CN115155599B - 一种包覆Ni-In@SiO2-Al2O3的中空介孔纳米催化剂及其制备方法和应用 - Google Patents
一种包覆Ni-In@SiO2-Al2O3的中空介孔纳米催化剂及其制备方法和应用 Download PDFInfo
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- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 22
- 229910018072 Al 2 O 3 Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- 238000000629 steam reforming Methods 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 239000011247 coating layer Substances 0.000 claims abstract description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract 7
- 239000011248 coating agent Substances 0.000 claims abstract 3
- 238000000576 coating method Methods 0.000 claims abstract 3
- 239000007787 solid Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229920002873 Polyethylenimine Polymers 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 150000002471 indium Chemical class 0.000 claims description 7
- 239000010410 layer Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 31
- 239000000377 silicon dioxide Substances 0.000 abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 11
- 239000007789 gas Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 19
- 229910052593 corundum Inorganic materials 0.000 description 19
- 229910001845 yogo sapphire Inorganic materials 0.000 description 19
- 229910052681 coesite Inorganic materials 0.000 description 16
- 229910052906 cristobalite Inorganic materials 0.000 description 16
- 229910052682 stishovite Inorganic materials 0.000 description 16
- 229910052905 tridymite Inorganic materials 0.000 description 16
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 238000000227 grinding Methods 0.000 description 4
- 239000002923 metal particle Substances 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
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- 230000005669 field effect Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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Abstract
本发明提供了一种包覆Ni‑In@SiO2‑Al2O3的中空介孔纳米催化剂及其制备方法和应用。催化剂由Ni、Si、Al、O、In元素组成，Ni‑In纳米颗粒以无定形状态存在于载体SiO2内部，所述载体SiO2外含有包覆层Al2O3作为催化剂的壳体。本发明提供的包覆Ni‑In@SiO2‑Al2O3的中空介孔纳米催化剂具有独特的中空二氧化硅壳结构，使得Ni‑In纳米颗粒能够保持高度的分散性，大大提高了催化剂的反应活性；由于In金属的添加，使得催化剂的抗积炭和耐高温能力均得到了大幅的提高；本发明的催化剂用于甲烷水蒸汽重整制氢反应，原料气甲烷的转化率以及合成气氢气的选择性高。
Description
技术领域
本发明属于催化剂制备领域，具体涉及一种包覆Ni-In@SiO2-Al2O3的中空介孔纳米催化剂及其制备方法和应用。
背景技术
氢气具有热转化效率高、环境零污染、能量密度高和输送成本低等优点，是目前最具吸引力的清洁高效能源，在石油化工和动力燃料行业中均有广泛应用，发展大规模和低成本制氢技术，已成为国家的能源战略方向。氢能与其他能源相比，具有明显的提取与应用优势，它不仅可通过传统的化石能源提取，还可以通过太阳能、风能等可再生能源制备，并具有热值高、无污染、利用形式多样、储运方便等优点。
我国天然气储量极为丰富，环境接受性良好。天然气的主要成分是甲烷，杂质含量少，因此甲烷不仅在自然界分布广泛，而且可以直接用作高效、优质、清洁的能源，还可以通过转化生产更有意义的化工原料。以天然气为原料制氢主要有水蒸汽重整、CO2重整和部分氧化法。其中甲烷水蒸汽重整后具有较高的氢气产率，故而常被用作制氢的一种高效方法。
目前甲烷水蒸气重整制氢催化剂多为负载型催化剂，活性组分有以Rh、Pt、Pb、Ir为主的贵金属，以及以Ni、Co、Fe为主的非贵金属。贵金属催化剂在高温下通常因活性组分易烧结和流失而造成失活，并且贵金属价格昂贵，不适于大规模工业化生产。与贵金属催化剂相比，非贵金属催化剂因具有良好的催化活性和稳定性，并且价格低廉。然而，在反应温度过高时，非贵金属催化剂表面易积炭以及金属颗粒易团聚失活等缺点。因此，开发一种天然气水蒸气重整制氢的长寿命高效率的催化剂就具有较高的应用价值。
发明内容
本发明为解决催化剂金属颗粒易团聚失活，以及抗积炭和耐高温能力差的问题。本发明提供了一种包覆Ni-In@SiO2-Al2O3的中空介孔纳米催化剂及其制备方法，该催化剂用于甲烷水蒸汽重整制氢反应，能够大大提高催化剂的反应活性，同时使得催化剂的抗积炭和耐高温能力均得到了大幅的提高。
本发明提供一种包覆Ni-In@SiO2-Al2O3的中空介孔纳米催化剂，所述催化剂由Ni、Si、Al、O、In元素组成，Ni-In纳米颗粒以无定形状态存在于载体SiO2内部，所述载体SiO2外含有包覆层Al2O3作为催化剂的壳体。
作为进一步的优选，所述催化剂中Ni和In两种元素的摩尔比为Ni：In＝1:(0～2)。
作为进一步的优选，所述载体SiO2与包覆层Al2O3的质量比为SiO2:Al2O3＝(0.5～15):(70～150)。
作为进一步的优选，所述催化剂的比表面积400m2/g～700m2/g，孔容0.5cm3/g～1.5cm3/g，孔径5nm～20nm。
作为进一步的优选，一种包覆Ni-In@SiO2-Al2O3的中空介孔纳米催化剂的制备方法，包括如下步骤：
步骤S1：将Al2O3载体在马弗炉中300℃～500℃下加热3h～6h后降至室温待用；
步骤S2：将高分子有机物聚乙烯亚胺PEI和表面活性剂CTAB混合于去离子水中，搅拌5～10分钟，用氢氧化钠和硝酸的水溶液调节pH至4，得到第一混合溶液；
步骤S3：将镍盐和铟盐混于一定量的去离子水中，完全溶解后加入步骤S2中得到的第一混合溶液，磁力搅拌约10h～12h，形成第二混合溶液；
步骤S4：在步骤S3形成的第二混合溶液加入硅源，搅拌至有白色的絮状物出现，静置处理后，将所述第二混合液移至离心管，用去离子水和乙醇分别离心洗涤3～5次，用滴管吸出上层溶液，将离心后的固体放入40℃～80℃的烘箱烘干8h～10h；
步骤S5：将步骤S4得到的固体粉末放入马弗炉在空气气氛下焙烧，以5℃/min～10℃/min升温至500℃～700℃，再恒温3h～5h，再将焙烧完的固体粉末放入陶瓷方舟在500℃～700℃下氢气还原3h～5h；
步骤S6：将步骤S5得到的固体粉末与步骤S1得到的Al2O3载体混合，加入去离子水制成湿物料，将所述湿物料加入挤条机中挤出成型后得到中空介孔纳米催化剂。
作为进一步的优选，所述步骤S3中的镍盐为Ni(NO3)2·6H2O，铟盐为In(NO3)3·4H2O。
作为进一步的优选，所述步骤S3中的镍盐和铟盐的摩尔比为1:(0～2)。
作为进一步的优选，所述步骤S4中的硅源为正硅酸四甲酯或正硅酸四乙酯。
作为进一步的优选，将所述包覆Ni-In@SiO2-Al2O3的中空介孔纳米催化剂用于甲烷水蒸气重整制氢反应。
本发明的技术方案具有如下优点或有益效果：
(1)本发明在传统的Ni基催化剂的基础上添加了In金属，并通过一种独特的合成方法合成了Ni-In@SiO2-Al2O3中空介孔纳米催化剂。这种催化剂具有独特的中空二氧化硅壳结构，通过限域效应能够很好的保护内部的Ni-In金属颗粒防止其在高温还原中团聚失活，使得Ni-In纳米颗粒能够保持高度的分散性，且壳层上丰富的孔结构也为反应提供了优异的传质通道，大大提高了催化剂的反应活性。
(2)本发明由于In金属的添加，使得催化剂的抗积炭和耐高温能力均得到了大幅的提高。
(3)本发明中的催化剂的催化性能优越，在甲烷水蒸气重整制氢反应中原料气甲烷的转化率最高可达97.5％，合成气中氢气选择性最高可达95.2％。
附图说明
图1是本发明的实施例1制备的催化剂Ni-In@SiO2的TEM谱图；
图2是本发明的实施例1制备的催化剂Ni-In@SiO2的XRD谱图。
具体实施方式
下面对本发明的具体实施方式作进一步说明。在此需要说明的是，对于这些实施方式的说明用于帮助理解本发明，但并不构成对本发明的限定。此外，下面所描述的本发明各个实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互组合。
下述实施例中的实验方法，如无特殊说明，均为常规方法，下述实施例中所用的试验材料，如无特殊说明，均为可通过常规的商业途径购买得到的。
实施例1：
A.先将1.5mL浓度为0.1M聚乙烯亚胺(PEI)和十六烷基三甲基溴化铵(CTAB)水溶液混合于36g的去离子水中，搅拌5分钟，用氢氧化钠和硝酸的水溶液调节溶液的pH至4左右，再向其中分别加入1.5mL浓度为0.1M的Ni(NO3)2·6H2O和In(NO3)3·4H2O的水溶液，继续稳定pH在4左右，磁力搅拌约12h。在上述搅拌后的溶液中加入1.2mL的硅酸四乙酯，搅拌2天至烧杯中有大量白色的絮状物出现。
B.将上述溶液静置12h后，将混合液移至离心管，用去离子水和乙醇分别离心洗涤3～5次，用滴管吸出上层溶液，并将离心后的固体放入60℃的烘箱烘干10h，再将烘干后得到的固体粉末放入马弗炉在空气气氛下焙烧，以10℃/min升温至500℃，再恒温3h，最后将焙烧完得到的固体粉末放入陶瓷方舟在500℃下氢气还原3h，得到Ni1-In1@SiO2催化剂。
C.将上述还原后的催化剂研磨成固体粉末，再与在马弗炉中500℃焙烧后的Al2O3载体按1：100的比例混合，加入去离子水，再将湿物料加入挤条机中挤出成型，得到Ni1-In1@SiO2-Al2O3催化剂，编号为1#。
实施例2：
A.先将1.5mL浓度为0.1M聚乙烯亚胺(PEI)和十六烷基三甲基溴化铵(CTAB)水溶液混合于36g的去离子水中，搅拌5分钟，用氢氧化钠和硝酸的水溶液调节溶液的pH至4左右，再向其中分别加入1.5mL浓度为0.1M的Ni(NO3)2·6H2O的水溶液，继续稳定pH在4左右，磁力搅拌约12h。在上述搅拌后的溶液中加入1.2mL的硅酸四乙酯，搅拌2天至烧杯中有大量白色的絮状物出现。
B.将上述溶液静置12h后，将混合液移至离心管，用去离子水和乙醇分别离心洗涤3～5次，用滴管吸出上层溶液，并将离心后的固体放入60℃的烘箱烘干10h，再将烘干后得到的固体粉末放入马弗炉在空气气氛下焙烧，以10℃/min升温至500℃，再恒温3h，最后将焙烧完得到的固体粉末放入陶瓷方舟在500℃下氢气还原3h，得到Ni@SiO2催化剂。
C.将上述还原后的催化剂研磨成固体粉末，再与在马弗炉中500℃焙烧后的Al2O3载体按1：100的比例混合，加入去离子水，再将湿物料加入挤条机中挤出成型，得到Ni@SiO2-Al2O3催化剂，编号为2#。
实施例3：
A.先将1.5mL浓度为0.1M聚乙烯亚胺(PEI)和十六烷基三甲基溴化铵(CTAB)水溶液混合于36g的去离子水中，搅拌5分钟，用氢氧化钠和硝酸的水溶液调节溶液的pH至4左右，再向其中分加入1.5mL和0.75mL浓度为0.1M的Ni(NO3)2·6H2O和In(NO3)3·4H2O的水溶液，继续稳定pH在4左右，磁力搅拌约12h。在上述搅拌后的溶液中加入1.2mL的硅酸四乙酯，搅拌2天至烧杯中有大量白色的絮状物出现。
B.将上述溶液静置12h后，将混合液移至离心管，用去离子水和乙醇分别离心洗涤3～5次，用滴管吸出上层溶液，并将离心后的固体放入60℃的烘箱烘干10h，再将烘干后得到的固体粉末放入马弗炉在空气气氛下焙烧，以10℃/min升温至500℃，再恒温3h，最后将焙烧完得到的固体粉末放入陶瓷方舟在500℃下氢气还原3h，得到Ni1-In0.5@SiO2催化剂。
C.将上述还原后的催化剂研磨成固体粉末，再与在马弗炉中500℃焙烧后的Al2O3载体按1：100的比例混合，加入去离子水，再将湿物料加入挤条机中挤出成型，得到Ni1-In0.5@SiO2-Al2O3催化剂，编号为3#。
实施例4：
A.先将1.5mL浓度为0.1M聚乙烯亚胺(PEI)和十六烷基三甲基溴化铵(CTAB)水溶液混合于36g的去离子水中，搅拌5分钟，用氢氧化钠和硝酸的水溶液调节溶液的pH至4左右，再向其中分加入1.5mL浓度为0.1M的Ni(NO3)2·6H2O和In(NO3)3·4H2O的水溶液，继续稳定pH在4左右，磁力搅拌约12h。在上述搅拌后的溶液中加入1.2mL的硅酸四甲酯，搅拌2天至烧杯中有大量白色的絮状物出现。
B.将上述溶液静置12h后，将混合液移至离心管，用去离子水和乙醇分别离心洗涤3～5次，用滴管吸出上层溶液，并将离心后的固体放入60℃的烘箱烘干10h，再将烘干后得到的固体粉末放入马弗炉在空气气氛下焙烧，以10℃/min升温至500℃，再恒温3h，最后将焙烧完得到的固体粉末放入陶瓷方舟在500℃下氢气还原3h，得到Ni1-In1@SiO2催化剂。
C.将上述还原后的催化剂研磨成固体粉末，再与在马弗炉中500℃焙烧后的Al2O3载体按1：100的比例混合，加入去离子水，再将湿物料加入挤条机中挤出成型，得到Ni1-In1@SiO2-Al2O3催化剂，编号为4#。
将上述实施例中得到的各编号催化剂用于甲烷水重整反应，取200mg上述制备的催化剂将其装入石英反应管的恒温区。原料气中稀释气体为氦气，其与原料气中甲烷的体积比约为He：CH4＝15：2，其中原料水蒸气由蠕动泵进液体去离子水后汽化(液体水流速＝0.2ml/min)。反应条件为，反应温度为800℃；操作压力为1MPa；水气比为3。
各催化剂的催化性能如下表所示
| 催化剂 | CH4转化率(％) | H2选择性(％) |
| 1# | 97.5 | 95.2 |
| 2# | 90.1 | 90.6 |
| 3# | 93.6 | 91.6 |
| 4# | 95.2 | 92.8 |
图1为实施例1制备的Ni-In@SiO2催化剂的透射电镜(TEM)图。在电镜图中可以观察到明显的中空结构，Ni-In纳米颗粒均匀的分散在SiO2壳内，催化剂颗粒大小为18～20nm，其内部空腔大小约为15～18nm。
图2为实施例1制备的Ni-In@SiO2催化剂的X射线粉末衍射(XRD)谱图，在该谱图中可以清楚的观察到SiO2的特征峰，结合上述的透射电镜图，可以说明催化剂在上述制备条件下形成了中空的SiO2壳结构。此外，在XRD上没有观察到Ni-In纳米颗粒的明显特征峰，说明在SiO2壳内的活性组分Ni-In高度均匀分散。
本发明在传统的Ni基催化剂的基础上添加了In金属，并通过一种独特的合成方法合成了Ni-In@SiO2-Al2O3中空介孔纳米催化剂。这种催化剂具有独特的中空二氧化硅壳结构，通过限域效应能够很好的保护内部的Ni-In金属颗粒防止其在高温还原中团聚失活，使得Ni-In纳米颗粒能够保持高度的分散性。在甲烷水蒸气重整制氢反应中原料气甲烷的转化率最高可达97.5％，合成气中氢气选择性最高可达95.2％。
最后说明的是，以上仅为本发明较佳的实施例，并非因此限制本发明的实施方式及保护范围，对于本领域技术人员而言，应当能够意识到凡运用本发明说明书及图示内容所作出的等同替换和显而易见的变化所得到的方案，均应当包含在本发明的保护范围内。
Claims (8)
1.一种包覆Ni-In@SiO2-Al2O3的中空介孔纳米催化剂，其特征在于，催化剂由Ni、Si、Al、O、In元素组成，Ni-In纳米颗粒以无定形状态存在于载体SiO2内部，所述载体SiO2外含有包覆层Al2O3作为催化剂的壳体，所述催化剂中Ni和In两种元素的摩尔比为Ni：In =1:（0～2），其中In含量不为0。
2.如权利要求1所述的包覆Ni-In@SiO2-Al2O3的中空介孔纳米催化剂，其特征在于，所述载体SiO2与包覆层Al2O3的质量比为SiO2:Al2O3=（0.5～15）:（70～150）。
3.如权利要求1所述的包覆Ni-In@SiO2-Al2O3的中空介孔纳米催化剂，其特征在于，所述催化剂的比表面积400m2/g～700m2/g，孔容0.5cm3/g～1.5cm3/g，孔径5nm～20nm。
4.一种如权利要求1所述的包覆Ni-In@SiO2-Al2O3的中空介孔纳米催化剂的制备方法，其特征在于，包括如下步骤：
步骤S1：将Al2O3载体在马弗炉中300℃～500℃下加热3h～6h后降至室温待用；
步骤S2：将高分子有机物聚乙烯亚胺PEI和表面活性剂CTAB混合于去离子水中，搅拌5～10分钟，用氢氧化钠和硝酸的水溶液调节pH至4，得到第一混合溶液；
步骤S3：将镍盐和铟盐混于一定量的去离子水中，完全溶解后加入步骤S2中得到的第一混合溶液，磁力搅拌约10h～12h，形成第二混合溶液；
步骤S4：在步骤S3形成的第二混合溶液加入硅源，搅拌至有白色的絮状物出现，静置处理后，将所述第二混合液移至离心管，用去离子水和乙醇分别离心洗涤3～5次，用滴管吸出上层溶液，将离心后的固体放入40℃～80 ℃的烘箱烘干8h～10h；
步骤S5：将步骤S4得到的固体粉末放入马弗炉在空气气氛下焙烧，以5℃/min～10℃/min 升温至500℃～700℃，再恒温3h～5h，再将焙烧完的固体粉末放入陶瓷方舟在500℃～700℃下氢气还原3h～5h；
步骤S6：将步骤S5得到的固体粉末与步骤S1得到的Al2O3载体混合，加入去离子水制成湿物料，将所述湿物料加入挤条机中挤出成型后得到中空介孔纳米催化剂。
5.如权利要求4所述的包覆Ni-In@SiO2-Al2O3的中空介孔纳米催化剂的制备方法，其特征在于，所述步骤S3中的镍盐为Ni(NO3)2·6H2O，铟盐为In(NO3)3·4H2O。
6.如权利要求4所述的包覆Ni-In@SiO2-Al2O3的中空介孔纳米催化剂的制备方法，其特征在于，所述步骤S3中的镍盐和铟盐的摩尔比为1:（0～2），其中铟盐的含量不为0。
7.如权利要求4所述的包覆Ni-In@SiO2-Al2O3的中空介孔纳米催化剂的制备方法，其特征在于，所述步骤S4中的硅源为正硅酸四甲酯或正硅酸四乙酯。
8.一种如权利要求1所述的包覆Ni-In@SiO2-Al2O3的中空介孔纳米催化剂的应用，其特征在于，将所述包覆Ni-In@SiO2-Al2O3的中空介孔纳米催化剂用于甲烷水蒸气重整制氢反应。
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| CN109967081B (zh) * | 2019-04-01 | 2021-10-19 | 大连理工大学 | 一种高活性、抗积碳甲烷干气重整催化剂及其制备方法 |
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| CN107552054A (zh) * | 2017-08-18 | 2018-01-09 | 南昌大学 | 一种甲烷干气重整核壳结构镍基催化剂及制备方法 |
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