CN111003689A - 在天然气管中运输氢气的方法和消除二氧化碳排放的方法 - Google Patents

在天然气管中运输氢气的方法和消除二氧化碳排放的方法 Download PDF

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CN111003689A
CN111003689A CN201911343345.6A CN201911343345A CN111003689A CN 111003689 A CN111003689 A CN 111003689A CN 201911343345 A CN201911343345 A CN 201911343345A CN 111003689 A CN111003689 A CN 111003689A
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卡尔·维尔纳·迪特里希
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Abstract

氢气是可再生能源的二次能源载体。通常采用水电解方法产生氢气，用于存储电能。在燃料电池中，氢气可以被再次转换成电能。天然气管网为氢气的存储提供了条件。但是，因为天然气和氢气在物理和燃烧性能上有差异，将氢气存储在天然气管网就受到了极大的限制。本申请描述了电解氢气和合成气反应生成甲烷，再将甲烷引入天然气管网的方法。从天然气管网取用引入的甲烷或类似天然气，在转化炉中再次转化为氢气和二氧化碳。必须在合成气中加入2摩尔的电解氢气用于形成1摩尔的甲烷。甲烷再次分解时将获得双倍量的氢气。合成气可以从生物质，例如木材、煤炭或碳化合物中获取。优选的方法是在转化炉中除了氢气形成的二氧化碳以外还使用等摩尔量的新鲜甲烷/天然气。以这种方式形成的合成气既经济又清洁。二氧化碳进入循环，而不会影响环境。二次能源载体氢气将作为类似天然气的甲烷存储和分布在天然气管网中，在取用时摩尔量加倍，并作为氢燃料电池用于再转化。

Description

在天然气管中运输氢气的方法和消除二氧化碳排放的方法
本案是以申请日为2014-12-04，申请号为201480064224.7，名称为“蓄能发电燃料电池”的发明专利为母案而进行的分案申请。
氢气是可再生能源的二次能源载体。它可以从风能和太阳能的水电解中获取，在天然气管网中存储和运输，并单独或与天然气一起被转化为电能。氢气通过燃料电池转化为电能，这一话题备受关注，因为其转化率高，而且可用于移动应用。
因为天然气和氢气在物理和燃烧性能上有差异，导致在使用终端存在问题，因此如WO 2013/043130“蓄能发电”中所述将氢气与合成气(一氧化碳+氢气)转化为甲烷，并将类似天然气的甲烷引入天然气管网，作为可再生能源存储和运输。
引入的甲烷可以作为天然气从天然气管网中取用，然后再次转化为电能。为了转化成燃料电池，可将取用的天然气/甲烷在蒸汽转化炉中再次转化成氢气。在该方法中，根据反应方程式1和2，在电解液中从可再生电能获取的氢气的摩尔量将翻倍：
1.合成气和氢气的反应(CO+H2)+2H2＝CH4+H2O
2.甲烷在蒸汽转化炉中分解CH4+4H2O＝4H2+CO2
如图1所示，在甲烷形成的过程中，1摩尔的甲烷需要在合成气(CO+H2)中加入2摩尔的电解氢气(H2)，甲烷/天然气在蒸汽转化炉再次分解时将获得4摩尔的氢气。
因此，本发明涉及合成气与通过水电解和电能获得的氢气一起转化为甲烷，并将甲烷引入天然气管网，从天然气管网引入的甲烷中取用等摩尔量的天然气/甲烷，在蒸汽转化炉中将取用的天然气/甲烷转化成氢气和二氧化碳，并将最后得到的氢气通过燃料电池转化为电能，其中，在合成气中加入2摩尔的氢气形成1摩尔的甲烷，甲烷在蒸汽转化炉再次分解时将获得4摩尔的氢气。
值得强调的是，这里所说的电解氢气作为可再生能源的二次能源载体，转化为类似天然气的甲烷，在天然气管网运输和存储，取用时在蒸汽转化炉中转化为双倍的氢气，然后氢气以最佳的能量转化形式转化为燃料电池。
在蒸汽转化炉中，除了氢气以外，还形成了二氧化碳，分离后或被存储或被释放。二氧化碳的释放会导致其在大气中的含量增加。如果在生成合成气时使用生物质，例如木材，则因此产生的二氧化碳释放对气候是无害的。
如果从生物质中获取二氧化碳，并在转化时存储/隔离，则作为生物质使用的植物在生长期从大气吸收的二氧化碳将永久存储在土壤里：根据本发明，一定比例的二氧化碳将转化成有机二氧化碳，从而使大气中的二氧化碳减少。
二氧化碳也可作为可再生能源的化学原料和存储材料。其中，氢气与存储的二氧化碳转化为甲烷，如上所示被引入天然气管网。还可以生成甲醇和甲醛。
总之，根据本发明，在转化过程中从甲烷/天然气得到的二氧化碳可以被：
1.释放
2.隔离
3.存储并用于转化成甲烷或作为化学原料使用。根据第3点，如果在氢气甲烷化过程中使用二氧化碳代替合成气，则每形成1摩尔甲烷需要4摩尔氢气，而不是如使用合成气时的2摩尔。
在本发明的一个特殊实施例中，转化所获得的二氧化碳被存储并与新鲜天然气在所谓的“干转化”反应中一起转化为合成气，根据本发明与电解氢气再次反应转化为甲烷。即，从转化炉中获得的二氧化碳将进入循环。
从转化炉中获得的二氧化碳可以在甲烷生成的地方与电解氢气一起运输。无论是运输还是存储，二氧化碳都必须以液体的形式保存在压力容器中或以所谓“干冰”的固体形式保存在绝热容器中。必须注意的是：再次使用的二氧化碳不得排放到大气中！二氧化碳也可作为气体保存。
从转化炉中获得的二氧化碳之所以适合再次使用是因为与燃烧碳化合物产生的二氧化碳不同，前者易于分离。甲烷与水蒸气反应的最终产物只有二氧化碳和氢气，通过氢气的变压吸附或二氧化碳的压力液化很容易将两者分离。
因此，本发明涉及二氧化碳与通过水电解和电能获得的氢气一起转化为甲烷，将甲烷引入天然气管网，从天然气管网取用甲烷或等摩尔量的天然气，其在转化炉中转化成氢气和二氧化碳，分离这两种气体(氢气和二氧化碳)，使用氢气在燃料电池中产生能源，二氧化碳重新甲烷化。在进行化学反应之前，二氧化碳可与氢气和天然气反应生成合成气。需要提醒的是：使用二氧化碳时需要4摩尔的氢气才能形成1摩尔的甲烷，而使用合成气只需要2摩尔的氢气。
合成气的制备是通过蒸汽加热和加压碳化合物和材料的已知方法，发生反应后形成几乎等摩尔量的一氧化碳(CO)和氢气(H2)的混合物。
在甲烷转化过程中，如果从转化炉中获得的二氧化碳被释放，则优选生物质，例如木材作为合成气的原料。有机二氧化碳的排放对气候是无害的。另外也可以使用生物和化石碳的材料混合物来制备合成气。引入天然气管网的甲烷中的有机含量可通过放射性碳(C14)方法来检测。只有生物炭包含C14(见WO 2013/034130，第18页第1和第2条)。
氢气一直被认为是波动风能和太阳能的二次能源载体。因为只有氢气能高效的转化为燃料电池。其缺点在于必须建立完全独立的基础设施用来分配和存储。
因此，本发明涉及氢气和合成气转化为甲烷，将所获得的类似天然气的甲烷引入天然气管网，在蒸汽转化炉中将再次转化为氢气，并转化为燃料电池形式的电能。
在专利申请WO 2013/152748“蓄能发电”中，电解氢气与合成气一起转化为甲烷，将甲烷引入天然气管网并存储，本发明增加了存储的甲烷在复原之前在蒸汽转化炉中再次转化为氢气，氢气用于燃料电池中发电。
特别有利的是，在转化炉中除了氢气以外，还使用形成的二氧化碳用于生成合成气。为此，将二氧化碳与等摩尔量的甲烷/天然气在已知的“干转化”反应中一起转化为合成气。二氧化碳进入循环，而不是到大气中。通过这种方式产生充足的合成气，既清洁又经济。含有二氧化碳的甲烷在重组时产生以下化学循环：
1.产生合成气CO2+CH4＝2(CO+H2)
2.电解氢气甲烷化(CO+H2)+2H2＝CH4+H2O
3.CH4在天然气管网的引入、存储和分布
4.CH4的取用和重组CH4+2H2O＝4H2+CO2
5.氢气和二氧化碳的分离，通过氢气发电并将二氧化碳返回到重新生成甲烷的地方。
在第1个化学循环中，天然气使合成气增加。上述循环只需要第4个循环所形成的二氧化碳的一半，因此在2中可以生成额外的可再生的甲烷，例如用于CNG燃料。
在第4个化学循环中，从天然气管网引入的甲烷(CH4)中取用等量的天然气。
在第5个化学循环中，分离的氢气可分配到区域管网或压力罐中。
再次提醒：在第2个化学循环中需要使用2摩尔的电解氢气，以形成1摩尔的甲烷，而在第4个化学循环中，在转化炉中1摩尔甲烷/天然气包含4摩尔氢气。在第2个化学循环中加入1摩尔合成气(从第1个化学循环中1/2摩尔的二氧化碳和第4个化学循环中1/2摩尔新鲜甲烷/天然气中获得)。
本发明中所述方法的副作用在于波动风能和太阳能以类似天然气的甲烷形式存储和分布在天然气管网。这有助于减少可再生能源过剩，减少电网的负担。
如同“蓄能发电”中所述，通过在电解氢气中加入廉价的合成气提高电解效率。在“蓄能发电”中转化效率加倍，在本发明中反应链的最后将获得双倍量的氢气。
在德国专利申请DE102012007136.1“废气转化成甲烷/化学蓄能发电”中描述从二氧化碳转化成甲烷的简单循环。在本发明中甲烷分解成氢气和二氧化碳，氢气用于发电，二氧化碳的存储和回收作为附加的方法步骤。在这两种情况下，二氧化碳都作为化学原料使用，从而避免了二氧化碳排放。甲烷转化为氢气的优点在于，在燃料电池中氢气的能量转化效率比甲烷/天然气高很多。
根据本发明，甲烷在蒸汽转化炉中转化为氢气，随后在燃料电池中发电，这与在机动车中燃烧甲烷/天然气所产生的能量相比，能效提高了几乎100％。
本发明中的燃料电池还可用于移动应用，因为氢气可以作为类似天然气的甲烷存储、分布和使用。此外，该方法中在总成本中占主导地位的电解效率也增加了一倍。因此，燃料电池在未来移动应用中深受欢迎，因为它将内燃机的燃料范围与电子移动的能源效率相结合。

Claims (11)

1.一种在天然气管网中运输氢气的方法，其中，将甲烷或天然气(NG)在重整器中生成的二氧化碳与通过电力电解产生的氢气转化为甲烷，并将反应生成的甲烷输送到天然气管网中，甲烷在天然气管网中运输，甲烷或等量的天然气从天然气管网中抽出，在重整器中转化为氢气和二氧化碳，将所述氢气和所述二氧化碳分离出来，所述氢气在燃料电池中转化为电能，然后将所述二氧化碳运送到与通过电能电解产生的氢气反应重新生成甲烷的地方而不排放到大气中。
2.根据权利要求1所述的方法，其中，1摩尔所述二氧化碳与4摩尔电解产生的氢气反应成甲烷。
3.根据权利要求1所述的方法，其中，所述二氧化碳与甲烷或天然气转化为合成气，所述合成气与电解产生的氢气反应。
4.根据权利要求1，2或3所述的方法，其中，所述二氧化碳以液态在压力罐中运输。
5.根据权利要求1，2或3所述的方法，其中，所述二氧化碳以固态在隔热容器中运输。
6.根据权利要求1，2或3所述的方法，其中，用于电解的电能是风能或太阳能。
7.根据权利要求1，2或3所述的方法，其中，所述燃料电池用于移动应用。
8.根据权利要求1，2或3所述的方法，其中，所述二氧化碳和所述氢气通过变压吸附分离。
9.根据权利要求1，2或3所述的方法，其中，通过在压力下将所述二氧化碳液化而使所述二氧化碳与所述氢气分离。
10.一种消除二氧化碳排放的将甲烷或天然气转化为电能的方法，其中甲烷或天然气在重整器中转化为氢气和二氧化碳，将所述氢气和所述二氧化碳分离，所述氢气在燃料电池转化为电力，所述二氧化碳用于和电能电解产生的氢气进行甲烷化反应，生成的甲烷被输送天然气管网中，并在天然气管网中存储和运输，所述二氧化碳从重整器的地方被运输到甲烷化反应处用于制甲烷而不排放到大气中。
11.根据权利要求10所述的方法，其中所述二氧化碳下以固态在隔热压力容器中或以液态在压力罐中运输。
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