CN104203403A - 热化学燃料制造用催化剂及热化学燃料制造方法 - Google Patents
热化学燃料制造用催化剂及热化学燃料制造方法 Download PDFInfo
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- CN104203403A CN104203403A CN201380015007.4A CN201380015007A CN104203403A CN 104203403 A CN104203403 A CN 104203403A CN 201380015007 A CN201380015007 A CN 201380015007A CN 104203403 A CN104203403 A CN 104203403A
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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Abstract
本发明提供包含能够热化学地制造燃料的钙钛矿氧化物的热化学燃料制造用催化剂及热化学燃料制造方法。这样的热化学燃料制造用催化剂是用于用第一温度和作为该第一温度以下的第二温度这两段热化学循环,由热能制造燃料的热化学燃料制造用催化剂,其特征在于,包含具有组成式AXO3±δ的钙钛矿氧化物,在此,0≤δ<1,A是稀土元素、碱土金属元素或碱金属元素中的任意一种以上,X是过渡金属元素或准金属元素中的任意一种以上,O是氧。
Description
技术领域
本发明涉及热化学燃料制造用催化剂和热化学燃料制造方法。
本申请基于2012年3月23日于美国申请的美国临时专利申请第61/615,122号和2012年8月31日于美国申请的美国专利申请第13/600,948号要求优先权,将其内容援引于此。
背景技术
热化学燃料生成法是指由从阳光等得到的热能制造化学燃料,将热能作为化学燃料贮藏的技术。通过高温(第一温度)-低温(第二温度)这两段热循环(热化学循环)制造燃料。实际上,若在高温下还原催化剂氧化物,并向其中导入作为原料气体的二氧化碳、水蒸气等,则催化剂氧化物吸收原料中的氧,能够制造混合气体、甲烷、烃、醇、氢等燃料。
作为氧化物系催化剂,主要报道了ZnO-Zn、Fe2O3-FeO、CeO2-Ce2O3、非化学计量组成的CeO2和它们的混合物、部分置换氧化物等。报道了使用了LaSrMnO3系钙钛矿氧化物的甲烷的水蒸气改质(CH4+H2O→6H2+CO),但这与使用了水、二氧化碳的热化学燃料生成(H2O→H2+1/2O2或CO2→CO+1/2O2)完全不同,使用了钙钛矿氧化物AXO3的热化学燃料制造此前没有报道过。
在能够通过热化学燃料生成法生成的燃料中,例如,氢是在燃烧后仅生成水的清洁能源,因此作为可再生能源被给予期待。
将水直接分解制造氢(H2O→H2+1/2O2)需要数千℃的高温,但是若使用热化学燃料生成法,则能够通过更低温的两段温度的热循环将水分解来制造氢(例如专利文献1)。
在两段温度(高温-低温)的热循环中,对于高温的加热已知利用太阳能的技术(例如专利文献2)。
太阳能是最丰富的可再生能源。为了充分利用这巨大的太阳能,必须将其大规模地以稳定的形式高效地保存。为了以化学的状态保存阳光,我们正在进行使用非化学计量组成的氧化物的太阳能热化学燃料制造的研究。驱动氧化物与气体物质之间的氧化还原反应的是两段热化学循环。氧化物在高温被还原,从氧化物中放出氧。另外,在导入二氧化碳和/或水蒸气的低温中,氧化物从导入的气体中夺取氧原子。其结果是生成混合气体、甲烷和氢燃料。热力学效率依赖于ZnO-Zn、Fe2O3-FeO、CeO2-Ce2O3、非化学计量组成的CeO2系和包含它们的若干组合的氧化物系催化剂,计算为15-75%。其它系的催化剂几乎未被研究。利用了太阳能的燃料制造中的最高转换效率在使用无添加(未掺杂)的二氧化铈、低温800℃-高温1630℃的太阳热化学循环中为0.8%,能够制造1.3~1.5升一氧化碳和氢。
作为热化学燃料生成法中使用的催化剂氧化物,已知氧化铈(二氧化铈)(非专利文献1)。在使用了无添加二氧化铈的太阳热化学效率实验中,对于太阳能反应器(太阳炉)而言,特别是若超过1250℃,则50%以下的能量作为热散失,40%以下的能量成为从孔径的阳光再反射而散失。因此,期待太阳能的转换效率的大幅进步。为了解决该问题,机械工程途径和材料科学途径是可行的。也可以集积热回收系统。课题在于如何从显示期望的特性的大量候补的氧化物中选择合适的氧化物结构和材料化学,组合合成法对于制作作为候补的氧化物也许是强有力的,但需要用于研究高温下的燃料生产率的迅速的方法。
现有技术文献
专利文献
专利文献1:日本特开2004-269296号公报
专利文献2:日本特开2009-263165号公报
专利文献3:美国专利申请公开第2009/0107044号说明书
发明内容
发明所要解决的课题
本发明的目的在于,提供包含能够热化学地制造燃料的钙钛矿氧化物的热化学燃料制造用催化剂及热化学燃料制造方法。
用于解决课题的方法
本发明提出一种热化学燃料制造用催化剂,特别是太阳能热化学水分解用的生物启发的(bio-inspired)催化剂钙钛矿。自然界的光合作用,更具体而言,水的氧化是以由具有突起的立方状的骨架构成的Mn4CaO5团簇为催化剂而发生的。予测可能在含有锰元素的同样的立方状结构中发生人工水分解。根据该假定,开始了使用锰基的钙钛矿(立方状结构,图示于图3的图表的右侧的结构)的热化学水分解实验。得知钙钛矿使水分解,制造出超过使用了氧化铈时的氢量的氢。据发明人所知,这是以使用非化学计量组成的钙钛矿氧化物的热化学水分解的最初的证实结果为基础的。Sr掺杂LaMnO3钙钛矿被用于甲烷的水蒸气改质,但利用钙钛矿氧化物的热化学水分解未被证实。相比于氧化铈的白色,钙钛矿的黑色对高效的太阳能吸收率是有效的,其结果是能够实现高效的太阳能燃料转换。
将钙钛矿氧化物作为热化学燃料制造用催化剂的一例用作制氢用催化剂的两段热化学循环反应由如以下所示的氧放出反应和氢生成反应这两段构成;
〔氧放出反应(高温还原反应)〕
AXO3±δ→AXO3±δ-α+(α/2)O2
〔氢生成反应(低温氧化反应)〕
AXO3±δ-α+αH2O→AXO3±δ+αH2
另外,总反应如下表示;
〔总反应〕
αH2O→αH2+(α/2)O2
另外,将钙钛矿氧化物作为热化学燃料制造用催化剂的一例用作热化学甲烷制造用催化剂的两段热化学循环反应由如以下所示的氧放出反应和甲烷生成反应这两段构成;
〔氧放出反应(高温还原反应)〕
AXO3±δ→AXO3±δ-α+(α/2)O2
〔甲烷生成反应(低温氧化反应)〕
AXO3±δ-α+(α/4)CO2+(α/2)H2O→AXO3±δ+(α/4)CH4
另外,总反应如下表示;
〔总反应〕
(α/4)CO2+(α/2)H2O→(α/4)CH4+(α/2)O2
另外,将钙钛矿氧化物作为热化学燃料制造用催化剂的一例用作热化学甲醇制造用催化剂的两段热化学循环反应由如以下所示的氧放出反应和甲醇生成反应这两段构成;
〔氧放出反应(高温还原反应)〕
AXO3±δ→AXO3±δ-α+(α/2)O2
〔甲醇生成反应(低温氧化反应)〕
AXO3±δ-α+(δ/3)CO2+(2α/3)H2O→AXO3±δ+(α/3)CH3OH
另外,总反应用以下方式表示;
〔总反应〕
(α/3)CO2+(2α/3)H2O→(α/3)CH3OH+(α/2)O2
另外,将钙钛矿氧化物作为热化学燃料制造用催化剂的一例用作一氧化碳制造用催化剂的两段热化学循环反应由如以下所示的氧放出反应和一氧化碳生成反应这两段构成;
〔氧放出反应(高温还原反应)〕
AXO3±δ→AXO3±δ-α+(α/2)O2
〔一氧化碳生成反应(低温氧化反应)〕
AXO3±δ-α+αCO2→AXO3±δ+αCO
另外,总反应如下表示;
〔总反应〕
αCO2→αCO+(α/2)O2
另外,将钙钛矿氧化物作为热化学燃料制造用催化剂的一例用作氢与一氧化碳的混合气体制造用催化剂的两段热化学循环反应由如以下所示的氧放出反应和氢与一氧化碳的混合气体生成反应这两段构成;
〔氧放出反应(高温还原反应)〕
AXO3±δ→AXO3±δ-α+(α/2)O2
〔氢与一氧化碳的混合气体生成反应(低温氧化反应)〕
2AXO3±δ-α+αH2O+αCO2→2AXO3±δ+αH2+αCO
另外,总反应如下表示;
〔总反应〕
αH2O+αCO2→αH2+αCO+(α/2)O2
为了达成上述的目的,本发明提供以下方法。
(1)一种热化学燃料制造用催化剂,其特征在于,其是用于用第一温度和作为该第一温度以下的第二温度这两段热化学循环,由热能制造燃料的热化学燃料制造用催化剂,包含具有组成式AXO3±δ(其中,0≤δ<1)的钙钛矿氧化物;在此,A是稀土元素、碱土金属元素或碱金属元素中的任意一种以上,X是过渡金属元素或准金属元素中的任意一种以上,O是氧。
(2)根据(1)中记载的热化学燃料制造用催化剂,其特征在于,所述A元素是选自La、Mg、Ca、Sr、Ba中的任意一种以上的元素,所述X元素是选自Mn、Fe、Ti、Zr、Nb、Ta、Mo、W、Hf、V、Cr、Co、Ni、Cu、Zn、Mg、Al、Ga、In、C、Si、Ge、Sn中的任意一种以上的元素。
(3)根据(2)中记载的热化学燃料制造用催化剂,其特征在于,所述A元素是La,所述X元素是Mn。
(4)根据(3)中记载的热化学燃料制造用催化剂,其特征在于,所述A元素的一部分被Sr、Ca、Ba中的任意一种以上置换。
(5)根据(3)中记载的热化学燃料制造用催化剂,其特征在于,所述X元素的一部分被Fe、Ni、V、Cr、Sc、Ti、Co、Cu、Zn中的任意一种以上置换。
(6)根据(1)中记载的热化学燃料制造用催化剂,其特征在于,所述A元素是La,所述X元素是Mn,所述La的一部分被Sr置换。
(7)根据(6)中记载的热化学燃料制造用催化剂,其特征在于,所述置换的Sr的浓度(x;x是以置换前的La量为1时的量)为0.1以上且小于1.0。
(8)根据(7)中记载的热化学燃料制造用催化剂,其特征在于,所述Mn的一部分被Fe置换。
(9)根据(8)中记载的热化学燃料制造用催化剂,其特征在于,所述置换的Fe的浓度(x;x是以置换前的Mn量为1时的量)为0.35以上且0.85以下。
(10)根据(1)中记载的热化学燃料制造用催化剂,其特征在于,所述A元素是Ba,所述X元素是Ti,所述Ti的一部分被Mn置换。
(11)根据(10)中记载的热化学燃料制造用催化剂,其特征在于,所述置换的Mn的浓度(x;x是以置换前的Ti量为1时的量)大于0且为0.5以下。
(12)一种热化学燃料的制造方法,其特征在于,使用(1)~(11)中的任意一项中记载的热化学燃料制造用催化剂。
(13)一种热化学燃料制造方法,其特征在于,其是使用(1)~(11)中的任意一项中记载的热化学燃料制造用催化剂,用第一温度和作为该第一温度以下的第二温度这两段热化学循环,由热能制造燃料热化学燃料制造方法,所述第一温度为600℃以上且1600℃以下,所述第二温度为400℃以上且1600℃以下。
(14)根据(13)中记载的热化学燃料制造方法,其特征在于,通过照射聚光太阳能进行加热或通过用废热进行加热从而得到所述第一温度。
(15)一种热化学燃料制造方法,其特征在于,其是使用第一温度和作为该第一温度以下的第二温度这两段热化学循环,由热能制造燃料热化学燃料制造方法,并具有:将具有组成式AXO3±δ(其中,0≤δ<1)的钙钛矿氧化物加热至第一温度进行还原的工序;使原料气体接触还原后的钙钛矿氧化物,使该钙钛矿氧化物氧化来制造燃料的工序。
(16)根据(15)中记载的热化学燃料制造方法,其特征在于,所述燃料为氢、一氧化碳、氢与一氧化碳的混合气体、甲烷、甲醇中的任意一种。
(17)根据(15)中记载的热化学燃料制造方法,其特征在于,所述原料气体为水蒸气。
(18)根据(15)中记载的热化学燃料制造方法,其特征在于,所述原料气体为二氧化碳和水蒸气。
需要说明的是,在本说明书中,“热化学燃料制造”是指,把通过组合多个化学反应而将水在比较平稳的热条件下分解为氧和氢的“热化学制氢”的概念扩展至含氢的广泛的燃料的概念。
另外,“一部分被···置换”的情况是指,置换的元素的浓度(x)以置换前的被置换元素的量为1时,为大于0且小于1中的任意的范围的情况。
另外,“第二温度”通过改变气氛,即使在与“第一温度”相同的温度下也能实现热化学燃料制造,但在气氛相同的情况下,“第二温度”为比“第一温度”低的温度。
另外,“组成式AXO3±δ(其中,0≤δ<1)”中的“δ”优选0≤δ≤0.5,更优选0≤δ≤0.3,进一步优选0≤δ≤0.2。
发明效果
根据本发明,能够提供包含能够热化学地制造燃料的钙钛矿氧化物的热化学燃料制造用催化剂及热化学燃料制造方法。
本发明提供使用了钙钛矿氧化物AXO3的最初的热化学燃料制造用催化剂。
根据本发明,由于使用铁、锰、钙、钡、钛等丰富的地壳存在元素且能够削减稀土元素的使用量,因此能够提供能预期大幅的成本削减的热化学燃料制造用催化剂及热化学燃料制造方法,由此能够以高效率将太阳能作为化学燃料进行转换贮藏。
附图说明
图1是表示La0.8Sr0.2Mn1-xFexO3±δ(x=0以上且1以下)的X射线衍射结果的图表。
图2是La0.8Sr0.2Mn1-xFexO3±δ的二次电子显微镜图像。
图3是表示将La0.8Sr0.2Mn1-xFexO3±δ用作热化学燃料(氢)制造用催化剂时的制氢量的图表。
图4是表示将La0.8Sr0.2Mn1-xFexO3±δ用作热化学燃料(氢)制造用催化剂时的制(生成)氢量的铁浓度(x)依存性的图表。
图5是表示使用了La0.8Sr0.2Mn1-xFexO3±δ的制氢量的循环特性的图表。
图6A是表示使用了La0.8Sr0.2Mn1-xFexO3±δ的制氢量和制氧量的循环特性的图表。
图6B是对于图6A中所示的制氢量和制氧量,表示该制氢量相对于制氧量之比的循环特性的图表。
图7是表示将(La0.8Sr0.2)MnO3±δ、(La0.8Sr0.2)(Mn0.85Ti0.15)O3±δ、(La0.8Sr0.2)(Mn0.85Fe0.15)O3±δ、(La0.8Sr0.2)(Mn0.85Ni0.15)O3±δ、(La0.8Sr0.2)(Mn0.85Mg0.15)O3±δ、La(Mn0.5Mg0.5)O3±δ用作热化学制氢用催化剂时的制氢量的图表。
图8是表示将(La0.8Sr0.2)MnO3±δ、(La0.8Sr0.2)(Mn0.85Ti0.15)O3±δ、(La0.8Sr0.2)(Mn0.85Fe0.15)O3±δ、(La0.8Sr0.2)(Mn0.85Ni0.15)O3±δ、(La0.8Sr0.2)(Mn0.85Mg0.15)O3±δ用作热化学制氢用催化剂时的制氢量的循环特性的图表。
图9是表示将(La0.8Sr0.2)CrO3±δ用作热化学制氢用催化剂,第一温度为1300℃、第二温度为800℃时的制氢量及制氧量的图表。
图10是表示将(La0.8Sr0.2)MnO3±δ用作热化学制氢用催化剂,第一温度为1400℃、第二温度为800℃时的制氢量及制氧量的图表。
图11是表示将Ba(Ti0.6Mn0.4)O3±δ用作热化学制氢用催化剂时的制氢量的图表。
图12是表示将La1-xSrxMnO3±δ(x=0、0.1、0.2)用作热化学制氢用催化剂时的制氢量的循环特性的图表。
图13是表示将La1-xSrxMnO3±δ(x=0.1、0.2、0.3、0.4、0.5)用作热化学制氢用催化剂时的制氢量的图表。
图14是表示将La0.8Sr0.2Mn1-xAlxO3±δ(x=0、0.25、0.5、0.75)用作热化学制氢用催化剂时的制氢量的图表。
图15是表示将(La0.8Sr0.2)MnO3±δ和(La0.8Ba0.2)MnO3±δ用作热化学制氢用催化剂时的制氢量的图表。
图16是表示将(La0.8Ba0.2)(Mn0.25Fe0.75)O3±δ用作热化学制氢用催化剂时的制氢量的图表。
具体实施方式
以下,对于应用了本发明的热化学燃料制造用催化剂和热化学燃料制造方法,用附图说明其构成。需要说明的是,对于以下的说明中使用的附图而言,有时为了容易理解特征,方便起见将作为特征的部分扩大表示,各构成要素的尺寸比率等不一定与实际相同。另外,在以下的说明中例示的实施例仅为一例,本发明并不受它们的限定,在不改变主旨的范围内可以进行适当改变而实施。
本发明的热化学燃料制造用催化剂是用于使用第一温度和作为该第一温度以下的第二温度这两段热化学循环,由热能制造燃料的热化学燃料制造用催化剂,包含具有组成式AXO3±δ(其中,0≤δ<1)的钙钛矿氧化物。在此,A是稀土元素、碱土金属元素或碱金属元素中的任意一种以上,X是过渡金属元素或准金属(半金属)元素中的任意一种以上,O是氧。
δ的值可以在不损害本发明的效果的范围内确定。
稀土元素可以列举例如Sc(钪)、Y(钇)、La(镧)、Pr(镨)、Nd(钕)、Pm(钷)、Sm(钐)、Eu(铕)、Gd(钆)、Tb(铽)、Dy(镝)、Ho(钬)、Er(铒)、Tm(铥)、Yb(镱)、Lu(镥)、Ce(铈)。
碱土金属元素可以列举例如Be(铍)、Mg(镁)、Ca(钙)、Sr(锶)、Ba(钡)、Ra(镭)。
碱金属元素可以列举例如Li(锂)、Na(钠)、K(钾)、Rb(铷)、Cs(铯)、Fr(钫)。
过渡金属元素可以列举例如Sc(钪)、Ti(钛)、V(钒)、Cr(铬)、Mn(锰)、Fe(铁)、Co(钴)、Ni(镍)、Cu(铜)、Zn(锌)等第一过渡元素(3d过渡元素),Y(钇)、Zr(锆)、Nb(铌)、Mo(钼)、Tc(锝)、Ru(钌)、Rh(铑)、Pd(钯)、Ag(银)、Cd(镉)等第二过渡元素(4d过渡元素),La(镧)、Pr(镨)、Nd(钕)、Pm(钷)、Sm(钐)、Eu(铕)、Gd(钆)、Tb(铽)、Dy(镝)、Ho(钬)、Er(铒)、Tm(铥)、Yb(镱)、Lu(镥)、Hf(铪)、Ta(钽)、W(钨)、Re(铼)、Os(锇)、Ir(铱)、Pt(铂)、Au(金)等第三过渡元素(4f过渡元素)。
准金属元素可以列举例如B(硼)、Si(硅)、Ge(锗)、As(砷)、Sb(锑)、Te(碲)、Se(硒)、Po(钋)、At(砹)。
作为这些的组合的例子,优选例示:A元素为La,X元素为Mn的化合物;A元素为La,X元素为Mn,且该La的一部分被Sr、Ca、Ba中的任意一种以上置换的化合物;A元素为La,X元素为Mn,且该La的一部分被Sr、Ca、Ba中的任意一种以上置换,且该Mn的一部分被Fe、Ni、V、Cr、Sc、Ti、Co、Cu、Zn中的任意一种以上置换的化合物;A元素为Ba,X元素为Ti,该Ti的一部分被Mn置换的化合物;A元素为Ba、Ca或Sr,且该Ba、Ca或Sr的一部分在0.01以上且0.5以下的范围内被置换的化合物;A元素为Ca或Sr,X元素为Ti或Zr的化合物等。
作为本发明的一个实施方式的热化学燃料制造方法,是使用本发明的热化学燃料制造用催化剂,用第一温度和作为该第一温度以下的第二温度这两段热化学循环,由热能制造燃料热化学燃料制造方法,第一温度为600℃以上且1600℃以下,第二温度为400℃以上且1600℃以下。
第一温度和/或第二温度可以通过例如照射聚光太阳能进行加热或通过用废热进行加热从而得到。
“废热”可以利用例如发电装置、高炉等的废热。
在本发明中,“两段”是指包括两个不同条件在内的阶段。由此,作为“两段”可以例示:第1阶段(第1步骤)与第2阶段(第2步骤)的温度不同的情况、第1阶段与第2阶段的温度相同,但第1阶段是不含水分的干燥气流,第2阶段是含有水蒸气的湿润气流的情况等。
制造氢作为燃料时,可以使第一温度为600℃以上且1600℃以下(例如1400℃),使第二温度为400℃以上且1600℃以下(例如800℃)。
制造一氧化碳作为燃料时,可以使第一温度为600℃以上且1600℃以下(例如1400℃),使第二温度为300℃以上且1600℃以下(例如450℃)。
制造氢与一氧化碳的混合气体作为燃料时,可以使第一温度为600℃以上且1600℃以下(例如1400℃),使第二温度为300℃以上且1600℃以下(例如800℃)。
制造甲烷作为燃料时,可以使第一温度为600℃以上且1600℃以下(例如1400℃),使第二温度为300℃以上且1600℃以下(例如450℃)。
制造甲醇作为燃料时,可以使第一温度为600℃以上且1600℃以下(例如1400℃),使第二温度为200℃以上且1600℃以下(例如350℃)。
作为本发明的另一实施方式的热化学燃料制造方法,是用第一温度和比该第一温度低的第二温度这两段热化学循环,由热能制造燃料热化学燃料制造方法,其具有:将具有组成式AXO3±δ(其中,0≤δ<1)的钙钛矿氧化物加热至第一温度进行还原的工序;和使原料气体接触还原后的钙钛矿氧化物,使该钙钛矿氧化物氧化来制造燃料的工序。
δ的值可以在不损害本发明的效果的范围内确定。
作为能够利用本发明的热化学燃料制造方法制造的燃料并没有限定,但可以列举例如氢、一氧化碳、氢与一氧化碳的混合气体、甲烷、甲醇。
作为原料气体并没有限定,但作为一例,可以举出水蒸气。可以使用水蒸气制造氢。另外,作为另一例,可以列举二氧化碳和水蒸气。可以使用二氧化碳和水蒸气,制造甲烷、甲醇。
首先,作为本发明的热化学燃料制造用催化剂的一例,对于制作热化学制氢用催化剂的方法,说明其概要。
热化学制氢用催化剂的制作可以使用公知的钙钛矿氧化物的制作方法。例如,将包含期望的钙钛矿氧化物的元素的原料(氧化物,氢氧化物,氧化氢氧化物等)的粉末以成为目标的组成比的方式进行秤量,并进行混合粉碎处理,接着进行预烧,随后进行终烧(日文:本焼),由此可以制作热化学制氢用催化剂。
更具体而言,对制作La0.8Sr0.2Mn1-xFexO3±δ的方法的一例进行说明。
通过固相反应,制造La0.8Sr0.2Mn1-xFexO3±δ的多孔的(多孔性)颗粒。首先,用磨碎机粉碎原料氧化物(La2O3、SrCO2、MnCO3、Fe2O3),在1000℃、空气中进行3小时预烧。接着,将得到的粉末与异丙醇一同放入模具中,在1500℃进行6小时烧成,得到多孔的颗粒。
通过X射线衍射确认La0.8Sr0.2Mn1-xFexO3±δ颗粒为钙钛矿结构(参照图1)。得到的颗粒的孔隙率约为60%。另外,由二次电子显微镜图像可知,得到的颗粒具有从数μm到大于100μm的各种尺寸的孔(参照图2)。
接着,对于使用得到的热化学制氢用催化剂来制造氢,说明其概要。
例如,可以使用该热化学制氢用催化剂,按照以下的方式制造氢。
将多孔的颗粒放入红外炉内,在含有10ppm的氧气的干燥氮气下将颗粒加热至1400℃(相当于两段热化学循环的“第一温度”)。此时,利用质谱法观测氧从颗粒中脱出。接着,将颗粒冷却至800℃(相当于两段热化学循环的“第二温度”)后,流过含有氩气的10%水蒸气。x=0时,在800℃观察到3ml/g(相当于使用无添加氧化铈时的氢产生量的~60%的量)的氢产生量。氢产生反应如图3所示,在10分以内结束。
氢产生量如图4所示,略有增加并再现9个循环。
光合作用中的水的氧化的催化剂中心被认为是,以较长键长与金属键合的氧位。作为在钙钛矿中得到较长金属-氧键长的尝试,锰的一部分被铁置换后的La0.8Sr0.2Mn1-xFexO3±δ具有与铁键合而显示出较长金属-氧键长的可能性。该La0.8Sr0.2Mn1-xFexO3±δ的分析结果如下所示。
图1是表示该La0.8Sr0.2Mn1-xFexO3±δ的X射线衍射结果的图表。横轴为衍射角度(度),纵轴为衍射强度(任意单位)。x为铁(Fe)的浓度(以置换前的Mn量为1时的量),对于0(相当于不含Fe的情况)、0.3(30at%)、0.5(50at%)、0.75(75at%)、1(100at%;Mn原子全部被Fe原子置换的情况)示出了X射线衍射结果。如图1所示,钙钛矿结构在La0.8Sr0.2Mn1-xFexO3±δ的所有铁浓度(x)下被保持。利用差示扫描热量计的测定到1400℃为止也没有显示相变的证据。
需要说明的是,可知粗线为热循环前,细线为热循环后,可知均显示出钙钛矿结构。
图2是La0.8Sr0.2Mn1-xFexO3±δ的二次电子显微镜图像。图中的a)、c)、e)、g)和i)为热循环前的图像,b)、d)、f)、h)和j)为800℃-1400℃的热循环后的图像。a)和b)为铁浓度x=0,c)和d)为铁浓度x=0.3,e)和f)为铁浓度x=0.5,g)和h)为铁浓度x=0.75,i)和j)为铁浓度x=1。如图的右下所示,标尺的尺寸为40μm。
可知对于任意一个试样而言,热循环后均保持多孔的结构。
图3是表示将La0.8Sr0.2Mn1-xFexO3±δ用作热化学制氢用催化剂时的氢的制造量的图表。横轴为时间(分钟),纵轴为每单位克数的制氢量(ml/g/min)。热(热化学)循环的第一温度为1400℃,第二温度为800℃。
如图3所示,铁(Fe)的浓度(x)为0(相当于不含Fe的情况)、0.3(30at%)、0.5(50at%)、0.75(75at%)时,Fe的含量越增加,制氢量变得越多,x=0.75时是不含Fe时(x=0)的约1.6倍。x=0.85(85at%)时比x=0.75时降低15%左右。Mn原子全部被Fe原子置换时(x=1)为x=0.75时的10%左右。
需要说明的是,将La0.6Sr0.4MnO3±δ用作热化学制氢用催化剂,第一温度为1400℃,第二温度为800℃的热(热化学)循环的情况下,能够得到7.5ml/g的制氢量。
图4是表示将La0.8Sr0.2Mn1-xFexO3±δ用作热化学制氢用催化剂时的制(生成)氢量的铁浓度(x)依存性的图表。横轴为铁的浓度,纵轴为每单位克数的制氢量(ml/g)。热循环的第一温度为1400℃,第二温度为800℃。
白色圆点表示的是第1循环的结果,黑色圆点表示的是第9循环的结果。
如图4所示,在x为0.35~0.85时,比二氧化铈的制氢量(4.0ml/g)多,x=0.75时的制氢量为5.3ml/g,比二氧化铈的制氢量多30%以上。
图5是表示将La0.8Sr0.2Mn1-xFexO3±δ用作热化学制氢用催化剂时的制氢量的循环特性的图表。横轴为循环数(次),纵轴为每单位克数的制氢量(ml/g)。热循环的第一温度为1400℃,第二温度为800℃。
铁浓度x=0、0.3、0.5、0.75和1时,制氢量随着循环逐渐增加。铁浓度x=0.85时,制氢量随着循环逐渐减少。需要说明的是,在图5中未表示,在15次循环变成一定。
与铁浓度无关,在任意情况下均能够得到稳定的循环特性。
图6A是表示使用了La0.8Sr0.2Mn1-xFexO3±δ的制氢量和制氧量的循环特性的图表。横轴为循环数(次),纵轴为每单位克数的制氢量和制氧量(ml/g)。图6B是表示该制氢量相对于制氧量之比的循环特性的图表。横轴为循环数(次),纵轴为制氢量相对于制氧量之比。热循环的第一温度为1400℃,第二温度为800℃。
如图6B所示,制氢量与制氧量之比(H2量/O2量)约为2,表示进行了水分解。
图7是表示将(La0.8Sr0.2)MnO3±δ、(La0.8Sr0.2)(Mn0.85Ti0.15)O3±δ、(La0.8Sr0.2)(Mn0.85Fe0.15)O3±δ、(La0.8Sr0.2)(Mn0.85Ni0.15)O3±δ、(La0.8Sr0.2)(Mn0.85Mg0.15)O3±δ、La(Mn0.5Mg0.5)O3±δ用作热化学制氢用催化剂时的制氢量的图表。制氢量用每单位克数的流量(ml/min/g)表示。横轴为时间(分钟),纵轴为每单位克数的流量(ml/min/g)。热(热化学)循环的第一温度为1400℃,第二温度为800℃。
如图7所示,将A位为La或者La与Sr,X位为Mn或者Mn与Ti、Fe、Ni、Mg中的任意一种的钙钛矿氧化物用于热化学制氢用催化剂时,也能热化学地制造氢。
图8是表示将(La0.8Sr0.2)MnO3±δ,(La0.8Sr0.2)(Mn0.85Ti0.15)O3±δ,(La0.8Sr0.2)(Mn0.85Fe0.15)O3±δ,(La0.8Sr0.2)(Mn0.85Ni0.15)O3±δ,(La0.8Sr0.2)(Mn0.85Mg0.15)O3±δ用作热化学制氢用催化剂时的制氢量的循环特性的图表。横轴为循环数(次),纵轴为每单位克数的制氢量(ml/g)。热循环的第一温度为1400℃,第二温度为800℃。
将(La0.8Sr0.2)MnO3±δ用作热化学制氢用催化剂时,制氢量随着循环逐渐增加,在4次循环左右变得基本一定。
将(La0.8Sr0.2)(Mn0.85Ti0.15)O3±δ用作热化学制氢用催化剂时,制氢量随着循环逐渐减少。
将(La0.8Sr0.2)(Mn0.85Fe0.15)O3±δ用作热化学制氢用催化剂时,制氢量随着循环逐渐减少。
将(La0.8Sr0.2)(Mn0.85Ni0.15)O3±δ用作热化学制氢用催化剂时,制氢量随着循环逐渐减少。在第9循环,变成与使用了(La0.8Sr0.2)MnO3±δ时基本相同的程度。
将(La0.8Sr0.2)(Mn0.85Mg0.15)O3±δ用作热化学制氢用催化剂时,制氢量随着循环逐渐减少。
使用了(La0.8Sr0.2)(Mn0.85Ti0.15)O3±δ和(La0.8Sr0.2)(Mn0.85Mg0.15)O3±δ时,制氢量为3ml/g左右。
使用了(La0.8Sr0.2)MnO3±δ、(La0.8Sr0.2)(Mn0.85Fe0.15)O3±δ和(La0.8Sr0.2)(Mn0.85Ni0.15)O3±δ时,制氢量在第1循环分别为5ml/g、6ml/g、7ml/g左右,随着接近10次循环,均变成6ml/g左右。
图9是表示将(La0.8Sr0.2)CrO3±δ用作热化学制氢用催化剂时的制氢量和制氧量的图表。制造量用每单位克数的流量(ml/min/g)表示。横轴为时间(分钟),纵轴为每单位克数的流量(ml/min/g)。实线表示制氧量,双点划线表示制氢量。热(热化学)循环的第一温度为1300℃,第二温度为800℃。
如图9所示,将(La0.8Sr0.2)CrO3±δ用作热化学制氢用催化剂时,也能够热化学地制造氢。
图10是表示将(La0.8Sr0.2)MnO3±δ用作热化学制氢用催化剂时的制氢量和制氧量的图表。热(热化学)循环的第一温度为1400℃,第二温度为800℃。横轴为时间(分钟),左侧纵轴为每单位克数的氢或氧的流量(ml/min/g)。实线表示氧的制造流量,虚线表示氢的制造流量。另外,右侧纵轴为温度(℃),如图表所示,在循环开始后,在第1步骤(上述氧放出反应(高温还原反应))中在1400℃保持40分钟,然后,在第2步骤(上述氢生成反应(低温氧化反应))中降温至800℃。
如图10所示,将(La0.8Sr0.2)CrO3±δ用作热化学制氢用催化剂时,能够以高的制氢量与制氧量之比(H2量/O2量),热化学地制造氢。
图11是表示将Ba(Ti0.6Mn0.4)O3±δ用作热化学制氢用催化剂时的制氢量的图表。横轴为时间(分钟),纵轴为每单位克数的制氢量(ml/g)。热(热化学)循环的第一温度为1400℃,第二温度为800℃。
如图11所示,将A位为Ba,X位为Mn和Ti的钙钛矿氧化物用作热化学制氢用催化剂时,也能热化学地制造氢。
图12是表示将La1-xSrxMnO3±δ(x=0、0.1、0.2)用作热化学制氢用催化剂时的制氢量的循环特性的图表。制造量用每单位克数的流量(sccm/g)表示。横轴为时间(分钟),纵轴为每单位克数的流量(sccm/g)。实线(LaMnO3)、虚线(LSM91)、点划线(LSM82)分别表示x=0、0.1、0.2的各个情况的流量。热(热化学)循环的第一温度为1500℃,第二温度为800℃。
对于制氢量而言,Sr浓度越高则越多,x=0.2时是x=0时的3倍以上。
图13是表示将La1-xSrxMnO3±δ(x=0.1、0.2、0.3、0.4、0.5)用作热化学制氢用催化剂时的制氢量的循环特性的图表。对于制造量而言,在各个情况下,左侧纵轴为每单位克数的流量(ml/min/g),右侧纵轴为每单位克数、每一循环的制造量(ml/循环/g)。图中的凡例所示的LSM91、LSM82、LSM73、LSM64、LSM55分别对应x=0.1、0.2、0.3、0.4、0.5的各个情况,该图表表示每单位克数的流量(ml/min/g)。另外,各个图线附近所示的圆圈标记表示各个情况的每一循环的制造量(ml/cycle/g)。热(热化学)循环的第一温度为1400℃,第二温度为800℃。
对于制氢量而言,Sr浓度越高则越多,x=0.4和x=0.5时是x=0.1时的6倍左右。
图14是表示将La0.8Sr0.2Mn1-xAlxO3±δ(x=0、0.25、0.5、0.75)用作热化学制氢用催化剂时的制氢量的循环特性的图表。对于制造量而言,在各个情况下,左侧纵轴为每单位克数的流量(ml/min/g),右侧纵轴为每单位克数、每一循环的制造量(ml/cycle/g)。图中的凡例所示的LSM82、LSMA827525、LSMA825050、LSMA822575分别对应x=0、0.25、0.5、0.75的各个情况,该图表表示每单位克数的流量(ml/min/g)。另外,各个图线附近所示的圆圈标记表示各个情况的每一循环的制造量(ml/循环/g)。热(热化学)循环的第一温度为1400℃,第二温度为800℃。
对于制氢量而言,随着Al浓度从零变到与Mn浓度相同的浓度而逐渐增多,若Al浓度进一步变高(x=0.75)则变少。
图15是表示将(La0.8Sr0.2)MnO3±δ和(La0.8Ba0.2)MnO3±δ用作热化学制氢用催化剂时的制氢量的图表。制造量用每单位克数的流量(ml/min/g)表示。横轴为时间(分钟),纵轴为每单位克数的流量(ml/min/g)。实线(LSM82)表示(La0.8Sr0.2)MnO3±δ,虚线(LBM82)表示(La0.8Ba0.2)MnO3±δ的流量。热(热化学)循环的第一温度为1400℃,第二温度为800℃。
将(La0.8Sr0.2)MnO3±δ的Sr置换为Ba的钙钛矿氧化物用于热化学制氢用催化剂时,制氢量几乎没有变化。
图16是表示将(La0.8Ba0.2)(Mn0.25Fe0.75)O3±δ用作热化学制氢用催化剂时的制氢量的图表。制造量用每单位克数的流量(ml/min/g)表示。横轴为时间(分钟),纵轴为每单位克数的流量(ml/min/g)。热(热化学)循环的第一温度为1400℃,第二温度分别为700℃(实线)、800℃(虚线)、1000℃(点划线)。
第二温度为700℃和800℃时,制氢量没有明显变化,相对于此,第二温度为1000℃时与第二温度为700℃和800℃时相比,制氢量少10%左右。
在太阳热化学制氢中,集中太阳能需要被钙钛矿氧化物吸收。太阳光谱遍布从紫外到可见和红外的范围(250nm~2500nm)。所吸收的光子将电子从低的状态激发至激发态,最终通过声子转换为热。在光吸收测定中,La0.8Sr0.2Mn0.25Fe0.75O3±δ钙钛矿极高效地吸收光,吸收氧化铈的约4倍。
构成钙钛矿的元素丰富地存在于地球上。铁和锰的地球丰度分别是碳的地球丰度的35倍和0.6倍。锶(Sr)在地壳中是铜(Cu)的5倍,镧(La)是铜的一半。
发明人通过在光化学系II中模仿Mn4CaO5团簇的催化剂中心,开发了热化学制氢用催化剂La0.8Sr0.2Mn1-xFexO3±δ钙钛矿。特别是,La0.8Sr0.2Mn0.25Fe0.75O3±δ在800℃~1400℃之间的热化学循环中制造5.3ml/g的氢。在无添加氧化铈基础上利用非化学计量组成钙钛矿的优点是:~4倍高效的光吸收率、扩大缩小可能的太阳能燃料制造用的地球上丰富存在元素的利用;以及1400℃的低温工作。在该体系中的、地球上丰富存在的锶能够完全熔解于镧,能够模仿催化剂钙钛矿中的稀土的利用。
产业上的可利用性
本发明能够以高效率将太阳能作为化学燃料进行转换贮藏,因此能够将得到的化学燃料用作各产业领域的清洁能源、化学产业的清洁工业原料。
Claims (18)
1.一种热化学燃料制造用催化剂,其特征在于,其是用于用第一温度和作为该第一温度以下的第二温度这两段热化学循环,由热能制造燃料的热化学燃料制造用催化剂,包含具有组成式AXO3±δ的钙钛矿氧化物,其中,0≤δ<1,A是稀土元素、碱土金属元素或碱金属元素中的任意一种以上,X是过渡金属元素或准金属元素中的任意一种以上,O是氧。
2.根据权利要求1所述的热化学燃料制造用催化剂,其特征在于,所述A元素是选自La、Mg、Ca、Sr、Ba中的任意一种以上的元素,所述X元素是选自Mn、Fe、Ti、Zr、Nb、Ta、Mo、W、Hf、V、Cr、Co、Ni、Cu、Zn、Mg、Al、Ga、In、C、Si、Ge、Sn中的任意一种以上的元素。
3.根据权利要求2所述的热化学燃料制造用催化剂,其特征在于,所述A元素是La,所述X元素是Mn。
4.根据权利要求3所述的热化学燃料制造用催化剂,其特征在于,所述A元素的一部分被Sr、Ca、Ba中的任意一种以上置换。
5.根据权利要求3所述的热化学燃料制造用催化剂,其特征在于,所述X元素的一部分被Fe、Ni、V、Cr、Sc、Ti、Co、Cu、Zn中的任意一种以上置换。
6.根据权利要求1所述的热化学燃料制造用催化剂,其特征在于,所述A元素是La,所述X元素是Mn,所述La的一部分被Sr置换。
7.根据权利要求6所述的热化学燃料制造用催化剂,其特征在于,所述置换的Sr的浓度x为0.1以上且小于1.0,x是以置换前的La量为1时的量。
8.根据权利要求7所述的热化学燃料制造用催化剂,其特征在于,所述Mn的一部分被Fe置换。
9.根据权利要求8所述的热化学燃料制造用催化剂,其特征在于,所述置换的Fe的浓度x为0.35以上且0.85以下,x是以置换前的Mn量为1时的量。
10.根据权利要求1所述的热化学燃料制造用催化剂,其特征在于,所述A元素是Ba,所述X元素是Ti,所述Ti的一部分被Mn置换。
11.根据权利要求10所述的热化学燃料制造用催化剂,其特征在于,所述置换的Mn的浓度x大于0且为0.5以下,x是以置换前的Ti量为1时的量。
12.一种热化学燃料的制造方法,其特征在于,使用权利要求1~11中的任意一项所述的热化学燃料制造用催化剂。
13.一种热化学燃料制造方法,其特征在于,其是使用权利要求1~11中的任意一项所述的热化学燃料制造用催化剂,用第一温度和作为该第一温度以下的第二温度这两段热化学循环,由热能制造燃料的热化学燃料制造方法,其中,所述第一温度为600℃以上且1600℃以下,所述第二温度为400℃以上且1600℃以下。
14.根据权利要求13所述的热化学燃料制造方法,其特征在于,通过照射聚光太阳能进行加热或通过用废热进行加热从而得到所述第一温度。
15.一种热化学燃料制造方法,其特征在于,其是用第一温度和作为该第一温度以下的第二温度这两段热化学循环,由热能制造燃料的热化学燃料制造方法,并具有:
将具有组成式AXO3±δ的钙钛矿氧化物加热至第一温度进行还原的工序,其中0≤δ<1;和
使原料气体接触还原后的钙钛矿氧化物,使该钙钛矿氧化物氧化来制造燃料的工序。
16.根据权利要求15所述的热化学燃料制造方法,其特征在于,所述燃料为氢、一氧化碳、氢与一氧化碳的混合气体、甲烷、甲醇中的任意一种。
17.根据权利要求15所述的热化学燃料制造方法,其特征在于,所述原料气体为水蒸气。
18.根据权利要求15所述的热化学燃料制造方法,其特征在于,所述原料气体为二氧化碳和水蒸气。
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