- 238000005201 scrubbing Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
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Abstract
一种生产高纯度CO2产物的方法和设备,包括:提供含有烃、氢气和/或CO的富CO2流,将其与富含甲烷(CH4)的流合并,并将其与氧气混合,从而形成CO2/O2混合物;使CO2/O2混合物经历催化氧化步骤,从而产生具有更高CO2和/或H2O浓度的纯化流;从所述纯化流中去除H2O以生产所述高纯度CO2产物流。例如,富CO2流源自生产氢气的设备的CO2去除工段。
Description
本发明涉及一种在生产氢气的设备或方法中,提高富CO2的流(例如,来自CO2去除单元的含有烃、氢气和/或CO的富CO2流)的纯度的方法和设备。更具体地,本发明涉及通过含有烃、氢气和/或CO的富CO2流的催化氧化(CATOX)来生产高纯度CO2产物的方法和设备。本发明还涉及一种从烃进料生产氢气的方法和设备,其中烃进料在任选的预重整器和用于生成合成气的自热重整器(ATR)中进行重整,在用于使合成气富含氢气的变换工段中使合成气进行水煤气变换转化,使经变换的气体经受二氧化碳去除步骤,由此产生所述富CO2流以及富H2流,并且任选地其中至少一部分富H2流用作低碳氢燃料,例如在用于预热烃进料的火焰加热器中。本发明还涉及CATOX单元用于纯化源自制氢设备的富CO2流的用途,该富CO2流含有烃、氢气和/或CO,同时不增加设备的碳排放。
对能够提供从CO2去除工段取出的高纯度富CO2流并同时提供高碳回收率的氢气设备的需求日益增加。因此,期望能够提供一种生产氢气的方法和设备,其能够生产高纯度的CO2产物,例如高达99.99%或甚至更高的CO2,同时保持至少95%的碳回收率。特别地,生产所谓的“蓝氢”,即从烃进料(如天然气)中生产氢气并捕获二氧化碳,需要在氢气方法/设备中具有至少95%的碳回收率。
在氢气生产中,该方法包括对烃进料进行蒸汽重整,然后进行水煤气变换(WGS)以及在CO2去除工段中去除CO2。来自CO2去除工段的CO2流通常含有少量杂质,如H2、H2O、MeOH(甲醇)、CH4、CO和惰性气体(如Ar)。常规简单的以胺吸收CO2,然后通过减压和加热进行胺再生,即胺洗涤单元,也会产生含有大量杂质的CO2流。来自CO2去除工段的杂质被携带在所谓的高压闪蒸气(HP闪蒸气)中。含有杂质的HP闪蒸气被输出或在火焰加热器中燃烧,其例如在重整期间预热烃进料。然而,这会增加CO2排放,并对碳回收率产生负面影响。
为了提高二氧化碳纯度,来自CO2去除工段中的CO2吸收器的富胺溶液可以在步骤中(减压)加压,例如在高压闪蒸步骤中的高压闪蒸罐中,然后在低压闪蒸罐中进行低压闪蒸步骤。在第一高压闪蒸步骤中,大部分杂质与一些CO2一起作为高压闪蒸气体释放到气相中。在低压闪蒸步骤中,主要将CO2作为富CO2流释放到最终产品中。富胺溶液在CO2再生中通过加热再生,向富CO2流释放更多的CO2。由于大部分杂质在来自高压闪蒸罐的高压闪蒸气体中释放,富CO2流以增加的纯度流出,例如>98vol%,例如98.5vol%或99vol%的CO2,但其仍将包含杂质,主要是H2,以及少量含碳化合物,特别是CH4和CO。期望将富CO2流的纯度进一步提高到99.9vol.%或99.99vol.%CO2或甚至更高。
US 2017/0152219 A1描述了一种制造尿素的方法。来自部分氧化步骤的合成气被引导至水煤气变换步骤以形成变换的合成气流,然后将其分离成第一和第二合成气子流。第一子流经受变压吸附以产生氢气,且第二子流经受变温吸附以产生二氧化碳。氢气与氮气反应生成氨,然后氨与二氧化碳反应生成尿素。在一个实施方案中,通过位于CO2与氨反应生成尿素的上游的催化氧化来去除在变温吸附中分离的CO2中的杂质。
EP 2281775 A1描述了一种利用共吹扫变压吸附单元生产氢气和二氧化碳的方法。变压吸附单元与二氧化碳纯化单元(例如低温单元或催化氧化器)一起用于处理来自任选的水煤气变换反应器的合成气。来自二氧化碳纯化单元的纯化的二氧化碳被再循环,以用作变压吸附单元的吸附床的共进料/共吹扫,从而产生具有更高CO2浓度的二氧化碳尾气。
需要提供一种替代的方法和设备,该方法和设备能够实现用于提高富CO2流的纯度的更简单的解决方案,特别是在用于生产氢气的方法和设备中。
因此,本发明的目的是提供一种用于提高富CO2流的纯度的替代方法和设备,即进一步提高其中的CO2浓度,从而获得高纯度CO2产物。
本发明的另一个目的是提高富CO2流的纯度,即进一步提高其中的CO2浓度,从而在用于生产氢气的方法和设备中获得高纯度CO2产物,同时避免CO2排放的增加,并在设备中保持至少95%的碳回收率。
本发明解决了这些和其他目的。
因此,在第一方面,本发明是一种生产高纯度CO2产物的方法,包括以下步骤:
i)提供含有烃、氢气和/或CO的富CO2流;将其与富含甲烷(CH4)的流(例如天然气流)合并;以及将其与氧气混合,从而形成CO2/O2混合物;
ii)使CO2/O2混合物经历催化氧化步骤,从而产生纯化流,该纯化流具有更高的CO2和/或H2O浓度,即高于与富含甲烷的流合并之前或之后的富CO2流中的CO2和/或H2O浓度,或高于所述CO2/O2混合物中的CO2和/或H2O浓度;
iii)从所述纯化流中去除H2O以生产所述高纯度CO2产物。
如本文所用,术语“催化氧化”,在本领域中是公知的,与其首字母缩写CATOX可互换使用,并指在氧气存在下,在催化剂上对富CO2流中的可燃杂质(如H2、H2O、MeOH、CH4、CO)和惰性气体(如Ar)的氧化。
CATOX步骤中的催化剂可以选自负载在载体上的金属和/或金属氧化物形式的钨、钒、钼、铂和钯;或选自负载在选自氧化铝、二氧化钛、二氧化硅和二氧化铈及其组合的载体上的金属和/或金属氧化物形式的钒、钨、铬、铜、锰、钼、铂、钯、铑或钌。
CATOX步骤的操作温度范围为100-600℃,例如150-400℃或200-350℃。例如,入口温度为约250℃,且出口温度为约350℃。出口通常用于预热进料/流出物换热器中的进料,在本发明中,该进料是CO2/O2混合物。
通过本发明,将富含甲烷(CH4)的流(例如天然气流)与所述富CO2流合并。这使得能够更好地控制氢气和氧气逸出。在CATOX步骤中,氧气通过与所有氢气的反应而被消耗,随后,剩余的氧气被富CO2流中存在的CH4所消耗。例如,天然气流可以是用于生成变换合成气的烃进料的一部分,这将在下面进一步解释。应当理解,富含CO2流、富含甲烷和氧气的流可以以各种方式合并,以形成CO2/O2混合物。
因此,应当理解,在步骤i)中,术语“由此形成CO2/O2混合物”是指还包括烃(例如CH4)、氢气和/或CO的CO2/O2混合物。
在根据本发明第一方面的实施方案中,CATOX步骤在两个或更多个步骤中进行,其间添加氧气。在一个特定实施方案中,通过分离氧气流并进料至两个或更多个步骤来提供氧气,即将氧气平行进料至CATOX单元,例如通过在进入后续或第二CATOX步骤之前将氧气与离开第一CATOX步骤的第一流混合来提供氧气。这进一步使得能够更好地控制由于任何过量的氢和/或氧而导致的氢气和氧气逸出。
如本文所用,术语“高纯度CO2产物”是指纯度高达99.8vol.%CO2或甚至更高,例如99.99vol%的CO2产物。应当理解,该高纯度CO2产物的CO2浓度高于含有烃、氢气和/或CO的富CO2流的CO2浓度。
如本文所用,术语“含有烃、氢气和/或CO的富CO2流”是指具有大量CO2的流,例如98vol%或更高,并且其还含有烃如CH4以及CO和H2。例如,小于0.05vol.%的CH4、小于0.05vol.%的CO和小于2vol.%的H2。
富CO2流是具有大量CO2的流,特别是如下面进一步解释的,是从二氧化碳去除工段的低压闪蒸步骤分离的流,并且具有98vol.%或更高的CO2浓度,例如99vol.%。
本发明能够将H2氧化成H2O并随后去除H2O以减少CO2产物中的H2含量,以及能够将其他组分如烃类进行氧化。
在根据本发明第一方面的实施方案中,在步骤iii)中,去除H2O包括将纯化流送至包括一个或多个冷却单元的冷却***,从而产生经冷却的纯化流,随后将经冷却的纯化流送至冷凝步骤,例如通过将纯化流送至冷凝物分离器,从而分离水作为冷凝物相。在特定实施方案中,冷却***包括第一冷却单元,用于在CATOX步骤之前,优选在进料/流出物换热器中预热所述CO2/O2混合物。在特定实施方案中,冷却***还包括使用来自空气分离单元(ASU)的N2的冷却单元,例如使用N2作为换热介质的换热器。
在根据本发明第一方面的实施方案中,氧气由空气分离单元(ASU)和/或水/蒸汽电解单元产生。因此,ASU优选还提供在进入催化氧化步骤ii)之前与富CO2流混合的氧气,以及用于重整步骤中使用的氧气,其中该重整步骤包括自热重整(ATR)。因此,可以更好地整合和利用ASU中产生的流,即不仅包括用于ATR的O2,而且还包括用于冷却***的N2。在另一个实施方案中,在进入催化氧化步骤ii)之前与富CO2流混合的氧气是通过提供水原料并使其通过电解单元(即水/蒸汽电解单元)而产生的。在特定实施方案中,电解单元是碱/聚合物电解质膜电解单元,即碱/PEM电解单元(碱性电池或聚合物电池单元)。这种电解单元利用水。在另一特定实施方案中,电解单元是固体氧化物电解单元。这种电解利用蒸汽。因此,更可持续的方法和设备是可能的,因为电解所需的电力可以由可再生能源如风能和太阳能提供。
应当理解,术语水原料包括水或蒸汽。还应理解,术语水/蒸汽是指水或蒸汽。
在根据本发明第一方面的实施方案中,步骤iii)还包括干燥步骤,优选在进行所述冷凝步骤之后。该干燥步骤能够最终去除水以提供基本上无水的纯化流。在特定实施方案中,干燥步骤在变温吸附单元中进行。这能够实现最高的CO2纯度,而不增加向大气的碳排放。变温吸附单元在本领域中是公知的。
在根据本发明第一方面的实施方案中,步骤i)的富CO2流源自CO2去除工段,所述CO2去除工段被布置成接收经变换的合成气流,其中CO2去除工段是胺洗涤单元,并且包括CO2吸收器、CO2汽提塔和低压闪蒸罐,所述富CO2流从所述低压闪蒸罐中分离。因此,根据该实施方案,富CO2流是源自低压闪蒸步骤的CO2产物流。例如,来自低压闪蒸罐的主要含有二氧化碳的塔顶流可在CO2分离器中进行分离步骤,从而分离富CO2流和可再循环到低压闪蒸罐中的冷凝流。在特定实施方案中,该富CO2流含有至少98vol.%的CO2,例如98.5vol.%或99vol.%的CO2。
在CO2去除工段,特别是胺洗涤单元中,通常期望在低压闪蒸步骤之前具有高压闪蒸步骤。然而,在根据本发明第一方面的另一特定实施方案中,CO2去除工段不存在高压闪蒸步骤。这能够减少与CO2去除工段相关的复杂性和成本,因为可以省略高压闪蒸罐(HP闪蒸罐)。此外,当操作具有HP闪蒸罐的CO2去除工段时,虽然可以将HP闪蒸气再循环回CO2去除工段的CO2吸收塔,但剩余的杂质最终留在从低压闪蒸罐分离的富CO2流中。这导致富CO2流的纯度比根据本发明使用CATOX获得的富CO2流低。HP闪蒸气也可以燃烧,将CO2释放到大气中,但富CO2流的纯度仍低于本发明。
因此,通过使用催化氧化,生成的CO2(其否则将以其他方式夹带在CO2去除工段的高压闪蒸气中)被捕获在从低压闪蒸罐中分离的富CO2流中,从而增加富CO2流的流量并避免增加向大气排放CO2。这对于需要将CO2排放减少到最低程度的蓝氢来说尤其重要。用于纯化CO2流的其他方法,例如变压吸附、膜过滤或低温,产生纯化流和尾气流。尾气流通常被燃烧,而将CO2释放到大气中。
特别是对于氢气设备,其中最大限度地捕获CO2是非常重要的,例如在生产蓝氢时,CATOX方法在不增加碳排放的情况下纯化CO2。在所有其他方法中,会产生尾气流,如果燃烧或必须以某种方式处理,会导致碳排放增加。
因此,本发明使用CATOX来纯化CO2,同时不增加设备中的碳排放。
至少部分的低压闪蒸气,例如以吹扫流的形式,经受催化氧化,从而也避免了杂质的积聚。在催化氧化步骤中,杂质被催化氧化为CO2和H2O。气体中氢气的氧化产生CATOX步骤所需的热量。可以通过冷凝从CO2流中去除H2O,然后任选地在诸如如上所述的变温吸附单元的单元中干燥。
在根据本发明第一方面的另一个实施方案中,CO2去除工段包括高压闪蒸罐,例如在所述低压闪蒸罐的上游,并且该方法还包括向所述富CO2流中添加氢气。这使得能够提供这样的CO2去除工段,该CO2去除工段能够产生源自低压罐的富CO2流以及高压闪蒸气流,该高压闪蒸气流可以用于例如火焰加热器中以在重整中预热烃进料。向富CO2流中添加的氢气由此确保提供CATOX步骤的必要负荷。氢气适宜地是源自从CO2去除工段取出的富H2流和/或源自水/蒸汽电解的氢气流中的流。
通过该方法获得的高纯度CO2产物优选被捕获和运输以在例如地质结构中封存,从而减少向大气的CO2排放。
优选地,CO2去除工段包含在用于生产氢气的方法或设备中,由此通过蒸汽重整(此处与术语重整可互换使用)产生的合成气经受水煤气变换以形成所述经变换的合成气流,随后在CO2去除工段中去除CO2。
因此,在根据本发明第一方面的实施方案中,步骤i),即包括提供含有烃、氢气和/或CO的富CO2流的步骤,包括:
-向重整工段供应烃进料,并将其转化为合成气流;
-从所述重整工段取出合成气流并将其供应至变换工段,在高温变换(HTS)步骤,并且任选地也在中温变换(MTS)和/或低温变换(LTS)变换步骤中变换合成气,由此提供经变换的合成气流;
-将经变换的合成气流从变换工段供应至CO2去除工段,适宜地所述胺洗涤单元,并将所述富CO2流与所述经变换的合成气流分离,从而提供富H2流。
因此,从CO2去除工段,不仅产生含有烃、氢气和/或CO的富CO2流,而且还产生富H2流。
如本文所用,术语富H2流是指含有95vol.%或更多,例如98vol.%或更多氢气的流,即具有高于95vol.%的氢气纯度,余量是少量的含碳化合物CH4、CO、CO2以及惰性气体N2、Ar。
通常使烃进料通过经由蒸汽重整(SMR)、二次重整(例如自热重整(ATR))和两步重整(串联SMR和ATR)的重整而产生合成气。SMR有利地是电加热蒸汽重整器(e-SMR,或可互换地,e-重整器),例如在申请人的专利申请WO2019/228797A1中公开的。也可包括使用预重整器的独立ATR特别适合根据本发明生产富H2流。
因此,在特定实施方案中,重整工段包括自热重整(ATR)。在另一特定实施方案中,重整工段还包括在将所述烃进料进料到ATR之前在一个或多个预重整器单元中预重整所述烃进料。
因此,优选地,所述方法或设备在ATR上游没有(即不存在)蒸汽甲烷重整器单元(SMR)。因此,重整可包括预重整,但其在没有初级重整(即没有初级重整单元)的情况下进行。因此,实现了设备尺寸的减小。
在一个特定实施方案中,该方法还包括在一个或多个火焰加热器中预热所述烃进料,并将至少一部分所述富H2流作为烃燃料进料到至少一个或多个火焰加热器。
通过使用富H2流的一部分作为燃料,即作为低碳氢燃料,可以以简单的方式使烃进料脱碳,该烃进料例如是天然气,由此捕获至少95%的碳,同时仍然在富H2流中实现高的氢纯度。
在根据本发明第一方面的实施方案中,该方法还包括提供氢化单元和硫吸收单元,用于在所述预重整之前或在送入所述ATR之前调节烃进料,例如用于硫去除,并在被进料到氢化单元之前将一部分富H2流(即作为H2再循环)与烃进料混合。
应当理解,重整工段是包括直到并包括ATR的单元的设备工段,即ATR,或者一个或多个预重整单元和ATR。重整工段还可包括一个或多个预重整单元和ATR上游的氢化单元和硫吸收器。
空气分离单元(ASU)被设置为接收空气流并产生含氧流,然后通过管道将其送入ATR。优选地,根据上述实施方案,含氧流包含添加到ATR中的蒸汽。包含氧化剂的流的实例是:氧气;氧气和蒸汽的混合物;氧气、蒸汽和氩气的混合物;和富氧空气。在ASU中,还产生氮气流,其有利地也可用于本发明的方法和设备,如上所述。
ATR出口处的合成气温度为900℃至1100℃,或950℃至1100℃,通常为1000℃至1075℃。从ATR(来自ATR的合成气)取出的该热流出物合成气包括一氧化碳、氢气、二氧化碳、蒸汽、残余甲烷和包括氮气和氩气的各种其他组分。
自热重整(ATR)在本领域和公开文献中被广泛描述。典型地,ATR包括燃烧器、燃烧室和布置在固定床中的催化剂,所有这些都包含在耐火衬里压力壳中。例如,AndreSteynberg和Mark Dry编辑的“Studies in Surface Science and Catalysis”,第152卷(2004),第4章中描述了ATR,还参见以下综述:“Tubular reforming and autothermalreforming of natural gas–an overview of available processes”,IbFuelProcessing Technology 42(1995)85-107。
优选地,在HTS单元上游添加蒸汽。在高温变换步骤之后,例如在一个或多个随后的MT或LT变换和/或HT变换步骤之前,可以任选地添加蒸汽,以使所述随后的HT、MT和/或LT变换步骤的性能最大化。用于进行HTS、MTS和LTS的催化剂和方法在本领域中是公知的。
在根据本发明第一方面的实施方案中,该方法不存在氢纯化步骤,例如变压吸附(PSA)。因此,不需要通过例如烧尽或燃烧来处理尾气,例如PSA尾气,从而进一步减少了CO2排放。在一个特定的实施方案中,该方法在所述CO2去除工段之后不存在氢气纯化步骤,例如变压吸附(PSA)。因此,该方法和/或设备被进一步简化,并且设备尺寸被减小。
在本发明的第二方面,还提供了一种用于生产高纯度CO2产物流的设备,即工艺设备,所述设备包括:
-管道,用于将氧气流(优选由空气分离单元(ASU)和/或水/蒸汽电解单元产生的氧气)与含有烃、氢气和/或CO的富CO2流混合;以及用于将富含甲烷(CH4)的流(例如天然气流)与所述富CO2流合并的管道,从而形成包含二氧化碳和氧气的混合物的入口气体;
-催化氧化(CATOX)单元,其被布置为接收所述包含二氧化碳和氧气的混合物的入口气体,所述CATOX单元包括用于将出口气体作为具有更高CO2和H2O浓度的纯化流排出的出口;
-冷却***,其被布置为接收来自CATOX单元的所述出口,所述冷却***包括用于冷却出口气体的一个或多个冷却单元;
-冷凝物分离器,其被布置为接收如此冷却的出口气体并用于去除H2O,从而形成包括所述高纯度CO2产物流的出口产物。
在本发明的第三方面,还提供了CATOX单元的令人惊讶的用途,该CATOX单元用于纯化含有烃、氢气和/或CO的富CO2流,该流源自生产氢气的方法或设备,特别是来自其CO2去除工段,同时不增加该设备的碳排放。
在根据本发明第三方面的实施方案中,所述方法包括:
-向重整工段供应烃进料,并将其转化为合成气流;
-从所述重整工段取出合成气流并将其供应至变换工段,在高温变换(HTS)步骤中,并且任选地也在中温变换(MTS)和/或低温变换(LTS)变换步骤中变换合成气,由此提供经变换的合成气流;
-将经变换的合成气流从变换工段供应至所述CO2去除工段,适宜地所述胺洗涤单元,并将所述富CO2流与所述经变换的合成气流分离,从而提供富H2流。
在根据本发明第三方面的另一个实施方案中,本发明还包括用于实施所述方法的设备,即,所述设备包括重整工段、变换工段和所述CO2去除工段。
同样适宜地,该方法或设备不存在氢气纯化单元,例如变压吸附(PSA)单元,例如CO2去除工段下游的PSA单元。
应当理解,本发明第一方面的任何实施方案和相关益处可以与本发明第二和第三方面的任何实施方案结合使用,反之亦然。
附图示出了根据本发明的一个实施方案的基于ATR的氢气方法和设备的布局,其具有富CO2流的进一步纯化。
参考该图,示出了一种设备/方法100,其中烃进料1(例如天然气)被送到包括预重整单元140和ATR 110的重整工段。重整工段还可以包括预重整单元140上游的氢化器和硫吸收器单元(未示出)。在进入氢化器之前,烃蒸汽1与从下游CO2去除工段170中产生的富H2流8分流出的氢再循环流8”’混合。在进入预重整单元140之前,烃进料1还与蒸汽13混合,并且所得的经预重整的烃进料2与通过混合氧气15和蒸汽13形成的氧化剂流一样被送入ATR110。蒸汽也可以单独添加,也如图所示。氧气流15由空气分离单元(ASU)145产生,空气14被送入该空气分离单元。在ATR 110中,烃进料2被转化为合成气流3,该合成气流从ATR110排出并传递至变换工段。该合成气通过耐火衬里出口工段和输送管线离开ATR,进入合成气中的废热锅炉(未示出),(即工艺气体冷却工段)。
变换工段包括高温变换(HTS)单元115,也可以在该高温变换单元115的上游添加另外的或额外的蒸汽13’。诸如低温变换(LTS)单元150的附加变换单元也可以包括在变换工段中。还可以在HTS单元115的下游和LTS单元150的上游添加另外或额外的蒸汽,以增加蒸汽/碳比(steam-to-carbon ratio)。从变换工段产生富含氢气的经变换的合成气流5,然后将其送入CO2去除工段170。CO2去除工段170包括CO2吸收器和CO2汽提塔(再生器),其从低压闪蒸罐(未示出)分离出富CO2流10,该富CO2流包含例如大于99vol.%的CO2和烃如CH4以及CO和H2。也从CO2去除工段170取出含有例如98vol.%或更高的氢气的富H2流8。任选地,可以从CO2去除工段170的高压闪蒸罐(未示出)产生高压闪蒸气体12。如图所示,设备100不存在氢气纯化单元,例如PSA。
富H2流8分流为供应到最终用户如炼油厂的H2产物8’、用于火焰加热器单元135的低碳氢燃料8”和用于与烃进料1混合的氢气再循环8”’。火焰加热器135提供对烃进料1和还任选的烃进料2的间接加热。
富CO2流10被压缩(未示出),例如与管线1(未示出)中进料的一部分天然气或单独的天然气流(未示出)混合,并与来自ASU的氧气流15混合,从而形成CO2/O2混合物流17。CO2/O2混合物在CATOX进料/流出物换热器180中预热,从而形成预热流18,然后将该预热流18送至CATOX单元190。从CATOX单元190,在例如本领域公知的催化剂固定床上进行催化氧化,从而产生纯化流19,该纯化流19具有比在与富含甲烷的流合并之前或之后的富CO2流10更高的CO2和H2O浓度,或比CO2/O2混合物流17和18更高的CO2和H2O浓度。该纯化流19被取出并用作进料/流出物换热器180中的换热介质。如此冷却的纯化流20在冷却***200中进一步冷却,冷却***200可包括CO2空气冷却器和CO2水冷却器(未示出)以及使用来自ASU的氮气16作为冷却介质的换热器。然后将氮气作为流21取出,同时在冷凝物分离器210中将水作为冷凝物流23从进一步冷却的纯化流22中去除,从而形成高纯度CO2产物流24,其CO2浓度为例如99.9vol.%或99.99vol.%或甚至更高。
Claims (15)
1.一种生产高纯度CO2产物的方法,包括以下步骤:
i)提供含有烃、氢气和/或CO的富CO2流;将其与富含甲烷(CH4)的流,例如天然气流,合并;以及将其与氧气混合,从而形成CO2/O2混合物;
ii)使CO2/O2混合物经历催化氧化步骤,从而产生纯化流,所述纯化流具有更高的CO2和/或H2O浓度,即高于在与富含甲烷的流合并之前或之后的富CO2流中的CO2和/或H2O浓度,或高于所述CO2/O2混合物中的CO2和/或H2O浓度;
iii)从所述纯化流中去除H2O以生产所述高纯度CO2产物。
2.根据权利要求1所述的方法,其中所述催化氧化步骤在两个或更多个步骤中进行,在步骤之间加入氧气。
3.根据权利要求1-2中任一项所述的方法,其中在步骤iii)中,H2O的去除包括将所述纯化流送至包括一个或多个冷却单元的冷却***,从而产生经冷却的纯化流,随后将所述经冷却的纯化流送至冷凝步骤。
4.根据权利要求3所述的方法,其中所述冷却***包括冷却单元,所述冷却单元使用来自空气分离单元(ASU)的N2。
5.根据权利要求1-4中任一项所述的方法,其中由空气分离单元(ASU)和/或水/蒸汽电解单元产生氧气。
6.根据权利要求1-5中任一项所述的方法,其中步骤iii)还包括干燥步骤,其优选在所述冷凝步骤之后。
7.根据权利要求6所述的方法,其中所述干燥步骤在变温吸附单元中进行。
8.根据权利要求1-7中任一项所述的方法,其中步骤i)的所述富CO2流源自CO2去除工段,所述CO2去除工段被布置成接收经变换的合成气流,其中所述CO2去除工段是胺洗涤单元,并且包括CO2吸收器、CO2汽提塔和低压闪蒸罐,从所述低压闪蒸罐中分离出所述富CO2流。
9.根据权利要求8所述的方法,其中所述CO2去除工段包括高压闪蒸罐,并且所述方法还包括向所述富CO2流中添加氢气。
10.根据权利要求1-9中任一项所述的方法,其中步骤i)包括:
-向重整工段供应烃进料,并将其转化为合成气流;
-从所述重整工段取出合成气流并将其供应至变换工段,在高温变换(HTS)步骤中,并且任选还在中温变换(MTS)和/或低温变换(LTS)变换步骤中变换合成气,由此提供经变换的合成气流;
-将所述经变换的合成气流从所述变换工段供应至CO2去除工段,适宜地供应至所述胺洗涤单元,并将所述富CO2流与所述经变换的合成气流分离,从而提供富H2流。
11.根据权利要求10所述的方法,其中所述重整工段包括自热重整(ATR),并且任选地还包括在将所述烃进料进料到所述ATR之前,在一个或多个预重整器单元中预重整所述烃进料。
12.根据权利要求10-11中任一项所述的方法,还包括在一个或多个火焰加热器中预热所述烃进料,并将至少一部分所述富H2流作为烃燃料进料到至少一个或多个火焰加热器。
13.根据权利要求1-12中任一项所述的方法,其中所述方法不存在氢纯化步骤,例如变压吸附(PSA),例如在所述CO2去除工段之后的PSA。
14.一种用于生产高纯度CO2产物的设备,所述设备包括:
-用于将氧气流,优选由空气分离单元(ASU)和/或水/蒸汽电解单元产生的氧气,与含有烃、氢气和/或CO的富CO2流混合的管道;以及用于将富含甲烷(CH4)的流,例如天然气流,与所述富CO2流合并的管道;从而形成包含二氧化碳和氧气的混合物的入口气体;
-催化氧化(CATOX)单元,其被布置为接收所述包含二氧化碳和氧气的混合物的入口气体,所述CATOX单元包括出口,所述出口用于取出出口气体作为具有更高CO2和/或H2O浓度的纯化流;
-冷却***,其被布置为接收来自CATOX单元的所述出口气体,所述冷却***包括用于冷却所述出口气体的一个或多个冷却单元;
-冷凝物分离器,其被布置为接收如此冷却的出口气体并用于去除H2O,从而形成包括所述高纯度CO2产物的出口产物。
15.CATOX单元用于纯化含有烃、氢气和/或CO的富CO2流且同时不增加设备的碳排放的用途,所述富CO2流源自生产氢气的方法或设备,特别是来自其CO2去除工段。
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