CN112547074A - 一种甲醇水蒸气重整制氢用催化剂、其制备方法及应用 - Google Patents
一种甲醇水蒸气重整制氢用催化剂、其制备方法及应用 Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 81
- 239000001257 hydrogen Substances 0.000 title claims abstract description 81
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 76
- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 238000001651 catalytic steam reforming of methanol Methods 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 19
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000007598 dipping method Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 7
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000005751 Copper oxide Substances 0.000 claims description 6
- 229910000431 copper oxide Inorganic materials 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 238000000629 steam reforming Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
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- 239000003345 natural gas Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- -1 cerium ions Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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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- B01J23/84—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 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
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Abstract
本发明属于催化剂技术领域,具体的涉及一种甲醇水蒸气重整制氢用催化剂、其制备方法及应用。所述甲醇水蒸气重整制氢用催化剂的制备方法,包括以下步骤:1)配置硝酸盐的水溶液至饱和,所述硝酸盐的水溶液中的金属离子由铜离子、锌离子和M离子组成;2)将氧化铝球浸渍于步骤1)所述硝酸盐的溶液中;3)将步骤2)浸渍后的氧化铝进行过滤、干燥、煅烧和冷却;4)共依次重复步骤2)和3)2‑5次,即得所述甲醇水蒸气重整制氢用催化剂。此外,本发明还提供了一种采用上述制备方法制备而成的甲醇水蒸气重整制氢用催化剂及其应用。上述催化剂具有比表面积大的优点,从而大大提高了催化效率,同时延长了催化剂的使用寿命。
Description
技术领域
本发明属于催化剂技术领域,具体涉及一种甲醇水蒸气重整制氢用催化剂、其制备方法及应用。
背景技术
能源的发展一直是人类社会文明进步的生命线,氢被称为“能源货币”,其热值仅次于核燃料,是汽油热值的三倍。氢是无毒的载能体,且燃烧后不产生温室气体和其它污染物,十分有利于节能减排,故被看作21世纪理想的洁净新能源。近年来,由于质子交换膜燃料电池技术的突破和不断发展,氢能源是化石能源向可再生能源过渡的重要桥梁之一。同时氢也是重要的化工原料,在加氢反应(如煤的液化和汽化、重油的重整、制药等)、金属材料加工制造等方面都大量使用。
目前,工业上大规模化石燃料制氢技术(如天然气、水煤气等制氢)己相当成熟,但反应条件苛刻,须在800℃左右进行,所采用的设备需要特殊材质,同时还要考虑转化用的蒸汽、氢气纯化等所需的热源等问题。另外,电解水制氢电耗约5-8kW·h/m3·H2,单位氢气成本更高。在精细化工和制药行业大量需求中小规模制氢,以上制氢方法经济性都较差。
近年来我国发展起来大量的甲醇裂解制氢装置,反应温度(200~300℃)相对温和、甲醇储存和运输方便、氢气中不含硫等特点。甲醇水蒸汽重整制氢的化学反应式为:CH3OH+H2O→CO2+3H2,与同等规模的天然气或轻油转化制氢装置相比,甲醇水蒸汽转化制氢的能耗仅是前者的50%。据测算,一套规模为1000m3/h的甲醇水蒸汽转化制氢装置的单位氢气成本不高于2元/m3·H2。并且甲醇原料易得、价格便宜,是排在合成氨、乙烯之后的第三大化工产品。随着我国经济高速发展,甲醇水蒸气重整制氢得到了快速推广,甲醇水蒸气重整制氢催化剂也快速扩大。
目前,国内的甲醇水蒸气重整制氢催化剂主要以Cu、Zn和Al催化剂为主,但是,铜基催化剂在水氛体系中易氧化,活性组分容易烧结、积炭、中毒等。甲醇水蒸汽重整制氢的副产物CO浓度较高(0.5-2%),不能满足质子交换膜燃料电池的要求(ppm级的CO能使燃料电池阳极Pt催化剂中毒)。为了满足质子交换膜燃料电池对氢燃料的要求,重整催化剂需具备更高的选择性。
发明内容
本发明的目的之一,是提供一种甲醇水蒸气重整制氢用催化剂的制备方法,以解决现有的催化剂催化效率不够高,造成生产效率低下的问题。
为了实现上述目的,本发明所采取的技术方案是:一种甲醇水蒸气重整制氢用催化剂的制备方法,包括以下步骤:
1)配置硝酸盐的水溶液至饱和,所述硝酸盐的水溶液中的金属离子由铜离子、锌离子和M离子组成;
2)将氧化铝球浸渍于步骤1)所述硝酸盐的溶液中;
3)将步骤2)浸渍后的氧化铝进行过滤、干燥、煅烧和冷却;
4)共依次重复步骤2)和3)2-5次,即得所述甲醇水蒸气重整制氢用催化剂。
本发明的甲醇水蒸气重整制氢用催化剂的制备方法的有益效果是:上述催化剂的制备方法,采用多次浸渍煅烧的方法,能够有效提高氧化铜和氧化锌在氧化铝载体表面的附着率,同时添加一定的M元素氧化物(即氧化物助剂),从而控制了其晶粒尺寸,提高铜离子和锌离子的氧化活性。
在上述技术方案的基础上,本发明还可以有如下进一步的具体选择或优化选择。
具体的,所述甲醇水蒸气重整制氢用催化剂以质量份数计,包括10-30份的氧化铜、5-20份的氧化锌、40-80份的氧化铝以及1-5份的M元素氧化物。其中,所述M元素氧化物选自氧化镁、氧化锰、氧化铈和氧化锆中的任意一种或两种以上的混合物。
具体的,在步骤2)中,所述浸渍的时间为10-30min。
具体的,在步骤3)中,所述过滤的孔径为0.5mm以下,所述干燥在真空下进行,真空度为-0.085,温度为60-100℃,时间为1-5小时;所述煅烧的温度为300-600℃,时间为4-10小时,所述冷却为冷却至室温。
具体的,所述氧化铝球的直径为0.5-2mm。
具体的,在步骤4)中,所述甲醇水蒸气重整制氢用催化剂还包括活化步骤,首先使用氮气置换空气,然后将所述的甲醇水蒸气重整制氢用催化剂升温至300℃,同时通入氢气,最后保温1-8小时。进一步的,所述氮气以压力为0.1-0.3Mpa,流量为0.1-3L/min的速度通入;所述升温的速率为5℃/min;所述氢气以压力为0.1-0.3Mpa,流量为0.1-3L/min的速度通入。上述活化步骤的添加,能够大大提高催化剂的催化活性。
需要说明的是,所述硝酸盐在高温煅烧下分解成金属氧化物。
本发明的目的之二,是提供一种甲醇水蒸气重整制氢用催化剂,其采用上述一种甲醇水蒸气重整制氢用催化剂制备方法制备而成。
本发明的甲醇水蒸气重整制氢用催化剂的有益效果是:氧化铝的作为载体既有一定的催化效果,而且具有比表面积大的优点,从而大大提高了催化效率,同时延长了催化剂的使用寿命。
本发明的目的之三,是提供上述甲醇水蒸气重整制氢用催化剂的制备方法制备得到的甲醇水蒸气重整制氢用催化剂在甲醇水蒸气重整制氢中的应用。
本发明的甲醇水蒸气重整制氢用催化剂的应用的有益效果是:上述催化剂制造成本低,制备方法简单方便,容易进行工业化大规模生产应用。
具体实施方式
为了更好地理解本发明,下面结合具体实施例进一步阐明本发明的内容,但本发明的内容不仅仅局限于下面的实施例。
实施例1:
根据本发明提供了一种甲醇水蒸气重整制氢用催化剂的制备方法制备所述甲醇水蒸气重整制氢用催化剂,具体的,包括以下步骤:
1)配置硝酸盐的水溶液至饱和,所述硝酸盐的水溶液中由铜离子、锌离子和镁离子组成;
2)将氧化铝球浸渍至步骤1)所述硝酸盐的溶液中20min,其中所述氧化铝球的直径为1mm;
3)将步骤2)所述浸渍后的氧化铝进行过滤、在真空下干燥、在400℃下煅烧4小时,随后冷却至室温;
4)依次重复步骤2)和3)5次,即得所述催化剂。所得催化剂成分以质量份数计,包括20份的氧化铜,10份的氧化锌和60份的氧化铝以及2份的氧化镁。
实施例2:
根据本发明提供了一种甲醇水蒸气重整制氢用催化剂的制备方法制备所述甲醇水蒸气重整制氢用催化剂,具体的,包括以下步骤:
1)配置硝酸盐的水溶液至饱和,所述硝酸盐的水溶液中由铜离子、锌离子、锰离子和铈离子组成;
2)将氧化铝球浸渍至步骤1)所述硝酸盐的溶液中30min,其中所述氧化铝球的直径为2mm;
3)将步骤2)所述浸渍后的氧化铝进行过滤、在真空下干燥、在600℃下煅烧6小时,随后冷却至室温;
4)依次重复步骤2)和3)2次,即得所述催化剂。所得催化剂成分以质量份数计,包括30份的氧化铜,5份的氧化锌和40份的氧化铝以及0.1份的氧化锰和0.5份氧化铈。
进一步的,所述催化剂进行活化处理,首先使用氮气置换空气,然后将所述的催化剂升温至300℃,同时通入氢气,最后保温5小时。其中,所述氮气以0.3Mpa的压力,流量为0.3L/min的速度通入,所述氢气以0.3Mpa的压力,流量为0.3L/min的速度通入,温度以5℃/分钟的速率升温。
实施例3:
根据本发明提供了一种甲醇水蒸气重整制氢用催化剂的制备方法制备所述甲醇水蒸气重整制氢用催化剂,具体的,包括以下步骤:
1)配置硝酸盐的水溶液至饱和,所述硝酸盐的水溶液中由铜离子、锌离子和镁离子和锆离子组成;
2)将氧化铝球浸渍至步骤1)所述硝酸盐的溶液中10min,其中所述氧化铝球的直径为0.5mm;
3)将步骤2)所述浸渍后的氧化铝进行过滤、在真空下干燥、在300℃下煅烧10小时,随后冷却至室温;
4)依次重复步骤2)和3)4次,即得所述催化剂。所得催化剂成分以质量份数计,包括10份的氧化铜,20份的氧化锌和40份的氧化铝以及2份的氧化镁和3份的氧化锆。
进一步的,所述催化剂进行活化处理,首先使用氮气置换空气,然后将所述的催化剂升温至300℃,同时通入氢气,最后保温2小时。其中,所述氮气以0.1Mpa的压力,流量为0.1L/min的速度通入,所述氢气以0.1Mpa的压力,流量为0.1L/min的速度通入,温度以5℃/分钟的速率升温。
实验例
分别将所实施例1-3所得的甲醇水蒸气重整制氢用催化剂与购自市售产品(江苏诺盟化工有限公司)的催化剂(对照例)进行甲醇裂解催化反应。其反应结果如下表1所示。
表1甲醇裂解催化反应结果
催化剂 | 甲醇的转化率(%) | 氢气含量(%) |
实施例1 | 83.3 | 76.7 |
实施例2 | 94.3 | 87.1 |
实施例3 | 96.7 | 91.5 |
对照例 | 56.4 | 62.4 |
由表1可知,本申请提供的甲醇水蒸气重整制氢用催化剂应用在甲醇裂解制氢的生产中,能够明显提高原料的转化率和目标产品氢气的气体浓度,因而具有更好的催化效果。进一步的,上述催化剂容易制备,且方法步骤简单,更加节省生产时间和人力成本。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种甲醇水蒸气重整制氢用催化剂的制备方法,其特征在于,包括以下步骤:
1)配置硝酸盐的水溶液至饱和,所述硝酸盐的水溶液中的金属离子由铜离子、锌离子和M离子组成;
2)将氧化铝球浸渍于步骤1)所述硝酸盐的溶液中;
3)将步骤2)浸渍后的氧化铝进行过滤、干燥、煅烧和冷却;
4)共重复步骤2)至3)2-5次,即得所述甲醇水蒸气重整制氢用催化剂。
2.根据权利要求1所述的甲醇水蒸气重整制氢用催化剂的制备方法,其特征在于:所述甲醇水蒸气重整制氢用催化剂以质量份数计,包括10-30份的氧化铜、5-20份的氧化锌、40-80份的氧化铝以及1-5份的M元素氧化物。
3.根据权利要求2所述的甲醇水蒸气重整制氢用催化剂的制备方法,其特征在于:所述M元素氧化物选自氧化镁、氧化锰、氧化铈和氧化锆中的任意一种或两种以上的混合物。
4.根据权利要求1所述的甲醇水蒸气重整制氢用催化剂的制备方法,其特征在于:在步骤2)中,所述浸渍的时间为10-30min。
5.根据权利要求1所述的甲醇水蒸气重整制氢用催化剂的制备方法,其特征在于:在步骤3)中,所述过滤的孔径为0.5mm以下;所述干燥在真空下进行,真空度为-0.085,温度为60-100℃,时间为1-5小时;所述煅烧的温度为300-600℃,时间为4-10小时;所述冷却为冷却至室温。
6.根据权利要求1所述的甲醇水蒸气重整制氢用催化剂的制备方法,其特征在于:在步骤2)中,所述氧化铝球的直径为0.5-2mm。
7.根据权利要求1-6任一项所述的甲醇水蒸气重整制氢用催化剂的制备方法,其特征在于:在步骤4)中,所述甲醇水蒸气重整制氢用催化剂还包括活化步骤,即首先使用氮气置换空气,然后将所述甲醇水蒸气重整制氢用催化剂升温至300℃,同时通入氢气,最后保温1-8小时。
8.根据权利要求7所述的甲醇水蒸气重整制氢用催化剂的制备方法,其特征在于:所述氮气以压力为0.1-0.3Mpa,流量为0.1-3L/min的速度通入;所述升温的速率为5℃/min;所述氢气以压力为0.1-0.3Mpa,流量为0.1-3L/min的速度通入。
9.权利要求1-8任一项所述的甲醇水蒸气重整制氢用催化剂的制备方法制备得到的甲醇水蒸气重整制氢用催化剂。
10.权利要求1-8任一项所述的甲醇水蒸气重整制氢用催化剂的制备方法制备得到的甲醇水蒸气重整制氢用催化剂在甲醇水蒸气重整制氢中的应用。
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