CN102686707A - 人工光合作用 - Google Patents
人工光合作用 Download PDFInfo
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- CN102686707A CN102686707A CN201080047245XA CN201080047245A CN102686707A CN 102686707 A CN102686707 A CN 102686707A CN 201080047245X A CN201080047245X A CN 201080047245XA CN 201080047245 A CN201080047245 A CN 201080047245A CN 102686707 A CN102686707 A CN 102686707A
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Abstract
本发明公开了一种用于在包含碳和氢的有机化合物中储存太阳能的方法。所述的方法包括提供水源和碳源。使用太阳能的一种形式活化水源中的水。经活化的水和碳源反应形成包含碳和氢的有机化合物。所述的有机化合物具有比碳源较高的能量含量。在一具体实施方式中,有机化合物被用作发电装置的燃料,例如燃料电池。在该实施方式中优选的有机化合物是甲醇。
Description
发明背景技术
1.发明领域
本发明一般性地涉及一种用于在含有碳和氢的有机化合物中储藏太阳能方法,并且特别地涉及一种用一种形式的太阳能来活化水的方法。
2.相关技术的描述
光合作用(photosynthesis)是植物和某些微生物体使用太阳能用于将二氧化碳和水转化成有机分子作为储藏能量的方法。此类有机化合物的实例包括糖、淀粉、纤维素、三酸甘油酯、树脂等等。
人类几乎100%依靠光合作用为它的能量需求。该以食物的形式为人类身体需求的能量是光合作用的直接产物(全部植物来源的食物),或者是光合作用的间接产物(肉,牛奶或其他动物来源的食物)。用于取暖和推动机器的能量也几乎总是源于光合作用,其为生物质或者化石燃料的形式。最显著地例外是太阳能、风能和核能,这些不依赖光合作用。
人类依靠自然光合作用来供应能量需求具有严重的缺陷。化石燃料的使用向空气中释放了二氧化碳,这被认为导致了气候变化。生物质的使用可以是碳中性的,但植物在将太阳能转化成有机分子是相对低效率的。这主要是由于叶绿素(在几乎所有植物中负责吸收太阳能的分子)仅仅能够吸收太阳光可见光光谱部分的一小部分,对光谱中的其他部分例如红外和紫外辐射一点也不吸收。根据统计,植物仅能使用它们接收到的太阳能的约3%。
自然光合作用的另外一个缺陷是就适宜生长的温度和气候而言植物需要特定的条件。因此,光合作用在温度低于约10℃时是缓慢的,并且在低于0℃时几乎不存在。类似的,在温度高于约30℃时,植物面临从土壤中吸收足够的水分以允许它们赶上通过的叶子蒸发的水分的挑战。在热气候期间许多植物减慢它们的光合作用以便保护它们自己不会干枯。
植物还需要供应足量的相当高品质的水。除了某些水生植物外,陆生植物通常耐盐不比它们耐干旱更好。外部过量供水也是有问题的,农作物可能会和在干旱中失去一样容易在洪水中失去。
最后,植物需要平衡供应用于它们健康的矿物元素和孢子元素(sporeelement)。这些营养需要通过土壤供应,在土壤中,植物生长,并且经常需要追加肥料。
总之,用于人类能量需求的植物的使用面临许多障碍和限制。
因此,存在对用于将太阳能存储在有机分子中的方法的需求。尤其是存在就温度要求而言比基于叶绿素的方法更加强大的方法的需求。此外存在对允许使用污染的水的方法的需求。
发明概述
本发明通过提供一种用于在包含碳和氢的有机化合物中储存太阳能的方法来解决这些问题,所述的方法包括以下步骤:
(i)提供水源和碳源;
(ii)在碳源存在下,使用太阳能的一种形式活化来自水源的水;
(iii)将碳源转化成包含碳和氢的有机化合物,所述的有机化合物具有比碳源较高的能量含量。
发明详述
碳源和氢反应形成具有比碳源自己较高的能量含量的含碳化合物的几种方法是已知的。
所述方法的实例是Sabatier反应:
CO2+4H2→CH4+2H2O (1)
所述Sabatier反应被研究,用于向火星的载人航天飞行供应能量的可能性。氢将供应自地球,将在微型化工装置中与火星的二氧化碳反应。
可逆的水轮换反应从二氧化碳和氢产生一氧化碳:
由双箭头可知,这个反应是可逆的,并且趋向于平衡。
Bosch反应:
CO2+2H2→C+2H2O (3)
可被看做是两步反应,第一步是可逆水轮换反应,接着是一氧化碳和氢的反应。
如反应方程式清晰的表示,这些反应需要供应氢。
这些以及其他反应可以在使用水和太阳能代替氢下进行。因此,本发明涉及一种在包含碳和氢的有机化合物中存储太阳能的方法,所述方法包括以下步骤:
(i)提供水源和碳源;
(ii)在碳源存在下,使用太阳能的一种形式活化来自水源的水;
(iii)将碳源转化成包含碳和氢的有机化合物,所述的有机化合物具有比碳源高的能量含量。
本发明所述的方法很重要的方面是输入太阳能,其产生活化形式的水,在碳源存在下发生。这个特征就允许碳源和活化形式的水反应。
本发明对活化水的具体形式没有限定。在一个实施方式中,水分子具有一个或两个处于激发态的O-H键,使得氢自由基可以被分裂下来并且和碳源反应。可以通过用太阳光子(尤其是在光谱的UV范围内)辐射水来实现激发态。活化水的形成可通过使用合适的具有对应于在可见光或者邻近光谱紫外光部分中的光子的能量的带隙的半导体来放大。合适的半导体材料的实例是二氧化钛(带隙3eV)。
在另一实施方式中,太阳能被用于形成氢自由基和/或氢分子。例如,太阳能可被用来在光电方法中产生电能。电能可被用于水分子的电解,凭借形成原子态的氢(生成瞬间的氢)。这种形式的氢与分子氢相比是远远更加活动的。原子态氢很容易和碳源反应。
在仍然另外一个实施方式中,一种形式的太阳能被用来将水分解成氢分子。尽管比原子氢活性差,分子氢可以和碳源反应,特别是在合适的催化剂存在下。
水源无需满足严格的纯度要求。特别是与自然光合作用法相比,通过本发明的方法施加在水质上的需求是非常低的。因此,所述方法可以用含有至少一种污染物质的水进行。
特别的,水源可以包含废水。废水可以是工业废水、城市废水、农业径流等等。
在特别优选的实施方式中,水源包括海水。矿物溶解在海水中赋予水具有高导电性,这对于电解法是优势。溶解在海水中的阳离子不与用于电子接受的质子竞争,因此它们的存在并不妨碍氢的形成。
多种材料可被用作用于本发发明方法的碳源。实例包括煤;合成聚合物废料;CO;CO2;以及它们的混合物。更优选的是用CO2作为碳源。
太阳能可以以其到达地球的形式使用,即,以光谱的红外、可见、紫外部分的电磁辐射的形式,即光子能(photonic energy)。将这种光子能转化成某些其他形式的能量、例如允许能量将被临时存储是可取的。临时存储使得当没有太阳照耀时也可以运行所述方法,例如在夜间。存在用于将太阳能转化成可以被存储在重复充电的电池例如锂离子电池中的光电能的相对较高级的技术。
本发明所述方法的本身可被用于以有机化合物的形式存储太阳能,诸如作为醇(例如乙醇或甲醇),烃类或者碳水化合物。出于成本效率和运输方面的考虑,优选的有机化合物在室温下是液体。有机化合物可以在燃料电池中被用作燃料用于产生电。因此,在24/7基础上(每天24小时,每周7天)可以获得太阳能。
一旦转化为光电能量,太阳能可很容易被转化为其他形式的能量,诸如微波能量。将光电能量转化回到例如以激光束的形式的光子能可能是可取的。激光允许能量以高度集中的形式用于所述的方法。
在一替代的实施方式中,太阳能被用于产生蒸汽,例如在集中太阳能热法(Concentrated Solar Thermal process,CST process)中。所述CST法使用透镜、镜子和跟踪系统以将大面积的太阳光聚集到小的区域。集中的热可被用于产生蒸汽,其可以在传统的蒸汽发生器中被用于产生电。
在一个CST的具体的实施方式中,集中的热被用于将水温升高到800-1200℃。使过热的蒸汽与包含过渡金属例如锌和/或镍的缺氧铁酸盐材料接触。铁酸盐被放置在惰性载体上以增加比表面积,例如,蜂窝陶瓷载体。在这些条件下,水被解离成氧和氢。氢可在本发明的方法的步骤(iii)中使用,或者原位,或者在从氢流中移除氧之后在分离的反应器中。
在仍然另外一个实施方式中,在光子增强热电子发射法(photonenhanced thermionic emission process,PETE process)中将太阳能转化。在PETE法中,用太阳辐射照射具有金属镀层的半导体材料。不同于仅仅使用可见光部分的光电(PV)法,PETE法的半导体能将太阳光谱的可见光和IR部分转化为电能,使得PETE法更有效率。在PETE法中使用的半导体材料必须能承受高温。合适的例子包括氮化镓和砷化镓。
有利的是在催化剂存在下实施步骤(iii)。优选的,所述催化剂是无机催化剂。合适的催化剂的选择在很大程度上取决于期望的碳源经过的转化反应的类型。
在一实施方式中,步骤(iii)包含Fischer-Torpsch反应。所述Fischer-Torpsch反应本质上是一氧化碳和氢的反应以形成烃,尤其是烷烃。
在该实施方式中,碳源包含一氧化碳,其与生成瞬间的氢,或者和分子氢,或者二者的混合物反应。在一替代的实施方式中,碳源包含CO2,在可逆水轮换反应中(参见前述方程式(2)),其首先和氢反应形成CO,由此,提供用于Fischer-Torpsch反应的碳源。
在Fischer-Torpsch催化剂存在下进行Fischer-Torpsch反应是期望的。实例包括包含Ni、Fe、Co、Ru、Ce或它们的组合的催化剂。有利的是使用能够吸收太阳光子能的催化剂载体,例如TiO2。步骤(iii)优选在太阳能例如以光子能的形式被供应到反应混合物时进行。
传统的Fischer-Torpsch法需要高温和高氢压力。本发明所述的方法可以在温和得多的条件下进行。据信这是由于氢的较高的反应性,并且可能通过将太阳光子能供应到反应混合物中而被放大。
在一替代的实施方式中,步骤(iii)包含Sabatier反应。用于Sabatier反应的碳源是二氧化碳。二氧化碳可以从燃烧燃料尤其是化石燃料的方法中获得。例如包括精炼厂、发电厂等。
Sabatier反应优选在Sabatier催化剂存在下进行。特别优选的是包含Ru的催化剂。
在一特别优选的实施方式中,Sabatier催化剂包含在半导体载体例如TiO2上的氢化金属例如Ni或者Ru。催化剂的金属部分仅仅被部分还原。例如,Ru/TiO2催化剂在Ar/H2(1∶1的比例)蒸汽中,在从200℃到250℃范围内的温度下被还原。RuO2完全还原需要500℃的还原温度。
Ru/TiO2催化剂允许Sabatier反应在大气压下,在从25℃到200℃范围内的温度下进行。当用太阳光子能照射反应混合物时,所述催化剂是特别有效的。
在仍然另外一实施方式中,所述催化剂是无机氧化物或者氢氧化物。这种类型的催化剂可和多种碳源包括煤和合成聚合物一起使用。
在这类催化剂中优选的是水滑石;类似水滑石的材料;粘土;氧化铝;层状氢氧根盐(layered hydroxy salt);混合金属氧化物;以及这些材料的煅烧产物。这里所使用的术语“类似水滑石”的材料是指具有水滑石普通结晶结构的混合金属氧化物,并且其中所有或者部分的Al3+为另外一种三价阳离子所代替,和/或所有或者部分Mg2+为另外一种二价阳离子所代替。
在步骤(iii)中产生的有机化合物的类型取决于碳源的性质,以及进行的反应的类型。例如,如果碳源是二氧化碳,反应是Sabatier反应,主要的(或者唯一的)反应产物是甲烷。如果碳源是二氧化碳或一氧化碳,反应是Fischer-Torpsch反应,反应产物是烃、主要是烷烃的混合物。
使用公知技术的方法,可将在Sabatier反应中产生的甲烷容易转化为甲醇。甲醇可以被用作燃料电池的燃料。
如果碳源是煤,反应产物是烃的混合物,饱和的或者不饱和的烃二者。不饱和的烃可包括芳香族烃。
如果碳源是合成聚合物,例如聚烯烃,反应产物是烃、特别是烷烃的混合物。含氧聚合物,例如聚酯,一般产生烃和含氧化合物的混合物,例如醇类和醛类。将聚酯类完全转化为烃是可能的。
在步骤(iii)中产生的有机化合物可被用作平台化学物质,以制备特别化学物质。有机化合物还可以被用作燃料。一般,当用作燃料时,有机化合物被燃烧成二氧化碳和水。在燃烧反应中形成的二氧化碳可以被循环用作所述方法中步骤(i)的碳源。在燃烧反应中形成的水也可以被循环用作步骤(i)的水源。然而,在燃烧反应中形成的水一般比本发明所述方法所需要的纯度高。
将燃烧反应中形成的水用于纯度是重要的的用途是期望的,例如在农业中用于灌溉和动物使用。在燃烧反应中形成的水甚至可以是足以供人类使用的质量,或者本身就是,或者经过一些纯化。
在一具体实施方式中,有机化合物被用作产生电能的装置、例如燃料电池中的燃料。在该实施方式中所述方法包括一额外的步骤:
(iv)将有机化合物转化为电能。
产生电能的装置的合适的例子包括传统的发电厂;发电机;以及燃料电池。优选的是燃料电池。
具体实施方式的详述
将结合在图1中示意性表示的具体实施方式进一步详细描述本发明。
反应器10包含水源11。光电板20接受太阳光子能21,其将被转化为光电能。向阳极22和阴极23供应光电能,这二者均被浸没在水源11中。阳极22和阴极23任选地由膜24分隔开。
管30从外部供给(没有表示出)中接收碳源31。碳源可以是CO。碳源31被泵送到管端32,其被浸没在水源11中。碳源31离开管端32进入到洞33。
在阳极22产生阳极气体25。阳极气体25可以是氧(源于在水源11中OH-电解),或者它可以是其他气体,例如Cl2,如果水源11包含Cl-离子。阳极气体25被收集在气体存储器中(未标示出)。
在阴极23产生氢气26。碳源31和氢气26这二者在水源11中向上升,和另外一个混合。气体混合物穿过催化床40,其中碳源31和氢气26反应。反应产物41是液态烃,其漂向水源11的表面。
在一替代的实施方式中,反应产物包含气态烃,其在水源11的表面上方被收集。
在仍然另一实施方式中,催化剂在水源11中被持续的搅拌形成浆料。
Claims (25)
1.一种用于在包含碳和氢的有机化合物中储存太阳能的方法,所述的方法包括以下步骤:
(i)提供水源和碳源;
(ii)在碳源存在下,使用太阳能的一种形式活化来自水源的水;
(iii)将碳源转化成包含碳和氢的有机化合物,所述的有机化合物具有比碳源较高的能量含量。
2.根据权利要求1所述的方法,其中水源包含水和至少一种污染物。
3.根据权利要求2所述的方法,其中水源包含废水。
4.根据权利要求2或3所述的方法,其中水源包含海水。
5.根据前述权利要求中任一项所述的方法,其中步骤(ii)包含形成氢自由基;氢分子或者它们的混合物。
6.根据前述权利要求中任一项所述的方法,其中碳源选自由煤;合成聚合物废料;CO;CO2;和它们的混合物组成的组。
7.根据前述权利要求中任一项所述的方法,其中太阳能的形式选自由光电能;微波能;光子能;和它们的组合组成的组。
8.根据前述权利要求中任一项所述的方法,其中太阳能在光子增强热电子发射(PETE)法中被转化。
9.根据前述权利要求中任一项所述的方法,其中太阳能在集中太阳能热(CST)法中被转化。
10.根据权利要求9所述的方法,其中CST法被用于将水分解为氢和氧,所述氢在所述方法的步骤(iii)中使用。
11.根据前述权利要求中任一项所述的方法,其中步骤(iii)在催化剂的存在下进行。
12.根据权利要求11所述的方法,其中所述的催化剂是无机催化剂。
13.根据前述权利要求中任一项所述的方法,其中步骤(iii)包括Fischer-Torpsch反应。
14.根据权利要求13所述方法,其中步骤(iii)在Fischer-Torpsch催化剂存在下进行。
15.根据权利要求14所述的方法,其中所述的催化剂包含Ni、Fe、Co、Ru、Ce或它们的组合。
16.根据前述权利要求中任一项所述的方法,其中步骤(iii)包含Sabatier反应。
17.根据权利要求16所述的方法,其中步骤(iii)在Sabatier催化剂存在下进行。
18.根据前述权利要求中任一项所述的方法,其中步骤(iii)在包含无机氧化物或者氢氧化物的催化剂的存在下进行。
19.根据权利要求18所述的方法,其中所述催化剂选自由水滑石;类水滑石的材料;粘土;氧化铝;层状氢氧化物的盐;混合金属氧化物;以及这些材料的煅烧产物组成的组。
20.根据前述权利要求中任一项所述的方法,其中在步骤(iii)中产生的包含碳和氢的有机化合物包含烃;碳水化合物;或者烃和碳水化合物的混合物。
21.根据前述权利要求中任一项所述的方法,进一步产生适用于农业的水。
22.根据前述权利要求中任一项所述的方法,进一步产生适用于人类使用的水。
23.根据权利要求1所述的方法,进一步包括以下步骤:
(iv)将有机化合物转化为电能。
24.根据权利要求23所述的方法,其中步骤(iv)在发电装置中进行,优选燃料电池。
25.根据权利要求23或24所述的方法,其中有机化合物包含甲醇。
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CN102686707A true CN102686707A (zh) | 2012-09-19 |
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US (1) | US8519012B2 (zh) |
EP (1) | EP2467451A1 (zh) |
CN (1) | CN102686707A (zh) |
AU (1) | AU2010285025A1 (zh) |
BR (1) | BR112012003866A2 (zh) |
CA (1) | CA2771660C (zh) |
WO (1) | WO2011020825A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104919023A (zh) * | 2013-01-04 | 2015-09-16 | 沙特阿拉伯石油公司 | 利用太阳辐射通过合成气制备单元将二氧化碳转化为烃类燃料 |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2681293A1 (en) * | 2011-03-04 | 2014-01-08 | Antecy B.V. | Catalytic process for converting carbon dioxide to a liquid fuel or platform chemical |
WO2012168355A1 (en) * | 2011-06-08 | 2012-12-13 | Antecy B.V. | Direct photoconversion of carbon dioxide to liquid products |
GB201202791D0 (en) | 2012-02-20 | 2012-04-04 | Simpson Robert | Methods and system for energy conversion and generation |
WO2013190065A1 (en) * | 2012-06-20 | 2013-12-27 | Antecy B.V. | Device for energy storage and conversion |
WO2014027116A1 (en) * | 2012-08-17 | 2014-02-20 | Antecy B.V. | Process for converting a gaseous feedstock to liquid organic compounds |
US8658311B2 (en) * | 2012-12-07 | 2014-02-25 | Bruce S. Kang | High temperature rechargeable battery for greenhouse gas decomposition and oxygen generation |
US9764959B2 (en) | 2014-05-07 | 2017-09-19 | The Governing Council Of The University Of Toronto | Nanostructured metal oxide compositions for applied photocatalysis |
US9364791B1 (en) * | 2015-02-12 | 2016-06-14 | Gas Technology Institute | Carbon dioxide decomposition |
US10967361B2 (en) | 2017-03-31 | 2021-04-06 | Academia Sinica | Carbon doped tin disulphide and methods for synthesizing the same |
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JP2006032674A (ja) * | 2004-07-16 | 2006-02-02 | Sanyo Electric Co Ltd | 太陽光発電装置及びそれを用いたヒートポンプ装置 |
US20060211777A1 (en) * | 2005-03-16 | 2006-09-21 | Severinsky Alexander J | Systems, methods, and compositions for production of synthetic hydrocarbon compounds |
CN1893220A (zh) * | 2005-07-01 | 2007-01-10 | 上海神力科技有限公司 | 可再生能源与燃料电池耦合发电装置 |
WO2008115933A1 (en) * | 2007-03-19 | 2008-09-25 | Doty Scientific, Inc. | Hydrocarbon and alcohol fuels from variable, renewable energy at very high efficiency |
US20080283411A1 (en) * | 2007-05-04 | 2008-11-20 | Eastman Craig D | Methods and devices for the production of Hydrocarbons from Carbon and Hydrogen sources |
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2010
- 2010-08-17 CN CN201080047245XA patent/CN102686707A/zh active Pending
- 2010-08-17 AU AU2010285025A patent/AU2010285025A1/en not_active Abandoned
- 2010-08-17 EP EP10745215A patent/EP2467451A1/en not_active Withdrawn
- 2010-08-17 CA CA2771660A patent/CA2771660C/en active Active
- 2010-08-17 WO PCT/EP2010/061959 patent/WO2011020825A1/en active Application Filing
- 2010-08-17 BR BR112012003866A patent/BR112012003866A2/pt not_active Application Discontinuation
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2012
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Patent Citations (5)
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JP2006032674A (ja) * | 2004-07-16 | 2006-02-02 | Sanyo Electric Co Ltd | 太陽光発電装置及びそれを用いたヒートポンプ装置 |
US20060211777A1 (en) * | 2005-03-16 | 2006-09-21 | Severinsky Alexander J | Systems, methods, and compositions for production of synthetic hydrocarbon compounds |
CN1893220A (zh) * | 2005-07-01 | 2007-01-10 | 上海神力科技有限公司 | 可再生能源与燃料电池耦合发电装置 |
WO2008115933A1 (en) * | 2007-03-19 | 2008-09-25 | Doty Scientific, Inc. | Hydrocarbon and alcohol fuels from variable, renewable energy at very high efficiency |
US20080283411A1 (en) * | 2007-05-04 | 2008-11-20 | Eastman Craig D | Methods and devices for the production of Hydrocarbons from Carbon and Hydrogen sources |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104919023A (zh) * | 2013-01-04 | 2015-09-16 | 沙特阿拉伯石油公司 | 利用太阳辐射通过合成气制备单元将二氧化碳转化为烃类燃料 |
CN104919023B (zh) * | 2013-01-04 | 2016-08-24 | 沙特阿拉伯石油公司 | 利用太阳辐射通过合成气制备单元将二氧化碳转化为烃类燃料 |
Also Published As
Publication number | Publication date |
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AU2010285025A1 (en) | 2012-04-05 |
CA2771660A1 (en) | 2011-02-24 |
CA2771660C (en) | 2017-12-19 |
US20120222951A1 (en) | 2012-09-06 |
BR112012003866A2 (pt) | 2017-08-29 |
EP2467451A1 (en) | 2012-06-27 |
WO2011020825A1 (en) | 2011-02-24 |
US8519012B2 (en) | 2013-08-27 |
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