CN101426885A - 提高烃生产中的碳效率 - Google Patents
提高烃生产中的碳效率 Download PDFInfo
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Abstract
本发明涉及一种利用煤或甲烷原料生产液体烃、优选内燃机燃料的方法。取决于原料的性质,原料经历气化和/或重整和/或水煤气变换过程,产生富含二氧化碳和氢气的合成气,而不是传统过程中富含一氧化碳和氢气的合成气。二氧化碳和氢气在费-托过程中结合产生所需的烃和水。产生富含二氧化碳和氢气的合成气所需的气化/重整过程的能量需要明显少于产生常规的富一氧化碳合成气的气化/重整过程的能量需要。与基于富一氧化碳合成气的传统过程相比,这种能耗的降低大幅减少释放到大气中的二氧化碳的量。未反应的富CO2合成气可以再循环,或者还可以用于熔融碳酸盐燃料电池中,或在诸如IGCC的涡轮机过程中产生能量或蒸汽。
Description
技术领域
本发明涉及通过费-托法(Fischer-Tropsch process)提高烃生产中的碳效率和减少二氧化碳的排放。
背景技术
费-托法主要用于将一氧化碳和氢气(亦称“合成气”)转变成用作燃料的液态烃。
使用费-托法合成烃的典型工艺流程图如下:
在上述过程中,气化器的原料通常是煤或甲烷气体。在该图中,Q1代表输入气化区段(在煤原料的情况下)或重整区段(在甲烷气的情况下)的能量,Q2代表从费-托合成过程中输出的能量。
在用煤作原料的情况下,起初,煤通过以下气化过程转变成一氧化碳(CO)和氢气(H2):
C+H2O→CO+H2
然后一氧化碳通过以下水煤气变换过程部分转变成二氧化碳(CO2)和氢气(H2):
CO+H2O→CO2+H2
控制水煤气变换过程,以提供费-托法所需的CO:H2摩尔比。通常CO:H2摩尔气体比是1:2。以该方式产生的二氧化碳通过该过程排出,从而导致碳效率低。
在使用甲烷(CH4)作进料的情况下,使用以下重整过程:
CH4+H2O→CO+3H2
与进料煤过程的情形一样,水煤气变换过程将一氧化碳部分转化为二氧化碳,以提供费-托法所需的1:2的CO:H2摩尔比。用该方式产生的二氧化碳通过该过程排出。
如上所指出的,CO和H2的气体组合物被称为“合成气”,可以用于费-托法来生产宽范围的基于碳的化学品,这些化学品中最重要的大概是内燃机用燃料。
合成气生产过程是吸热的,因此,需要相当多的能量。这还导致二氧化碳的大量排放,对上述合成燃料工厂产生不利影响,其原因是二氧化碳是所谓的“温室气体”。另一方面,逐渐减少且日渐昂贵的原油储备,加上明显大的天然气资源和低品位煤,对这类工厂的建立和运行产生不利的影响。
应当注意,以下术语在用于本说明书中时具有以下含义:
1.“碳效率”是指在该过程的全部进料(包括提供能量的所有进料流)中作为所需产物中的碳出现的碳的量;和
2.“富CO2合成气”是其中含有CO2、H2和CO气体混合物。在该混合物中,CO2成分多于常规合成气中通常存在的二氧化碳。该CO2用作反应剂,并转化成所需产物。
发明目的
本发明的一个目的是提高烃生产中的碳效率,并且随之减少二氧化碳的排放。
发明内容
根据本发明,提供了一种从合适原料产生的富CO2合成气生产烃的方法,包括以费-托法反应富CO2合成气,以根据全过程质量平衡来产生烃:
还规定在必要时使用水煤气变换方法以改变富CO2合成气并获得所需CO2浓度。
还规定使用富CO2合成气中的CO以根据以下过程产生烃:
还规定在气化器/重整器中通过使用多于一种原料、优选煤和天然气或甲烷的联合气化器过程和重整过程生产合成气体,作为一个替代方案,仅通过使用固体原料、优选煤的气化器过程生产,作为另一替代方案,仅通过使用天然气、优选甲烷的重整过程生产。
还规定甲烷来源于天然气储藏,或者作为替代方案,通过微生物降解废品产生甲烷。
还规定调节输入气化器/重整器阶段的能量,以使化学反应朝有利于产生CO2的方向移动,并且以将CO2与氢气结合使用以通过费-托法形成烃类化合物。
还规定循环未反应的二氧化碳、一氧化碳和氢气以用于发电和/或产生蒸汽。
本发明延及使用未消耗的(作为替代方案,废弃的)CO2和H2用于燃料电池,优选用于熔融碳酸盐燃料电池,以提供电能。
附图说明
下面将参考附图以举例的方式描述本发明,其中:
图1是根据本发明一个实施方案的费-托反应器的示意图;以及
图2是能够利用过量或废弃二氧化碳和氢气产生电能的一个熔融碳酸盐燃料电池实施方案的示意图。
具体实施方式
参考图1,用于生产烃的费-托法(1)包括将原料送入气化器/重整过程(3)的原料入口(2),在气化器/重整过程(3)中,原料转变成富CO2合成气(4),富CO2合成气(4)到达费-托合成区段(5),在其中转变成费-托法产物,该产物优选是液态烃和水。未反应的气体或不需要的气体产物可以循环回到气化器/重整过程,或进料至费-托合成区段(7)。
在使用煤作原料的情形中,煤被处理生产一氧化碳和氢气。该气化过程如下:
C+H2O→CO+H2
在使用来自天然气源的甲烷作原料的情形中,甲烷通过下述重整过程转化成一氧化碳和氢气:
CH4+H2O→CO+3H2
然后,来自上述任意一个过程的一氧化碳通过以下水煤气变换过程部分转变成二氧化碳和氢气:
CO+H2O→CO2+H2
上述反应全部发生在气化器/重整过程(3)中,并可以通过改变气化/重整过程的操作条件来改变二氧化碳浓度,以符合特定的需要。
在气化器/重整过程(3)中生产的合成气经管道输送至费-托合成区段(5),在费-托合成区段(5)中合成气至少部分转化成烃,取决于反应动力学,该烃可以适合于用作内燃机燃料、润滑油或地板蜡等几种产品。主要利用二氧化碳和氢气的费-托法如下:
CO2+3H2→-CH2-+2H2O
富CO2合成气中的一氧化碳可以按下式与氢气反应产生烃:
CO+2H2→-CH2-+H2O
未反应的二氧化碳、一氧化碳和氢气可以经过导管(7)从费-托合成区段(5)再循环进入气化器/重整过程阶段(3),或返回费-托合成区段。
通过产生富CO2合成气而不是常规过程中的富CO合成气,气化/重整过程(8)所需的能量明显减少。
除了上述之外,未反应的二氧化碳,一氧化碳和氢气可用于在例如IGCC过程中发电和/或产生蒸汽。
除了上述内容并参考图2,过量或废弃的二氧化碳和氢气可以用于熔融碳酸盐燃料电池(10)。该燃料电池(10)利用诸如钠或镁的盐类高温化合物作为电解质(11)。氧(12)和二氧化碳(13)被送到电池(10)的阴极(14)端,并在该处转化成三氧化碳,该三氧化物迁移至供给作为电子供体的氢气(16)的电池(10)阳极(15)端。该反应在电池的阳极(15)端产生水(17)。
当来自电解质的碳酸根离子在反应中耗尽时,必须将二氧化碳注入电池来补偿这种消耗。
可以设想,从富CO2合成气生产合成碳产物的作为常规费-托法的上述替代方案和生产合成气的常规方法的上述替代方案产生明显较少的排放到大气中的二氧化碳,因此对环境更加友好。
数据
下表提供了与在基于富CO合成气的传统费-托法以及基于富CO2合成气的本专利方法中所需的进料以及产生的产物有关的数据。所涉及的进料是煤。还提供了这两种方法的二氧化碳排放和碳效率。
从煤原料生产1吨烃
常规方法:富CO合成气
进料(吨) | 产物(吨) | |
区段1-气化 | ||
煤(碳) | 1.29 | |
水 | 1.93 | |
一氧化碳 | 3 | |
氢气 | 0.43 | |
从能量输入产生的二氧化碳 | 1.57 | |
区段2-费-托合成 | ||
一氧化碳 | 3 | |
氢气 | 0.43 | |
烃 | 1 | |
二氧化碳 | 1.57 | |
水 | 0.64 | |
二氧化碳总排放 | 3.14 | |
碳效率 | 50% |
替代方法:富CO2合成
进料(吨) | 产物(吨) | |
区段1-气化 | ||
煤(碳) | 1.29 | |
水 | 3.86 | |
二氧化碳 | 4.71 | |
氢气 | 0.86 | |
从能量输入产生的二氧化碳 | 1.08 | |
区段2-费-托合成 | ||
一氧化碳 | 4.71 | |
氢气 | 0.86 | |
烃 | 1 |
二氧化碳 | 1.57 | |
水 | 2.57 | |
二氧化碳总排放 | 2.65 | |
碳效率 | 54% |
这些计算是基于本方法的理想化目标,但是设想本领域的技术人员将会能够使本方法适于符合特定的条件和期望的输出。此外,应该理解,可以使用替代进料来代替煤或与煤联合使用。这类替代进料的实施例包括得自天然气矿藏或通过天然废弃物发酵产生的富甲烷天然气。
Claims (19)
2.根据权利要求1所述的从富CO2合成气产生烃的方法,其中所述方法包括在必要时利用水煤气变换方法改变所述富CO2合成气并获得所需CO2浓度。
3.根据权利要求1或2所述的从富CO2合成气产生烃的方法,其中所述富CO2合成气中的CO也用于根据以下过程产生烃:
4.根据权利要求1至3中任一项所述的从富CO2合成气产生烃的方法,其中通过使用多于一种原料的联合气化器过程和重整过程产生合成气。
5.根据权利要求4所述的从富CO2合成气产生烃的方法,其中所述原料是煤和天然气或甲烷。
6.根据权利要求1至3中任一项所述的从富CO2合成气产生烃的方法,其中仅通过使用固体原料的气化器过程产生合成气。
7.根据权利要求6所述的从富CO2合成气产生烃的方法,其中所述固体原料是煤。
8.根据权利要求1至3中任一项所述的从富CO2合成气产生烃的方法,其中仅通过使用天然气的重整过程产生合成气。
9.根据权利要求8所述的从富CO2合成气产生烃的方法,其中所述气体是甲烷。
10.根据权利要求9所述的从富CO2合成气产生烃的方法,其中所述甲烷来源于天然气储藏。
11.根据权利要求9所述的从富CO2合成气产生烃的方法,其中通过微生物降解废品产生所述甲烷。
12.根据前述权利要求中任一项所述的从富CO2合成气产生烃的方法,其中调节输入气化器/重整器阶段的能量,以使所述化学反应朝有利于CO2产生的方向移动,并且以将由此产生的所述CO2与氢气结合,以通过费-托法形成烃类化合物。
13.根据权利要求12所述的从富CO2合成气产生烃的方法,其中未反应的二氧化碳、一氧化碳和氢气循环至所述气化器/重整器。
14.根据权利要求12所述的从富CO2合成气产生烃的方法,其中未反应的二氧化碳和氢气用于产生电。
15.根据权利要求12所述的从富CO2合成气产生烃的方法,其中未反应的二氧化碳、一氧化碳和氢气用于产生蒸汽。
16.根据权利要求14所述的从富CO2合成气产生烃的方法,其中未反应的二氧化碳和氢气用于在燃料电池中发电。
17.根据权利要求16所述的从富CO2合成气生产烃的方法,其中所述燃料电池是熔融碳酸盐燃料电池。
19.一种用于从通过权利要求1至17中任一项所述的方法产生的二氧化碳和氢气产生电的方法。
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Cited By (17)
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CN102597173A (zh) * | 2009-09-08 | 2012-07-18 | 俄亥俄州立大学研究基金会 | 具有原位co2捕集的合成燃料和化学品生产 |
CN102597182A (zh) * | 2009-08-04 | 2012-07-18 | Sk新技术株式会社 | 通过甲烷热分解和二氧化碳转化将含碳材料气化的方法 |
CN103261089A (zh) * | 2010-12-08 | 2013-08-21 | Sk新技术株式会社 | 减少二氧化碳排放的气化方法 |
US9371227B2 (en) | 2009-09-08 | 2016-06-21 | Ohio State Innovation Foundation | Integration of reforming/water splitting and electrochemical systems for power generation with integrated carbon capture |
CN106164221A (zh) * | 2014-03-24 | 2016-11-23 | 沙索技术有限公司 | 费‑托合成 |
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- 2007-04-24 US US12/226,312 patent/US8168684B2/en not_active Expired - Fee Related
- 2007-04-24 EA EA200870369A patent/EA200870369A1/ru unknown
- 2007-04-24 AP AP2008004677A patent/AP2435A/xx active
- 2007-04-24 CN CN200780014393XA patent/CN101426885B/zh not_active Expired - Fee Related
- 2007-04-24 EP EP07734375A patent/EP2021435A2/en not_active Withdrawn
- 2007-04-24 CA CA2652905A patent/CA2652905C/en active Active
- 2007-04-24 AU AU2007242514A patent/AU2007242514B2/en not_active Ceased
- 2007-04-24 WO PCT/IB2007/001057 patent/WO2007122498A2/en active Application Filing
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Also Published As
Publication number | Publication date |
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EA200870369A1 (ru) | 2009-04-28 |
UA97804C2 (ru) | 2012-03-26 |
AU2007242514B2 (en) | 2011-09-22 |
AP2435A (en) | 2012-08-31 |
US20090317669A1 (en) | 2009-12-24 |
AU2007242514A1 (en) | 2007-11-01 |
CA2652905C (en) | 2014-07-15 |
WO2007122498A2 (en) | 2007-11-01 |
EP2021435A2 (en) | 2009-02-11 |
CN101426885B (zh) | 2013-03-27 |
AP2008004677A0 (en) | 2008-12-31 |
ZA200809985B (en) | 2009-11-25 |
CA2652905A1 (en) | 2007-11-01 |
US8168684B2 (en) | 2012-05-01 |
WO2007122498A3 (en) | 2008-06-19 |
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