CN116745028A - 用于甲烷重整的催化剂和制备其的方法 - Google Patents
用于甲烷重整的催化剂和制备其的方法 Download PDFInfo
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- CN116745028A CN116745028A CN202280009657.7A CN202280009657A CN116745028A CN 116745028 A CN116745028 A CN 116745028A CN 202280009657 A CN202280009657 A CN 202280009657A CN 116745028 A CN116745028 A CN 116745028A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000003054 catalyst Substances 0.000 title claims abstract description 112
- 238000002407 reforming Methods 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims description 68
- 239000000126 substance Substances 0.000 claims abstract description 94
- 229910052751 metal Inorganic materials 0.000 claims abstract description 78
- 239000002184 metal Substances 0.000 claims abstract description 77
- 150000001875 compounds Chemical class 0.000 claims abstract description 70
- 239000011247 coating layer Substances 0.000 claims abstract description 54
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 38
- 229910002367 SrTiO Inorganic materials 0.000 claims description 21
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 19
- 239000001569 carbon dioxide Substances 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000012018 catalyst precursor Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 238000002453 autothermal reforming Methods 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 239000006262 metallic foam Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 238000000629 steam reforming Methods 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 24
- 239000010936 titanium Substances 0.000 description 19
- 230000000694 effects Effects 0.000 description 14
- 238000006057 reforming reaction Methods 0.000 description 13
- 239000011148 porous material Substances 0.000 description 12
- 238000004817 gas chromatography Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000008188 pellet Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000003893 lactate salts Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- -1 organic acid salts Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
根据本申请的一个示例性实施方案的用于甲烷重整的催化剂包含:多孔金属载体;第一涂层,设置在所述多孔金属载体上并且包含由化学式1表示的钙钛矿基化合物;和第二涂层,设置在所述第一涂层上并且包含由化学式2表示的钙钛矿基化合物。
Description
技术领域
本申请要求在韩国知识产权局于2021年11月18日提交的韩国专利申请No.10-2021-0159456的优先权和权益,该专利申请的全部内容通过引用并入本说明书中。
本申请涉及一种用于甲烷重整的催化剂和制备该催化剂的方法。
背景技术
作为减少由全球变暖引起的温室气体的活动的一部分,已经对二氧化碳转化技术进行了大量的研究。二氧化碳转化技术之一的二氧化碳重整反应是一种通过使甲烷和二氧化碳反应来得到由氢气和一氧化碳组成的合成气的技术。
合成气是一种来自多种下游原料的具有高开发价值的材料。作为工业上得到合成气(H2/CO)的方法,天然气的重整反应可以大致分为蒸汽重整工艺、二氧化碳(CO2)重整工艺、催化部分氧化工艺、自热重整工艺、三重整工艺,如下面的反应方案1至5等。
[反应方案1]
CH4+H2O→3H2+COΔH=226kJ/mol
[反应方案2]
CH4+CO2→2H2+2COΔH=261kJ/mol
[反应方案3]
CH4+0.5O2→2H2+COΔH=-44kJ/mol
[反应方案4]
自热重整:反应方案1+反应方案3
[反应方案5]
三重整:反应方案1+反应方案2+反应方案3
同时,在重整工艺中可以使用各种催化剂用于重整活性。其中,当在重整工艺中使用贵金属催化剂时,存在将天然气转化为氢气的效率高的优势,但是存在由于贵金属催化剂价格昂贵而经济可行性劣化的问题。
因此,在重整工艺中通常使用具有高的氢转化效率且相对便宜的镍催化剂。然而,在这种情况下,存在由于在镍催化剂的表面上不可避免地产生碳,因而镍催化剂失活的问题。
因此,本领域需要开发一种耐碳沉积并且可以有效地应用于甲烷重整工艺的催化剂。
发明内容
技术问题
本申请致力于提供一种用于甲烷重整的催化剂和制备该催化剂的方法。
技术方案
本申请的一个示例性实施方案提供了一种用于甲烷重整的催化剂,包含:
多孔金属载体;
第一涂层,设置在所述多孔金属载体上并且包含由下面化学式1表示的钙钛矿基化合物;和
第二涂层,设置在所述第一涂层上并且包含由下面化学式2表示的钙钛矿基化合物。
[化学式1]
SrTiO3
[化学式2]
Sr1-xAxTiαByO3-δ
在化学式2中,
A选自Y、Sc、La和镧系元素,
B是Ni、Co、Fe、Mn、Cr、Mo、Ru或Rh,
x是0以上且小于1的实数,
y是0以上且小于0.3的实数,
δ是0以上且小于1的实数,
α是大于0.7且1以下的实数,并且
满足(x+y)>0。
此外,本申请的另一示例性实施方案提供了一种制备用于甲烷重整催化剂的方法,所述方法包括:
制备各个包含由化学式1表示的钙钛矿基化合物的前体的第一溶液;和包含由化学式2表示的钙钛矿基化合物的前体的第二溶液;
通过用所述第一溶液涂覆多孔金属载体来制备设置有第一涂层的催化剂前体,然后进行第一热处理过程;和
通过用所述第二溶液涂覆设置有所述第一涂层的催化剂前体来制备设置有第二涂层的催化剂,然后进行第二热处理过程。
有益效果
根据本申请的一个示例性实施方案的用于甲烷重整的催化剂不仅可以改善多孔金属载体与包含由化学式2表示的钙钛矿基化合物的第二涂层之间的粘合力,而且还可以通过形成包含由化学式1表示的无催化剂组分的钙钛矿基化合物的第一涂层来防止多孔金属载体的副反应。
此外,根据本申请的一个示例性实施方案的用于甲烷重整的催化剂的特征在于,由于钙钛矿基化合物负载在具有高导热性的多孔金属载体上,因此,与现有技术中的粒料型或粉末型催化剂相比,容易控制反应热。
另外,根据本申请的一个示例性实施方案的用于甲烷重整的催化剂在甲烷重整反应的过程中即使在高空速下也可以表现出高活性,因为可以增加催化剂的活性表面积。
附图说明
图1是示出根据本申请的实施例1的用于甲烷重整的催化剂的表面的一组电子显微镜照片。
具体实施方式
下文中,将更详细地描述本说明书。
在本说明书中,当一个构件设置在另一构件“上”时,这不仅包括一个构件与另一构件接触的情况,还包括在两个构件之间还存在又一构件的情况。
在本说明书中,当一个部分“包含”一个构成要素时,除非另外具体地说明,否则这不是指排除另一构成要素,而是指还可以包含另一构成要素。
目前,在重整器领域中广泛使用的催化剂的情况中,通常使用粉末型催化剂和粒料型负载催化剂。虽然粉末型催化剂由于催化剂优异的分散度而可以具有优异的性能,但是在工业中难以直接使用粉末型催化剂。例如,当使用粉末型催化剂驱动重整器时,催化剂与反应后产生的物质一起出来,并且在这种情况下,粉末形式的催化剂逐渐积累在出口部分处的料流管中,最终,会出现阻塞整个管的现象。因此,存在粉末型催化剂不能用于工业中使用的重整器的缺点。
另外,粒料型负载催化剂目前常用于工业重整器中。由于传质速率的限制,与粉末型催化剂相比,其仅在催化剂性能方面性能劣化,但是存在由于使用了载体而粒料型负载催化剂可以长时间使用的优势。然而,通常被用作粒料型负载催化剂的γ-Al2O3粒料具有弱的结构强度,因此会容易断裂,由此,存在在反应器中产生压差的缺点。此外,由于粒料型负载催化剂的特性而体积大,因此,当在大容量重整器中使用粒料型负载催化剂时,其体积变得相当大。此外,所有的重整反应都对反应温度敏感,但是现有的粒料型催化剂具有的缺点是,由于热导性大大降低,热量不均匀地分布在整个反应器中。另外,由于重整反应非常快,在粒料型载体或挤出的催化剂的情况下,催化剂的效率系数为0.3以下,因此存在催化剂的利用率劣化的缺点。
因此,本申请意在通过用催化剂涂覆具有高传热传质速率的多孔金属载体的方法,来缓解作为粉末型的缺点的阻塞料流管的现象,并且改善作为粉末型和粒料型的共同缺点的传热传质速率。此外,本申请意在提供一种用于甲烷重整的催化剂,其能够一次负载大量的催化剂并且抑制由粘合剂引起的副作用。
根据本申请的一个示例性实施方案的用于甲烷重整的催化剂包含:多孔金属载体;第一涂层,设置在所述多孔金属载体上并且包含由化学式1表示的钙钛矿基化合物;和第二涂层,设置在所述第一涂层上并且包含由化学式2表示的钙钛矿基化合物。
在本申请的一个示例性实施方案中,由化学式1表示的钙钛矿基化合物是无催化剂组分的化合物,由化学式2表示的钙钛矿基催化剂是包含催化剂组分(化学式2的A和/或B)的化合物,并且这些化合物彼此不同。
在本申请的一个示例性实施方案中,化学式2可以由下面的化学式3或化学式4表示。
[化学式3]
SrTiαByO3-δ
[化学式4]
Sr1-xYxTiαByO3-δ
在化学式3和化学式4中,
B是Ni或Ru,
x是大于0且小于1的实数,
y是大于0且小于0.3的实数,
δ是大于0且小于1的实数,
α是大于0.7且1以下的实数。
在本申请的一个示例性实施方案中,所述多孔金属载体可以由能够在800℃以上的高温下保持热稳定性的材料组成。
在本申请的一个示例性实施方案中,所述多孔金属载体可以是包括NiFeCrAl、NiCrAl、SiC或α-Al2O3的金属泡沫。
所述多孔金属载体是具有多种形状的载体,具有小的热容量和优异的传热能力,因此,可以成型为期望的形状来使用。对多孔金属载体的形式、尺寸等没有特别地限制,并且所述多孔金属载体的孔隙率可以为10%至99%、50%至96%和85%至96%。所述多孔金属载体的平均孔径(cell size)可以为400μm至2,000μm和450μm至1,500μm。当多孔金属载体的平均孔径小于400μm时,会难以用前体溶液涂覆多孔金属载体,并且当多孔金属载体的平均孔径大于2,000μm时,能被覆盖的催化剂的表面积会减少,因此,由于该范围在工艺中会不利,该平均孔径范围不优选。本领域技术人员可以考虑多孔金属载体的材料、孔径、孔隙率等,使用本领域已知的方法适当地制备所述多孔金属载体。根据本申请的一个示例性实施方案,如下面将详细描述的实施例中,可以应用具有各种材料、孔径等的多孔金属载体。
在本申请的一个示例性实施方案中,基于所述多孔金属载体的总重量,由化学式1表示的钙钛矿基化合物的含量可以为1重量%至20重量%和1.5重量%至18重量%。当由化学式1表示的钙钛矿基化合物的含量超过20重量%时,能够涂覆由化学式2表示的钙钛矿基化合物的剩余容量会减少,因此,由于与多孔金属载体的体积相比,催化剂的活性会降低,因而上述重量范围不优选。此外,当由化学式1表示的钙钛矿基化合物的含量小于1重量%时,由于含量太少,会难以得到由第一涂层引起的效果。
在本申请的一个示例性实施方案中,由化学式1表示的钙钛矿基化合物:由化学式2表示的钙钛矿基化合物的重量比可以为1∶1至1∶20和1∶1.1至1∶15。由化学式1表示的钙钛矿基化合物:由化学式2表示的钙钛矿基化合物的重量比超出所述范围的情况不优选,因为与多孔金属载体的体积相比,催化剂的活性会降低。
在本申请的一个示例性实施方案中,化学式2的(α+y)可以为1。此外,在本申请的一个示例性实施方案中,化学式2的(α+y)可以是大于0.90且小于1的实数。在化学式2中,B如Ni取代一部分Ti,并且(α+y)的理论化学计量比为1,但是当在制备由化学式2表示的钙钛矿基化合物的过程中Ti的含量略低于理论化学计量比时,化学式2中的Ti会更容易地被B如Ni取代。
在本申请的一个示例性实施方案中,基于用于甲烷重整的催化剂的总重量,由化学式2表示的钙钛矿基化合物的含量可以为3重量%至40重量%、6重量%至35重量%和7重量%至30重量%。当基于用于甲烷重整的催化剂的总重量,由化学式2表示的钙钛矿基化合物的含量小于3重量%时,由于催化剂表面上的活性位点相对少,反应性会降低,因此,所述含量不优选。另外,当由化学式2表示的钙钛矿基化合物的含量超过40重量%时,与多孔金属载体相比,包含相对大量的催化剂组分,使得难以保持孔隙结构,会难以将催化剂组分与多孔金属载体粘合,因此,甲烷重整反应的实际效益会降低。
在本申请的一个示例性实施方案中,所述第一涂层可以设置在多孔金属载体上的整个表面上。
在本申请的一个示例性实施方案中,所述用于甲烷重整的催化剂的表面的至少一部分可以包含突出形状。所述突出形状可以是球形的、椭圆形的或它们的组合,但不限于此。
在本申请的一个示例性实施方案中,包含由化学式1表示的钙钛矿基化合物的第一涂层可以用于将包含由化学式2表示的钙钛矿基化合物的第二涂层固定在多孔金属载体上。此外,包含由化学式2表示的钙钛矿基化合物的第二涂层可以以突出的形式存在于第一涂层上,因此,通过增加催化剂的反应表面积可以改善甲烷重整反应的性能。
此外,根据本申请的一个示例性实施方案,通过同时使用:包含由化学式1表示的钙钛矿基化合物的第一涂层;和包含由化学式2表示的钙钛矿基化合物的第二涂层,与当单独使用催化剂粒子时相比,在多孔金属载体上负载的催化剂的总含量会增加。另外,根据本申请的一个示例性实施方案,催化剂的耐久性和性能会得到改善,因为可以防止在高温(750℃以上)下长时间操作条件下,作为多孔金属载体的主要成分的金属(Ni、Cr等)以金属氧化物(NiO、Cr2O3等)的形式暴露于表面的现象,并且通过使用包含由化学式1表示的钙钛矿基化合物的第一涂层,可以防止化学式2的催化剂的成分比例或相发生变化。
在本申请的一个示例性实施方案中,所述用于甲烷重整的催化剂可以应用于蒸汽重整工艺、二氧化碳(CO2)重整工艺、催化部分氧化工艺、自热重整工艺、三重整工艺或混合重整工艺,并且对甲烷重整工艺没有特别地限制。
根据本申请的一个示例性实施方案的制备用于甲烷重整的催化剂的方法包括:制备各个包含由化学式1表示的钙钛矿基化合物的前体的第一溶液和包含由化学式2表示的钙钛矿基化合物的前体的第二溶液;通过用所述第一溶液涂覆多孔金属载体来制备设置有第一涂层的催化剂前体,然后进行第一个热处理过程;和通过用所述第二溶液涂覆设置有所述第一涂层的催化剂前体来制备设置有第二涂层的催化剂,然后进行第二热处理过程。
在根据本申请的一个示例性实施方案的制备用于甲烷重整的催化剂的方法中,多孔金属载体、由化学式1表示的钙钛矿基化合物、由化学式2表示的钙钛矿基化合物等的详细情况与上述相同。
特别地,包含由化学式1表示的钙钛矿基化合物的前体的第一溶液以及包含由化学式2表示的钙钛矿基化合物的前体的第二溶液可以各自以溶胶或凝胶的形式应用。
所述钙钛矿基化合物的前体是构成钙钛矿基化合物的金属的前体,并且可以通过调节其含量来调节钙钛矿基化合物的金属摩尔比。另外,对金属的前体没有特别地限制,可以组合使用金属元素的铵盐、硝酸盐、碳酸盐、氯化物、乳酸盐、氢氧化物、有机酸盐、氧化物,或它们的混合物。
根据本申请的一个示例性实施方案的制备用于甲烷重整的催化剂的方法包括:制备各个包含由化学式1表示的钙钛矿基化合物的前体的第一溶液;和包含由化学式2表示的钙钛矿基化合物的前体的第二溶液。
所述第一溶液和所述第二溶液可以各自独立地还包含溶剂,并且作为所述溶剂,可以使用本领域已知的溶剂,但不特别限于此。
根据本申请的一个示例性实施方案的制备用于甲烷重整的催化剂的方法包括:通过用所述第一溶液涂覆多孔金属载体来制备设置有第一涂层的催化剂前体,然后进行第一热处理过程;和通过用所述第二溶液涂覆设置有所述第一涂层的催化剂前体来制备设置有第二涂层的催化剂,然后进行第二热处理过程。
作为第一溶液和第二溶液的涂覆方法,可以使用本领域已知的方法,可以使用浸涂、洗涂等,但方法不限于此。
第一热处理过程和第二热处理过程可以各自独立地包括进行干燥和烧制。干燥可以在50℃至150℃的温度下进行1小时至48小时,并且可以在60℃至100℃的温度下进行5小时至36小时,但不限于此。此外,烧制可以在350℃至1,100℃的温度下在空气气氛中进行1小时至10小时,并且可以在500℃至1,000℃的温度下在空气气氛中进行1.5小时至8小时,但不限于此。当烧制在低于350℃的温度下进行时,不能适当地形成钙钛矿相,当烧制在高于1,100℃的温度下进行时,多孔金属载体的耐久性会劣化,因此,该温度不优选。
在本申请的一个示例性实施方案中,所述方法还可以包括:在第二热处理过程之后,测量在多孔金属载体上负载的催化剂的重量。另外,通过测量在多孔金属载体上负载的催化剂的重量,可以将用上述第二溶液涂覆设置有第一涂层的催化剂前体,然后进行第二热处理过程的工艺重复进行1次至10次,直至在多孔金属载体上负载期望的量的催化剂。
根据本申请的一个示例性实施方案的用于甲烷重整的催化剂不仅可以改善多孔金属载体与包含由化学式2表示的钙钛矿基化合物的第二涂层之间的粘合力,而且可以通过形成包含由下面化学式1表示的无催化剂组分的钙钛矿基化合物的第一涂层来防止多孔金属载体的副反应。
此外,根据本申请的一个示例性实施方案的用于甲烷重整的催化剂的特征在于,由于钙钛矿基化合物负载在具有高导热性的多孔金属载体上,因此,与相关技术中的粒料型或粉末型催化剂相比,容易控制反应热。
另外,根据本申请的一个示例性实施方案的用于甲烷重整的催化剂由于可以增加催化剂的活性表面积,因此,即使在甲烷重整反应的过程中在高空速下,也可以表现出高活性。
下文中,将参照用于具体描述本申请的实施例详细地描述本申请。然而,根据本申请的实施例可以以各种形式修改,并且不应理解为本申请的范围局限于下面详细描述的实施例。提供本申请的实施例是为了向本领域普通技术人员更完整地说明本申请。
<实施例>
<实施例1>
1)制备包含钙钛矿基化合物(SrTiO3)的前体的第一溶液。
通过柠檬酸盐法制备钙钛矿基化合物组分溶液。将硝酸锶(Sr(NO3)3H2O)与柠檬酸和乙二醇一起溶解在蒸馏水中。将钛酸异丙酯(Ti(OCH(CH3)2)4)溶解在乙醇中之后,将这两种溶液在70℃下混合。之后,将混合物搅拌3小时之后,将混合物冷却至室温并储存。在这种情况下,溶液的浓度为0.1M。
2)制备包含由化学式2表示的钙钛矿基化合物(SrTi0.97Ni0.03O3-δ,0<δ<1)的前体的第二溶液。
除了基于金属,加入并使用相对于钛3摩尔%的硝酸镍(Ni(NO3)2)之外,以与上面的1)相同的方式进行工艺。
3)制备用于甲烷重整的催化剂
用第一溶液浸涂多孔金属载体(NiCrAl,平均孔径:1,200μm)(形成第一涂层),然后在70℃下干燥24小时,并且在300℃至900℃的空气气氛中热处理3小时。
之后,用第二溶液浸涂其中形成有第一涂层的多孔金属载体(形成第二涂层),然后在70℃下干燥24小时,并在300℃至900℃的空气气氛中热处理3小时。将第二溶液的浸涂、干燥和热处理重复数次,以最终制备其中第一涂层(SrTiO3)和第二涂层(SrTi0.97Ni0.03O3-δ,0<δ<1)设置在多孔金属载体上的催化剂。基于用于甲烷重整的催化剂的总重量,钙钛矿基化合物(SrTiO3)的含量为7重量%,由化学式2表示的钙钛矿基化合物(SrTi0.97Ni0.03O3-δ,0<δ<1)的含量为20重量%。
根据本申请的实施例1的用于甲烷重整的催化剂的表面的一组电子显微镜照片示于下面图1中。
由化学式1或化学式2表示的钙钛矿基化合物的含量可以通过下面的公式1计算。
[公式1]
由化学式1或化学式2表示的钙钛矿基化合物的含量(重量%)=(催化剂的总重量-多孔金属载体的重量)/(催化剂的总重量)×100
<实施例2>
除了在第二溶液的制备过程中,基于金属,以相对于锶12摩尔%的量加入硝酸钇(Y(NO3)2),并且加入硝酸镍(Ni(NO3)2)使得钛∶镍的摩尔比变为0.80∶0.15之外,以与实施例1相同的方式进行工艺。
<实施例3>
除了在第二溶液的制备过程中,基于金属,以相对于锶12摩尔%的量加入硝酸钇(Y(NO3)2),并且加入硝酸镍(Ni(NO3)2)使得钛∶镍的摩尔比变为0.80∶0.20之外,以与实施例1相同的方式进行工艺。
<实施例4>
除了在第二溶液的制备过程中,基于金属,以相对于钛5摩尔%的量加入和使用氯化钌(RuCl3)代替硝酸镍(Ni(NO3)2)之外,以与实施例1相同的方式进行工艺。
<实施例5>
除了在第二溶液的制备过程中,基于金属,以相对于锶8摩尔%的量加入硝酸钇(Y(NO3)2),并且加入氯化钌(RuCl3)使得钛∶钌的摩尔比变为0.80∶0.15之外,以与实施例1相同的方式进行工艺。
<实施例6>
除了基于用于甲烷重整的催化剂的总重量,将钙钛矿基化合物(SrTiO3)的含量调节为1.7重量%之外,以与实施例3相同的方式进行工艺。
<实施例7>
除了基于用于甲烷重整的催化剂的总重量,将钙钛矿基化合物(SrTiO3)的含量调节为13重量%之外,以与实施例3相同的方式进行工艺。
<实施例8>
除了基于用于甲烷重整的催化剂的总重量,将钙钛矿基化合物(SrTiO3)的含量调节为17重量%之外,以与实施例3相同的方式进行工艺。
<实施例9>
除了使用NiFeCrAl(平均孔径:1,200μm)代替NiCrAl作为多孔金属载体之外,以与实施例3相同的方式进行工艺。
<实施例10>
除了使用NiCrAl 800(平均孔径:800μm)代替NiCrAl作为多孔金属载体之外,以与实施例3相同的方式进行工艺。
<实施例11>
除了使用NiCrAl_1500(平均孔径:1,500μm)代替NiCrAl作为多孔金属载体之外,以与实施例3相同的方式进行工艺。
<比较例1>
单独使用多孔金属载体(NiCrAl,平均孔径:1,200μm)作为比较例1。
<比较例2>
除了仅用第一溶液涂覆多孔金属载体而不用第二溶液涂覆催化剂前体之外,以与实施例1相同的方式进行工艺。
<比较例3>
除了仅用第二溶液涂覆催化剂前体而不用第一溶液涂覆多孔金属载体之外,以与实施例1相同的方式进行工艺。
<比较例4>
除了仅用第二溶液涂覆催化剂前体而不用第一溶液涂覆多孔金属载体之外,以与实施例3相同的方式进行工艺。
实施例和比较例中的多孔金属载体、第一涂层和第二涂层的配置如下表1中所示。
[表1]
多孔金属载体 | 第一涂层 | 第二涂层 | |
实施例1 | NiCrAl | SrTiO3 | SrTi0.97Ni0.03O3-δ |
实施例2 | NiCrAl | SrTiO3 | Sr0.88Y0.12Ti0.80Ni0.15O3-δ |
实施例3 | NiCrAl | SrTiO3 | Sr0.88Y0.12Ti0.80Ni0.20O3-δ |
实施例4 | NiCrAl | SrTiO3 | SrTi0.95Ru0.05O3-δ |
实施例5 | NiCrAl | SrTiO3 | SR0.92Y0.08Ti0.80Ru0.15O3-δ |
实施例6 | NiCrAl | SrTiO3 | Sr0.88Y0.12Ti0.80Ni0.20O3-δ |
实施例7 | NiCrAl | SrTiO3 | Sr0.88Y0.12Ti0.80Ni0.20O3-δ |
实施例8 | NiCrAl | SrTiO3 | Sr0.88Y0.12Ti0.80Ni0.20O3-δ |
实施例9 | NiFeCrAl | SrTiO3 | Sr0.88Y0.12Ti0.80Ni0.20O3-δ |
实施例10 | NiCrAl_800 | SrTiO3 | Sr0.88Y0.12Ti0.80Ni0.20O3-δ |
实施例11 | NiCrAl_1500 | SrTiO3 | Sr0.88Y0.12Ti0.80Ni0.20O3-δ |
比较例1 | NiCrAl | - | - |
比较例2 | NiCrAl | SrTiO3 | - |
比较例3 | NiCrAl | - | SrTi0.97Ni0.03O3-δ |
比较例4 | NiCrAl | - | Sr0.88Y0.12Ti0.80Ni0.20O3-δ |
<试验例1>甲烷的干重整反应的评价
引入固定床反应器***进行甲烷的干重整反应。使用石英管反应器(内径=1/2英寸,长度=50cm)并且装入实施例和比较例的各个催化剂(约2g)。首先,催化剂在10%的H2/N2条件下在800℃下进行还原工艺1小时至2小时之后,进行100小时的催化反应。为了更清楚地比较催化剂之间的活性差异,在严格的空速下评价催化剂的活性特性。
气体组成:CH4∶CO2∶N2=1∶1.2∶0.96
流速:气时空速(GHSV)=2,500hr-1(基于CH4)
反应温度:750℃
反应压力:1巴
使用气相色谱(GC)通过分析产生的气体的组成来计算反应100小时之后的反应转化率,并示于下表2中。
转化率(Xi,%)=[(Fiin-Fiout)/Fiin]×100(Fi=i的流速)
<GC分析条件>
1)GC型号:Agilent 6890
2)烘箱温度:40℃/7min-90℃/5min-180℃/6min
3)检测器:TCD,250℃
4)样品:0.25mL
5)阀箱温度:150℃
[表2]
催化剂类型 | GHSV(hr-1) | CH4转化率(%) | CO2转化率(%) | H2/CO |
实施例1 | 2,500 | 44 | 52 | 0.76 |
实施例2 | 2,500 | 58 | 65 | 0.76 |
实施例3 | 2,500 | 60 | 69 | 0.76 |
实施例4 | 2,500 | 61 | 65 | 0.78 |
实施例5 | 2,500 | 61 | 64 | 0.78 |
实施例6 | 2,500 | 57 | 62 | 0.75 |
实施例7 | 2,500 | 62 | 70 | 0.78 |
实施例8 | 2,500 | 58 | 64 | 0.75 |
比较例1 | 2,500 | 18 | 20 | 0.54 |
比较例2 | 2,500 | 3 | 4 | 0.20 |
比较例3 | 2,500 | 42 | 50 | 0.73 |
比较例4 | 2,500 | 50 | 58 | 0.72 |
如表2的结果所示,可以确认,当将实施例1和比较例3彼此比较或将实施例3和比较例4彼此比较时,根据本发明的用于甲烷重整的催化剂,与没有涂覆第一涂层的比较例3和比较例4相比,其中包含多孔金属载体、包含由化学式1表示的钙钛矿基化合的第一涂层和包含由化学式2表示的钙钛矿基化合的第二涂层的根据本发明的用于甲烷重整的催化剂具有优异的CH4转化率和CO2转化率。
<试验例2>甲烷的干重整反应的评价
引入固定床反应器***进行甲烷的干重整反应。使用石英管反应器(内径=1/2英寸,长度=50cm)并且装入实施例和比较例的各个催化剂(约2g)。首先,催化剂在10%的H2/N2条件下在800℃下进行还原工艺1小时至2小时之后,进行100小时的催化反应。为了更清楚地比较催化剂之间的活性差异,在严格的空速下评价催化剂的活性特性。
气体组成:CH4∶CO2∶N2=1∶1.2∶0.96
流速:气时空速(GHSV)=1,500hr-1(基于CH4)
反应温度:800℃
反应压力:1巴
使用气相色谱(GC)通过分析产生的气体的组成来计算反应100小时之后的反应转化率,并示于下表3中。
转化率(Xi,%)=[(Fiin-Fiout)/Fiin]×100(Fi=i的流速)
<GC分析条件>
1)GC型号:Agilent 6890
2)烘箱温度:40℃/7min-90℃/5min-180℃/6min
3)检测器:TCD,250℃
4)样品:0.25mL
5)阀箱温度:150℃
[表3]
催化剂类型 | GHSV(hr-1) | CH4转化率(%) | CO2转化率(%) | H2/CO |
实施例3 | 1,500 | 91 | 89 | 0.84 |
实施例5 | 1,500 | 91 | 90 | 0.85 |
实施例9 | 1,500 | 90 | 88 | 0.84 |
实施例10 | 1,500 | 92 | 91 | 0.85 |
实施例11 | 1,500 | 88 | 87 | 0.84 |
比较例4 | 1,500 | 89 | 88 | 0.82 |
如表3的结果所示,可以确认,当将实施例3和比较例4彼此比较时,与没有涂覆第一涂层的比较例4相比,其中包含多孔金属载体、包含由化学式1表示的钙钛矿基化合的第一涂层和包含由化学式2表示的钙钛矿基化合的第二涂层的根据本发明的用于甲烷重整的催化剂具有优异的CH4转化率和CO2转化率。
如上面结果所示,可以确认,在本申请的实施例中,与比较例相比,H2/CO的比例会提高。因此,可以确认,在本申请的实施例中,由多孔金属载体引起的副反应减少。
因此,根据本申请的一个示例性实施方案的用于甲烷重整的催化剂不仅可以改善多孔金属载体与包含由化学式2表示的钙钛矿基化合物的第二涂层之间的粘合性,而且可以通过形成包含由下面化学式1表示的无催化剂组分的钙钛矿基化合物的第一涂层来防止多孔金属载体的副反应。
此外,根据本申请的一个示例性实施方案的用于甲烷重整的催化剂的特征在于,由于钙钛矿基化合物负载在具有高导热性的多孔金属载体上,因此,与相关技术中的粒料型或粉末型催化剂相比,容易控制反应热。
另外,根据本申请的一个示例性实施方案的用于甲烷重整的催化剂由于可以增加催化剂的活性表面积,因此,在甲烷的重整反应的过程中即使在高空速下也可以表现出高活性。
Claims (8)
1.一种用于甲烷重整的催化剂,包含:
多孔金属载体;
第一涂层,设置在所述多孔金属载体上并且包含由下面化学式1表示的钙钛矿基化合物;和
第二涂层,设置在所述第一涂层上并且包含由下面化学式2表示的钙钛矿基化合物:
[化学式1]
SrTiO3
[化学式2]
Sr1-xAxTiαByO3-δ
其中,在化学式2中,
A选自Y、Sc、La和镧系元素,
B是Ni、Co、Fe、Mn、Cr、Mo、Ru或Rh,
x是0以上且小于1的实数,
y是0以上且小于0.3的实数,
δ是0以上且小于1的实数,
α是大于0.7且1以下的实数,并且
满足x+y>0。
2.根据权利要求1所述的用于甲烷重整的催化剂,其中,化学式2由下面化学式3或化学式4表示:
[化学式3]
SrTiαBuO3-δ
[化学式4]
Sr1-xYxTiαByO3-δ
在化学式3和化学式4中,
B是Ni或Ru,
x是大于0且小于1的实数,
y是大于0且小于0.3的实数,
δ是大于0且小于1的实数,
α是大于0.7且1以下的实数。
3.根据权利要求1所述的用于甲烷重整的催化剂,其中,所述多孔金属载体是包括NiFeCrAl、NiCrAl、SiC或α-Al2O3的金属泡沫。
4.根据权利要求1所述的用于甲烷重整的催化剂,其中,基于所述用于甲烷重整的催化剂的总重量,所述由化学式2表示的钙钛矿基化合物的含量为3重量%至40重量%。
5.根据权利要求1所述的用于甲烷重整的催化剂,其中,所述用于甲烷重整的催化剂应用于蒸汽重整工艺、二氧化碳(CO2)重整工艺、催化部分氧化工艺、自热重整工艺、三重整工艺或混合重整工艺。
6.一种制备用于甲烷重整的催化剂的方法,所述方法包括:
分别制备包含由下面化学式1表示的钙钛矿基化合物的前体的第一溶液;和包含由下面化学式2表示的钙钛矿基化合物的前体的第二溶液;
通过用所述第一溶液涂覆多孔金属载体来制备设置有第一涂层的催化剂前体,然后进行第一热处理过程;和
通过用所述第二溶液涂覆所述设置有第一涂层的催化剂前体来制备设置有第二涂层的催化剂,然后进行第二热处理过程:
[化学式1]
SrTiO3
[化学式2]
Sr1-xAxTiαByO3-δ
其中,在化学式2中,
A选自Y、Sc、La和镧系元素,
B是Ni、Co、Fe、Mn、Cr、Mo、Ru或Rh,
x是0以上且小于1的实数,
V是0以上且小于0.3的实数,
δ是0以上且小于1的实数,
α是大于0.7且1以下的实数,并且
满足x+y>0。
7.根据权利要求6所述的方法,其中,化学式2由下面化学式3或化学式4表示:
[化学式3]
SrTiαByO3-δ
[化学式4]
Sr1-xYxTiαByO3-δ
在化学式3和化学式4中,
B是Ni或Ru,
x是大于0且小于1的实数,
y是大于0且小于0.3的实数,
δ是大于0且小于1的实数,
α是大于0.7且1以下的实数。
8.根据权利要求6所述的方法,其中,所述多孔金属载体是包括NiFeCrAl、NiCrAl、SiC或α-Al2O3的金属泡沫。
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