CN112264110A - Supported nickel metal catalyst for hydrogen production and preparation method and application thereof - Google Patents
Supported nickel metal catalyst for hydrogen production and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 239000002184 metal Substances 0.000 title claims abstract description 110
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 110
- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 239000001257 hydrogen Substances 0.000 title claims abstract description 60
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 60
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 45
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 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 90
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 88
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 88
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 26
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 19
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 19
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 47
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 42
- 239000004202 carbamide Substances 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 24
- 239000012266 salt solution Substances 0.000 claims description 20
- 238000011065 in-situ storage Methods 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 11
- 239000000969 carrier Substances 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 230000036961 partial effect Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000002407 reforming Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 15
- 230000008901 benefit Effects 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 description 28
- 238000001816 cooling Methods 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- 238000000629 steam reforming Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- 230000003100 immobilizing effect Effects 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 5
- 230000001976 improved effect Effects 0.000 description 5
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 229910018054 Ni-Cu Inorganic materials 0.000 description 3
- 229910003271 Ni-Fe Inorganic materials 0.000 description 3
- 229910018481 Ni—Cu Inorganic materials 0.000 description 3
- 229910018505 Ni—Mg Inorganic materials 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 3
- PZFKDUMHDHEBLD-UHFFFAOYSA-N oxo(oxonickeliooxy)nickel Chemical compound O=[Ni]O[Ni]=O PZFKDUMHDHEBLD-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910018062 Ni-M Inorganic materials 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- NFFYXVOHHLQALV-UHFFFAOYSA-N copper(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Cu].[Cu] NFFYXVOHHLQALV-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/78—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 alkali- or alkaline earth metals
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B3/34—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 by reaction of hydrocarbons with gasifying agents
- C01B3/38—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 by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—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 by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a supported nickel metal catalyst for hydrogen production and a preparation method and application thereof. The supported nickel metal catalyst for hydrogen productionThe preparation comprises the following components: al (Al)2O3Carrier, NiMAL-LDHs type hydrotalcite and NiMAL-LDO type hydrotalcite, wherein the NiMAL-LDHs type hydrotalcite and the NiMAL-LDO type hydrotalcite are loaded on the Al2O3At least a portion of the surface of the support; wherein M is selected from Mg2+、Ca2+、Fe2+、Cu2+At least one of (a). The supported nickel metal catalyst for hydrogen production has excellent hydrogen production reaction activity and stability and material structure stability, and has the advantages of simple preparation method, low cost and the like.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a supported nickel metal catalyst for hydrogen production and a preparation method and application thereof.
Background
Hydrogen is widely applied to chemical industry and oil refining industry as a clean and pollution-free secondary energy, and is helpful to solve the problems of shortage of fossil energy, increasingly serious environmental pollution and the like in China. The heat value of the hydrogen is high, only water is generated by combustion, and no carbon is discharged. The main component of natural gas is methane (CH)4) The highest carbon to hydrogen ratio among all hydrocarbons is considered the most suitable hydrogen production resource. Among the hydrogen production technologies using methane as raw material, the technology of methane steam reforming is the most mature, and H in the produced product gas2The ratio of/CO is also higher, and the method is suitable for preparing the synthesis gas with high hydrogen content.
The methane steam reforming is an endothermic reaction, and the reaction temperature is generally 700-900 ℃. The conversion rate of methane can be improved by increasing the reaction temperature, but the carbon deposition of the catalyst is easily caused, so that the energy consumption is increased, and the sintering of the catalyst is easily caused to be inactivated. Ni/Al2O3Is the most common nickel-based catalyst, and the applicable reaction conditions are as follows: the water-carbon ratio is 3-3.5, the reaction temperature is 820 ℃, the reaction pressure is 1.5-3.0 MPa, and the methane conversion rate can reach 90-92%. Ni/Al2O3The catalyst has good performance, but is easy to sinter or generate carbon deposition to be inactivated. Therefore, it is necessary to pass throughThese methods, such as addition of auxiliaries and selection of suitable carriers, improve the activity and stability of the catalyst.
The active component Ni exists in the catalyst in the form of NiO. To activate the catalyst, a high temperature reduction is required before use. The activity of the catalyst can be improved by appropriately increasing the amount of Ni supported and the degree of dispersion of Ni, but excessive Ni supporting causes aggregation of Ni, resulting in a decrease in the degree of dispersion thereof, thereby decreasing the activity of the catalyst.
Al preparation in Journal of Natural Gas Science and Engineering 2015,25:359-2O3Respectively obtaining alumina Hollow Sphere (HS) and alumina Nano Particle (NP) structures, and finding that Ni/Al2O3Nanoparticle (NP) catalysts have better catalytic activity due to better metal site distribution, Ni/Al2O3The Hollow Sphere (HS) type catalyst showed low activity. The core-shell structure catalyst shows excellent stability due to the physical confinement effect of the shell layer on the nano particles, the preparation method mainly comprises atomic layer deposition, microemulsion, ammonia evaporation, hydrothermal synthesis and the like, and the shell layer thickness and the pore size distribution can be accurately controlled by the methods. An Applied catalyst B, Enviromental2020,118921 adopts an AlN degradation method to synthesize stable Al on the surface of a Ni/AlN catalyst2O3Shell layer of Ni2+The Ni-based nano-particles are easy to enter AlN tetrahedrons to form strong interaction, generate chemical confinement effect and contribute to the dispersion and stabilization of Ni NPs. AlN also has a high thermal conductivity, which is beneficial to the heat transfer of the catalyst. The core-shell catalyst has both physical and chemical confinement, and can effectively improve the carbon deposition resistance and sintering resistance in the DRM process.
However, the existing supported nickel metal catalysts for hydrogen production are still to be further improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide a supported nickel metal catalyst for hydrogen production and a preparation method thereof. The supported nickel metal catalyst for hydrogen production has excellent hydrogen production reaction activity and stability and material structure stability, and has the advantages of simple preparation method, low cost and the like.
In one aspect of the invention, a supported nickel metal catalyst for hydrogen production is provided. According to an embodiment of the invention, the supported nickel metal catalyst for hydrogen production comprises: al (Al)2O3Carrier, NiMAL-LDHs type hydrotalcite and NiMAL-LDO type hydrotalcite, wherein the NiMAL-LDHs type hydrotalcite and the NiMAL-LDO type hydrotalcite are loaded on the Al2O3At least a portion of the surface of the support; wherein M is selected from Mg2+、Ca2+、Fe2+、Cu2+At least one of (a).
In the supported nickel metal catalyst for hydrogen production according to the above embodiment of the present invention, NiMAl-LDHs type hydrotalcite (nickel-M composite metal hydroxide type hydrotalcite) is supported on Al in an in-situ growth manner2O3Compared with the direct supported Ni, the nickel metal catalyst prepared by adopting the surface in-situ growth method has higher catalytic reaction activity and stability on at least part of the surface of the carrier, can reduce the use amount of Ni, and has obvious material cost advantage. Meanwhile, the auxiliary metal M can form an alloy with Ni, so that the removal of carbon from the surface of the catalyst is accelerated, and the formation of carbon deposition of the catalyst is effectively inhibited.
According to analysis and indication means such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), Scanning Electron Microscope (SEM) and the like, in the supported nickel metal catalyst for hydrogen production, NiMAL-LDO (Ni-M composite metal oxide type hydrotalcite) is mainly positioned in Al2O3And because of lattice positioning and space confinement effect of LDHs crystal, the catalytic active metal Ni, the catalytic assistant metal M and Al are mutually isolated and highly dispersed and are the same as Al2O3Firm combination; meanwhile, the NiMAL-LDHs is in Al2O3The surface mainly exists in an oriented growth form, namely a NiMAL-LDHs laminate and Al2O3Angle of surface>0 DEG and mostly close to 90 DEG (i.e., close to perpendicular Al)2O3Surface), therefore, from NiMAL-LDHs in Al2O3Surface of each otherThe staggered junctions and arrangements form near-net or local microchannel-like surface confinement spatial structures that are substantially maintained during the transformation of NiMAl-LDHs to NiMAl-LDO oriented structures. This indicates that the Ni metal catalyst has excellent material structure stability and is favorable for CH4And H2The raw material molecules such as O and the like are adsorbed in the limited space on the surface of the catalyst and fully participate in the reaction, and simultaneously can also be a product H2Molecules provide overflow space of surface local confinement, which provides guarantee for improving and promoting the reactivity and stability of the supported Ni metal catalyst.
In addition, the supported nickel metal catalyst for hydrogen production according to the above embodiment of the present invention may also have the following additional technical features:
according to some embodiments of the invention, the Al2O3The carrier is spherical Al2O3Clover type Al2O3Flaky Al2O3Columnar Al2O3At least one of (a). The inventor finds that Al2O3The structure of the carrier has influence on the performance of the catalyst, and spherical Al is adopted2O3Clover type Al2O3Flaky Al2O3Columnar Al2O3One or a mixture of more of the catalyst is used as a catalyst carrier, so that the hydrogen production reaction activity and stability of the catalyst and the structural stability of the material can be further improved.
According to some embodiments of the present invention, the content of Ni in the supported nickel metal catalyst for hydrogen production of the present invention may be 1.0 wt% to 70 wt%, such as 1.0 wt%, 2.0 wt%, 5.0 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, etc., based on the mass of the supported nickel metal catalyst for hydrogen production, as measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES).
In another aspect of the present invention, the present invention provides a method for preparing the supported nickel metal catalyst for hydrogen production of the above embodiment. According to an embodiment of the invention, the method comprises: benefit toBy applying urea solution to Al2O3Pre-activating the carrier to obtain the carrier containing activated Al2O3A urea solution of a carrier; preparation of Ni-containing alloy2+And M2+Mixed metal salt solution of (2), mixing the mixed metal salt solution with the activated Al-containing solution2O3Mixing urea solutions of carriers, and sequentially carrying out loading reaction to ensure that the NiMAL-LDHs type hydrotalcite is on Al2O3At least partial surface of the carrier grows in situ to obtain NiMAL-LDHs/Al2O3A material; mixing the NiMAL-LDHs/Al2O3The material is subjected to first roasting treatment in an oxidizing atmosphere to obtain NiMAL-LDO/Al2O3A material; mixing the NiMAL-LDO/Al2O3And carrying out second roasting treatment on the material in a reducing atmosphere to obtain the supported nickel metal catalyst for hydrogen production.
According to the method for preparing the supported nickel metal catalyst for hydrogen production, provided by the embodiment of the invention, Al is excited by using a cheap and easily-obtained weak alkaline urea solution based on a hydrothermal synthesis principle2O3Surface Al3+Source, realizing initial carrier Al2O3The surface is pre-activated, and the urea can be used as a precipitator to promote Al3+And Ni added subsequently2+And M2+The metal ion particles are deposited on Al2O3Surface immobilization is carried out to complete the surface in-situ synthesis of the NiMAL-LDHs type hydrotalcite and realize the synchronous dispersion and immobilization of the catalytic active metal Ni and the auxiliary metal M.
Due to the structural characteristics of materials such as LDHs and LDO derivatives thereof, catalytic active metal Ni, promoter metal M and Al atoms are highly isolated from each other and are in a uniform dispersion state under the influence of lattice positioning, space confinement and other effects, and the characteristics can be effectively maintained even after undergoing complex processes such as microstructure transformation, transformation and even partial collapse caused by the structural transformation from LDHs to LDO, and corresponding heat treatment such as drying, roasting and the like. This shows that in the prepared supported Ni metal catalyst, the active metal Ni and the auxiliary metal M are in Al2O3Surface migration, accumulation and evenThe phenomena of falling off, loss and the like are obviously inhibited; meanwhile, LDOs and derivatives thereof are staggered to form local microscopic domain-limited space and channel which can be CH4And H2Adsorption of raw material molecules such as O and product molecule H2The surface overflow provides important microstructural space support and guarantee. In addition, NiMAL-LDHs is in Al2O3The in-situ growth of the surface and the subsequent structural conversion to NiMAL-LDO can realize Al2O3The improvement and regulation of physical texture and surface physicochemical property; the catalyst is beneficial to the dispersion and isolation of the catalytic active metal Ni and the auxiliary metal M, the usage amount of the catalyst can be greatly reduced, and the material cost control is facilitated. Benefit from the carrier Al2O3The in-situ growth process of the surface NiMAl-LDHs and the introduction process of the active metal Ni and the auxiliary metal M are synchronized, in the obtained supported Ni catalyst, the active metal Ni particles have the characteristics of small particle size, narrow distribution, obvious inhibition on the formation of large particle size particles and the like, and the immobilization stability of the supported Ni catalyst is obviously improved.
In addition, the method for preparing the supported nickel metal catalyst for hydrogen production according to the above embodiment of the present invention may further have the following additional technical features:
according to some embodiments of the present invention, the concentration of the urea solution may be 0.05-4.0 mol/L, such as 0.05mol/L, 0.1mol/L, 0.5mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, etc. By controlling the concentration of the urea solution within the above range, the alkalinity is suitable for Al2O3The activating effect of the carrier is better.
According to some embodiments of the invention, the Al is2O3The particle size of the carrier may be 10 to 100 mesh, for example, 10 mesh, 20 mesh, 30 mesh, 50 mesh, 60 mesh, 80 mesh, 90 mesh, 100 mesh, and the like. Thus, Al2O3The carrier has better loading effect on NiMAL-LDHs type hydrotalcite.
According to some embodiments of the invention, the urea solution is mixed with Al2O3The liquid-solid ratio of the carrier is 100mL: 0.25-5.0 g, namely, 0.25-5.0 g of Al is added into each 100mL of urea solution2O3And (3) a carrier. By controlling the urea solution and Al2O3The liquid-solid ratio of the carrier is in the range, which is further beneficial to the Al of the urea solution2O3The activation of the carrier improves the activity and stability of the catalyst.
According to some embodiments of the invention, the pre-activation comprises: mixing urea solution with Al2O3Mixing carriers, performing microwave ultrasonic treatment at 20-60 deg.C (such as 20 deg.C, 30 deg.C, 40 deg.C, 50 deg.C, 60 deg.C) for 5-30 min (such as 5min, 10min, 15min, 20min, 25min, 30min, etc.), placing the obtained material in an autogenous pressure kettle, and standing at 70-150 deg.C (such as 70 deg.C, 80 deg.C, 100 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C, etc.) for 12-48 h (such as 12h, 18h, 24h, 30h, 36h, 48h, etc.) to obtain a mixture containing activated Al2O3Urea solution of the carrier.
According to some embodiments of the invention, Ni is in the mixed metal salt solution described above2+And M2+The molar ratio of (1) to (10-1000): 1, for example, 10:1, 20:1, 50:1, 80:1, 100:1, 200:1, 300:1, 400:1, 600:1, 800:1, 1000:1, etc. By controlling Ni in mixed metal salt solution2+And M2+The molar ratio of the active metal Ni to the auxiliary metal M in the prepared catalyst is in the range, the ratio of the active metal Ni to the auxiliary metal M in the prepared catalyst is proper, and the activity and the stability of the catalyst are better.
According to some embodiments of the invention, Ni is in the mixed metal salt solution described above2+And M2+The concentration of (b) is 0.001 to 0.5mol/L, for example, 0.001mol/L, 0.005mol/L, 0.01mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, etc. Specifically, nickel salt, M salt and mixed metal salt solution can be supplemented into the reaction system according to the actual needs in the reaction according to the reaction progress so as to maintain Ni in the reaction system2+And M2+Is in the above range.
According to some embodiments of the invention, the above-described load reaction comprises: mixing a mixed metal salt solution with a solution containing activated Al2O3Mixing urea solution of carrier, and performing microwave ultrasonic treatment at 20-60 deg.C (such as 20 deg.C, 30 deg.C, 40 deg.C, 50 deg.C, 60 deg.C) for 5-30 min (such as 5 deg.C)min, 10min, 15min, 20min, 25min, 30min, etc.); then placing the obtained material in an autogenous pressure kettle, standing for 12-48 h (such as 12h, 18h, 24h, 30h, 36h, 48h and the like) at 70-150 ℃ (such as 70 ℃, 80 ℃, 100 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ and the like) to obtain the NiMAL-LDHs/Al2O3A material. Under the above reaction conditions, Al may be added2O3The in-situ growth of NiAl-LDHs is realized on the surface of the carrier, and simultaneously, the auxiliary metal M can be synchronously introduced in the in-situ growth process of the NiAl-LDHs, so that Al is added2O3The in-situ growth of NiMAL-LDHs is realized on the surface of the carrier.
According to some embodiments of the present invention, the first baking treatment is performed at 300 to 500 ℃ for 6 to 12 hours. Specifically, the roasting temperature can be 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃ and the like, and the roasting time can be 6h, 7h, 8h, 9h, 10h, 11h, 12h and the like. Under the roasting condition, at least part of NiMAl-LDHs in the material is converted into NiMAl-LDO, and the surface confinement space structure of LDHs can be basically maintained in the conversion process, which not only shows that the Ni metal catalyst has excellent material structure stability, but also is beneficial to CH4And H2The raw material molecules such as O and the like are adsorbed in the limited space on the surface of the catalyst and fully participate in the reaction, and simultaneously can also be a product H2The molecule provides a surface local confinement overflow space, which provides guarantee for improving and promoting the reactivity and stability of the supported Ni metal catalyst
According to some embodiments of the invention, the oxidizing atmosphere may be an air atmosphere.
According to some embodiments of the present invention, the second baking treatment is performed at 300 to 800 ℃ for 2 to 12 hours. Specifically, the roasting temperature can be 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃ and the like, and the roasting time can be 2h, 4h, 6h, 8h, 10h, 12h and the like. The second calcination treatment under the above conditions can effectively reduce nickel in the catalyst for application in the hydrogen production reaction.
According to some embodiments of the invention, the reducing atmosphere may be H2An atmosphere.
In a further aspect of the invention, the invention also provides the application of the supported nickel metal catalyst for hydrogen production in the hydrogen production reaction by reforming methane steam. As mentioned above, the catalyst has the advantages of excellent hydrogen production reaction activity and stability, material structure stability, simple preparation method, low cost and the like, and can significantly improve performance parameters such as methane conversion rate, hydrogen selectivity and the like in the reaction when being applied to the hydrogen production reaction by methane steam reforming.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
For ease of understanding, the method of preparing the foregoing supported nickel metal catalyst for hydrogen production according to specific embodiments of the present invention is described in detail below. According to an embodiment of the invention, the method comprises:
(1)Al2O3pre-activation: firstly, weighing a certain amount of urea to prepare a urea solution, wherein the concentration of the urea is 0.05-4.0 mol/L; then, Al with a particle size of 10 to 100 mesh is added2O3Putting the mixture into the urea solution to be treated,wherein, Al2O3The addition amount is 0.25-5.0 g per 100mL of urea solution; then, fully stirring and mixing under the microwave ultrasonic condition, and treating for 5-30 min at 20-60 ℃; finally, placing the mixture into an autogenous pressure kettle, standing the mixture for 12 to 48 hours at the temperature of between 70 and 150 ℃, and naturally cooling the mixture to room temperature; wherein, Al2O3The shape of the utility model is one or a mixture of a plurality of spherical, clover, sheet and columnar shapes;
(2) NiMAL-LDHs in Al2O3Surface in-situ growth: firstly, weighing a certain amount of soluble divalent metal salt of catalytic active metal Ni and auxiliary metal M, and fully dissolving the soluble divalent metal salt in deionized water to prepare Ni2+And M2+Mixed with a metal salt solution of (2), wherein Ni2+:M2+10:1 to 1000:1 (molar ratio); then, the mixed metal salt solution is added into the mixed solution system prepared in the step (1), and Ni is added into the mixed solution system2+And M2+The respective concentration is kept between 0.001mol/L and 0.5 mol/L; then, fully stirring and mixing under the microwave ultrasonic condition, and treating for 5-30 min at 20-60 ℃; finally, placing the mixture into an autogenous pressure kettle again, standing the mixture for 12 to 48 hours at the temperature of between 70 and 150 ℃, and naturally cooling the mixture to room temperature; after being filtered and washed by deionized water, the NiMAL-LDHs is realized in Al2O3The surface grows in situ to obtain NiMAL-LDHs/Al2O3(ii) a Wherein M is selected from Mg2+、Ca2+、Fe2+、Cu2+At least one of;
(3) preparation of supported Ni metal catalyst: the NiMAL-LDHs/Al obtained in the step (2)2O3Roasting for 6-12 hours at the roasting temperature of 300-500 ℃ in the air atmosphere, and then naturally cooling to room temperature to obtain the NiMAL-LDO/Al2O3(ii) a Finally, in H2And (3) carrying out reduction treatment for 2-12 h at 300-800 ℃ in the atmosphere to finish the preparation of the supported Ni metal catalyst.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
(1)Al2O3Pre-activation: firstly, weighing a certain amount of urea to prepare a urea solution, wherein the concentration of the urea is 0.5 mol/L; then, Al having a particle size of 20 mesh2O3Put into the urea solution, wherein Al2O3The addition amount is 2g per 100mL of urea solution; then, fully stirring and mixing under the microwave ultrasonic condition, and treating for 15min at 35 ℃; finally, placing the mixture into an autogenous pressure kettle, standing the mixture for 48 hours at the temperature of 80 ℃, and naturally cooling the mixture to room temperature;
(2) NiFeAl-LDHs in Al2O3Surface in-situ growth: firstly, weighing a certain amount of soluble divalent metal salt of catalytic active metal Ni and auxiliary agent metal Fe, and fully dissolving the soluble divalent metal salt in deionized water to prepare Ni2+And Fe2+Mixed with a metal salt solution of (2), wherein Ni2+:Fe2+100:1 (molar ratio); then, the mixed metal salt solution is added into the mixed solution system prepared in the step (1), and Ni is added into the mixed solution system2+And Fe2+The respective concentrations are kept at 0.2 mol/L; then, fully stirring and mixing under the microwave ultrasonic condition, and treating for 15min at 35 ℃; finally, placing the mixture into an autogenous pressure kettle again, standing the mixture for 12 hours at the temperature of 100 ℃, and naturally cooling the mixture to the room temperature; after being filtered and washed by deionized water, the NiFeAl-LDHs is realized in Al2O3The surface grows in situ to obtain NiFeAl-LDHs/Al2O3；
(3) Preparation of supported Ni metal catalyst: the NiFeAl-LDHs/Al obtained in the step (2) is added2O3Roasting for 10 hours at the roasting temperature of 350 ℃ in the air atmosphere, and then naturally cooling to room temperature to obtain the NiFeAl-LDO/Al2O3(ii) a Finally, in H2And (3) carrying out reduction treatment for 3h at 600 ℃ in the atmosphere to finish the preparation of the supported Ni metal catalyst.
The prepared load type Ni metal catalyst (NiFeAl-LDO/Al)2O3) Measured by ICP-AES, the Ni content was 12%, reduced with hydrogen and used for steam reforming of methaneIn the first hydrogen production process, the methane conversion rate is 90% and the hydrogen selectivity is 90%. With Al2O3Supported Ni metal catalyst (Ni-Fe/Al) prepared by directly immobilizing Ni and Fe2O3) And Al2O3Supported Ni metal catalyst (Ni/Al) prepared by directly immobilizing Ni2O3) For reference, when the catalyst was used in the hydrogen production reaction of steam reforming of methane under the same Ni content and reaction conditions, the methane conversion rate was 85% (Ni-Fe/Al), respectively2O3) And 75% (Ni/Al)2O3) The hydrogen selectivity was 83% (Ni-Fe/Al)2O3) And 76% (Ni/Al)2O3)。
Example 2
(1)Al2O3Pre-activation: firstly, weighing a certain amount of urea to prepare a urea solution, wherein the concentration of the urea is 1 mol/L; then, Al having a particle size of 40 mesh2O3Put into the urea solution, wherein Al2O3The addition amount is 2.5g per 100mL of urea solution; then, fully stirring and mixing under the microwave ultrasonic condition, and treating for 20min at 25 ℃; finally, placing the mixture into an autogenous pressure kettle, standing the mixture for 24 hours at the temperature of 100 ℃, and naturally cooling the mixture to room temperature;
(2) NiMgAl-LDHs in Al2O3Surface in-situ growth: firstly, weighing a certain amount of soluble divalent metal salt of catalytic active metal Ni and auxiliary agent metal Mg, and fully dissolving the soluble divalent metal salt in deionized water to prepare Ni2+And Fe2+Mixed with a metal salt solution of (2), wherein Ni2+:Mg2+10:1 (molar ratio); then, the mixed metal salt solution is added into the mixed solution system prepared in the step (1), and Ni is added into the mixed solution system2+And Mg2+The respective concentrations are kept at 0.2 mol/L; then, fully stirring and mixing under the microwave ultrasonic condition, and treating for 20min at 25 ℃; finally, placing the mixture into an autogenous pressure kettle again, standing the mixture for 12 hours at the temperature of 80 ℃, and naturally cooling the mixture to the room temperature; after being filtered and washed by deionized water, the NiMgAl-LDHs in Al is realized2O3The surface grows in situ to obtain NiMgAl-LDHs/Al2O3；
(3) Preparation of supported Ni metal catalyst: the NiMgAl-LDHs/Al obtained in the step (2)2O3Roasting for 6 hours at the roasting temperature of 400 ℃ in the air atmosphere, and then naturally cooling to room temperature to obtain the NiMgAl-LDO/Al2O3(ii) a Finally, in H2And (3) carrying out reduction treatment for 4h at 500 ℃ in the atmosphere to finish the preparation of the supported Ni metal catalyst.
The prepared supported Ni metal catalyst (NiMgAl-LDO/Al)2O3) The content of Ni is 12% by ICP-AES, when the Ni is reduced by hydrogen and used in the hydrogen production reaction process of methane steam reforming, the conversion rate of methane is 91%, and the selectivity of hydrogen is 91%. With Al2O3Supported Ni metal catalyst (Ni-Mg/Al) prepared by directly immobilizing Ni and Mg2O3) And Al2O3Supported Ni metal catalyst (Ni/Al) prepared by directly immobilizing Ni2O3) For reference, when the catalyst was used in the hydrogen production reaction of steam reforming of methane under the same Ni content and reaction conditions, the methane conversion rate was 86% (Ni-Mg/Al), respectively2O3) And 75% (Ni/Al)2O3) The hydrogen selectivity was 84% (Ni-Mg/Al)2O3) And 76% (Ni/Al)2O3)。
Example 3
(1)Al2O3Pre-activation: firstly, weighing a certain amount of urea to prepare a urea solution, wherein the concentration of the urea is 3 mol/L; then, Al having a particle size of 60 mesh was added2O3Put into the urea solution, wherein Al2O3The addition amount is 4g per 100mL of urea solution; then, fully stirring and mixing under the microwave ultrasonic condition, and treating for 10min at 45 ℃; finally, placing the mixture into an autogenous pressure kettle, standing the mixture for 15 hours at the temperature of 120 ℃, and naturally cooling the mixture to room temperature;
(2) NiCuAl-LDHs in Al2O3Surface in-situ growth: firstly, weighing a certain amount of soluble divalent metal salt of catalytic active metal Ni and auxiliary agent metal Cu, and fully dissolving the soluble divalent metal salt in deionized water to prepareProduction of Ni2+And Cu2+Mixed with a metal salt solution of (2), wherein Ni2+:Cu2+500:1 (molar ratio); then, the mixed metal salt solution is added into the mixed solution system prepared in the step (1), and Ni is added into the mixed solution system2+And Mg2+The concentration of each is kept at 0.25 mol/L; then, fully stirring and mixing under the microwave ultrasonic condition, and treating for 5min at 40 ℃; finally, placing the mixture into an autogenous pressure kettle again, standing the mixture for 12 hours at the temperature of 120 ℃, and naturally cooling the mixture to the room temperature; after being filtered and washed by deionized water, the NiCuAl-LDHs is realized in Al2O3The surface grows in situ to obtain NiCuAl-LDHs/Al2O3；
(3) Preparation of supported Ni metal catalyst: NiCuAl-LDHs/Al obtained in the step (2)2O3Roasting for 8 hours at the roasting temperature of 400 ℃ in the air atmosphere, and then naturally cooling to room temperature to obtain NiCuAl-LDO/Al2O3(ii) a Finally, in H2And (3) carrying out reduction treatment for 8h at 350 ℃ in the atmosphere to finish the preparation of the supported Ni metal catalyst.
The supported Ni metal catalyst (NiMgCu-LDO/Al) prepared above2O3) The content of Ni is 15% by ICP-AES, when the Ni is reduced by hydrogen and used in the hydrogen production reaction process of methane steam reforming, the conversion rate of methane is 92%, and the selectivity of hydrogen is 91%. With Al2O3Supported Ni metal catalyst (Ni-Cu/Al) prepared by directly immobilizing Ni and Cu2O3) And Al2O3Supported Ni metal catalyst (Ni/Al) prepared by directly immobilizing Ni2O3) For reference, when the catalyst was used in the hydrogen production reaction of steam reforming of methane under the same Ni content and reaction conditions, the methane conversion rate was 87% (Ni-Cu/Al), respectively2O3) And 75% (Ni/Al)2O3) The hydrogen selectivity was 87% (Ni-Cu/Al)2O3) And 76% (Ni/Al)2O3)。
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A supported nickel metal catalyst for hydrogen production, comprising:
Al2O3a carrier;
NiMAl-LDHs type hydrotalcite and NiMAl-LDO type hydrotalcite, wherein the NiMAl-LDHs type hydrotalcite and the NiMAl-LDO type hydrotalcite are loaded on the Al2O3At least a portion of the surface of the support; wherein M is selected from Mg2+、Ca2+、Fe2+、Cu2+At least one of (a).
2. The supported nickel metal catalyst for hydrogen production as claimed in claim 1, wherein the Al is present in the nickel metal catalyst2O3The carrier is spherical Al2O3Clover type Al2O3Flaky Al2O3Columnar Al2O3At least one of (a).
3. The supported nickel metal catalyst for hydrogen production as claimed in claim 1, wherein the Ni content is 1.0 wt% to 70 wt% of the mass of the supported nickel metal catalyst for hydrogen production.
4. A method for preparing the supported nickel metal catalyst for hydrogen production as described in any one of claims 1 to 3, comprising:
by using urea solution to Al2O3Pre-activating the carrier to obtain the carrier containing activated Al2O3A urea solution of a carrier;
preparation of Ni-containing alloy2+And M2+Mixed metal salt solution of (2), mixing the mixed metal salt solution with the activated Al-containing solution2O3Mixing urea solutions of carriers, and sequentially carrying out loading reaction to ensure that the NiMAL-LDHs type hydrotalcite is on Al2O3At least partial surface of the carrier grows in situ to obtain NiMAL-LDHs/Al2O3A material;
mixing the NiMAL-LDHs/Al2O3The material is subjected to first roasting treatment in an oxidizing atmosphere to obtain NiMAL-LDO/Al2O3A material;
mixing the NiMAL-LDO/Al2O3And carrying out second roasting treatment on the material in a reducing atmosphere to obtain the supported nickel metal catalyst for hydrogen production.
5. The method according to claim 4, wherein the concentration of the urea solution is 0.05-4.0 mol/L;
optionally, the Al2O3The particle size of the carrier is 10-100 meshes;
optionally, the urea solution is mixed with the Al2O3The liquid-solid ratio of the carrier is 100mL: 0.25-5.0 g.
6. The method of claim 4, wherein the pre-activating comprises: mixing the urea solution with the Al2O3Mixing carriers, carrying out microwave ultrasonic treatment for 5-30 min at 20-60 ℃, then placing the obtained material in an autogenous pressure kettle, and standing for 12-48 h at 70-150 ℃ so as to obtain the product containing the activationAl2O3Urea solution of the carrier.
7. The method of claim 4, wherein the mixed metal salt solution is Ni2+And M2+The molar ratio of (10-1000) to (1);
optionally, Ni in the mixed metal salt solution2+And M2+The concentration of (b) is 0.001 to 0.5 mol/L.
8. The method of claim 4, wherein the loading reaction comprises: mixing the mixed metal salt solution with the activated Al-containing solution2O3Mixing urea solutions of the carriers, and carrying out microwave ultrasonic treatment for 5-30 min at the temperature of 20-60 ℃; then placing the obtained material in an autogenous pressure kettle, and standing for 12-48 h at the temperature of 70-150 ℃ to obtain the NiMAL-LDHs/Al2O3A material.
9. The method according to claim 4, wherein the first roasting treatment is performed at 300 to 500 ℃ for 6 to 12 hours;
optionally, the oxidizing atmosphere is an air atmosphere;
optionally, the second roasting treatment is completed for 2-12 hours at the temperature of 300-800 ℃;
optionally, the reducing atmosphere is H2An atmosphere.
10. The supported nickel metal catalyst for hydrogen production as set forth in any one of claims 1 to 3 or the supported nickel metal catalyst for hydrogen production as set forth in any one of claims 4 to 9 is used in a hydrogen production reaction by reforming methane steam.
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