CN108940287B - Ni-based bimetallic nanocapsule catalyst and preparation and application thereof - Google Patents
Ni-based bimetallic nanocapsule catalyst and preparation and application thereof Download PDFInfo
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- CN108940287B CN108940287B CN201810712246.XA CN201810712246A CN108940287B CN 108940287 B CN108940287 B CN 108940287B CN 201810712246 A CN201810712246 A CN 201810712246A CN 108940287 B CN108940287 B CN 108940287B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 239000002088 nanocapsule Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000002775 capsule Substances 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 12
- 239000002028 Biomass Substances 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 238000006057 reforming reaction Methods 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000000149 penetrating effect Effects 0.000 claims abstract description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 3
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- FDCJDKXCCYFOCV-UHFFFAOYSA-N 1-hexadecoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC FDCJDKXCCYFOCV-UHFFFAOYSA-N 0.000 claims description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 230000003301 hydrolyzing effect Effects 0.000 claims description 9
- 229910018054 Ni-Cu Inorganic materials 0.000 claims description 8
- 229910018481 Ni—Cu Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 6
- 229910017709 Ni Co Inorganic materials 0.000 claims description 5
- 229910003267 Ni-Co Inorganic materials 0.000 claims description 5
- 229910003262 Ni‐Co Inorganic materials 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 3
- TXJGDUZLRLVYJU-UHFFFAOYSA-N nonan-4-yloxybenzene Chemical compound CCCCCC(CCC)OC1=CC=CC=C1 TXJGDUZLRLVYJU-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 43
- 230000000694 effects Effects 0.000 abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 230000008021 deposition Effects 0.000 abstract description 8
- 239000002923 metal particle Substances 0.000 abstract description 8
- 238000005245 sintering Methods 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 238000004873 anchoring Methods 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 238000007709 nanocrystallization Methods 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 50
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 48
- 239000007789 gas Substances 0.000 description 31
- 229910002092 carbon dioxide Inorganic materials 0.000 description 28
- 239000001569 carbon dioxide Substances 0.000 description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- 238000002156 mixing Methods 0.000 description 14
- 230000009467 reduction Effects 0.000 description 11
- 238000000576 coating method Methods 0.000 description 9
- 239000000693 micelle Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 239000006004 Quartz sand Substances 0.000 description 7
- 238000001833 catalytic reforming Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- CKQAOGOZKZJUGA-UHFFFAOYSA-N 1-nonyl-4-(4-nonylphenoxy)benzene Chemical compound C1=CC(CCCCCCCCC)=CC=C1OC1=CC=C(CCCCCCCCC)C=C1 CKQAOGOZKZJUGA-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
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- 230000000704 physical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
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- 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
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Abstract
The invention discloses a Ni-based bimetallic nanocapsule catalyst and preparation and application thereof, wherein the catalyst consists of a capsule shell layer and a metal core; the shell layer of the capsule is silicon oxide, and the metal core is bimetallic nickel-copper or nickel-cobalt particles; the total content of nickel and copper or nickel and cobalt in the nano capsule catalyst is 10-20 wt%, the particle size of nickel and copper or nickel and cobalt bimetallic particles is 1-4 nm, the capsule cavity is (6.5-7.5) nm x (15-60) nm, and the thickness of a capsule shell layer is 5.5 +/-3 nm; the nano-capsule catalyst has a two-stage pore channel structure, wherein pores with the diameter of 3-4 nm are from penetrating pore channels of a shell layer, and pores with the diameter of 12-15 nm are from a hollow cavity of a capsule. The catalyst has unique space confinement structure (high nanocrystallization of metal particles, anchoring of the metal particles in a shell layer, proper shell cavity space and steric hindrance of a capsule structure) and the synergistic effect of double metals, can effectively inhibit sintering of active components and formation of carbon deposition under high-temperature reaction, and has good activity and stability in the biomass gas reforming reaction.
Description
Technical Field
The invention relates to a catalyst with a nano-capsule structure, in particular to a Ni-based bimetallic nano-capsule catalyst, a preparation method thereof and application of the catalyst in biomass gas reforming reaction.
Background
The biomass gas mainly comes from the anaerobic degradation of biomass in crop straws, forest waste and industrial wastewater, and comprises the main components of methane (50-70%) and carbon dioxide (30-50%), wherein the components of the methane and the carbon dioxide are in proportion, so that the biomass gas can be used as a natural raw material for preparing synthesis gas by reforming methane and carbon dioxide, and further can be applied to the fields of hydrogen production, fuel cells or synthetic oil products and the like. However, the biomass gas composition is usually slightly more than carbon dioxide, and excessive methane is easy to promote the sintering of active metal of the catalyst and generate serious carbon deposition, so that the requirement on the catalyst is high.
The nickel-based catalyst is considered as a preferred catalyst for industrial application due to its excellent activity, low cost and abundant content. However, for most high temperature reactions, a prerequisite for industrial catalysts is that a higher metal content (>10 wt%) and smaller nanocrystalline grain size (<5nm) must be provided, but the fact is that in most cases Ni nanoparticles always tend to sinter and form carbon deposits with high metal content. Therefore, the main challenge in designing high stability industrial Ni-based catalysts is how to make high activity Ni nanoparticles stable under high loading and high temperature conditions.
In order to overcome the negative effects of Ni nano-particle sintering and carbon deposition on the activity and stability of the catalyst, on one hand, the Ni nano-particles can be subjected to bimetal synergistic modification, the electronic effect and the geometric effect of the catalyst are improved, multi-coordination active sites on the surfaces of the metal particles are effectively separated, and the formation of carbon deposition sites is inhibited; on the other hand, the porous oxide can be coated on the active metal to form core-shell structure modification, and metal sintering and carbon deposition are inhibited by coating metal sites. If the two methods are combined, the reaction activity and the long-period stability of the reforming catalyst are expected to be greatly improved. For example, Chinese patent medicineLi CN104998649A discloses a SiO2The preparation method of the @ NiCo core-shell structure catalyst has higher methane and carbon dioxide reforming catalytic efficiency. However, core-shell structured catalysts have insufficient active Ni sites for rapid diffusion and conversion of reactants due to limited active metal exposure (Ni particles are typically larger than 10nm, the larger the particle the less active surface is exposed) and dense shell thickness. In addition, the metal particles encapsulated in the shell cavity can move freely, resulting in poor metal-support interaction, which is not suitable for the reforming reaction process with high methane concentration.
Disclosure of Invention
The invention aims to provide a Ni-based bimetallic nanocapsule catalyst which has a synergistic effect of a space confinement structure and bimetal, simultaneously meets the requirements of higher metal content (>10 wt%) and smaller nanocrystalline grain size (<5nm), and can effectively inhibit sintering of active components and formation of carbon deposition under high-temperature reaction.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a Ni-based bimetallic nanocapsule catalyst consists of a capsule shell layer and a metal core; the shell layer of the capsule is silicon oxide, and the metal core is bimetallic nickel-copper or nickel-cobalt particles; the total content of nickel and copper or nickel and cobalt in the nano capsule catalyst is 10-20 wt%, the particle size of nickel and copper or nickel and cobalt bimetallic particles is 1-4 nm, the capsule cavity is (6.5-7.5) nm x (15-60) nm, and the thickness of a capsule shell layer is 5.6 +/-3 nm; the nano-capsule catalyst has a two-stage pore channel structure, wherein pores with the diameter of 3-4 nm are from penetrating pore channels of a shell layer, and pores with the diameter of 12-15 nm are from a hollow cavity of a capsule.
The catalyst has a unique synergistic effect of a space confinement structure (metal particles are highly nano-sized, the metal particles are anchored in a shell layer, a proper shell cavity reaction space and a capsule structure have steric hindrance) and bimetal, can effectively inhibit sintering of active components and formation of carbon deposition under a high-temperature reaction, and shows excellent activity and stability in a biomass gas reforming reaction.
The preparation method of the nano capsule catalyst comprises the following steps:
(1) weighing 10-50 g of surfactant in a container, adding cyclohexane to 100mL, heating at 40-60 ℃, and stirring;
(2) adding 5-10 mL of 1.5-2.0 mol/L Ni-Co salt mixed solution or Ni-Cu salt mixed solution, wherein the molar ratio of Ni-Co or Ni-Cu is 4-1: 1, stirring to mix uniformly, and adding 2-8 mL of hydrazine hydrate;
(3) after aging for 0.5-24 h, increasing the stirring speed, adding 15mL of mixed solution of concentrated ammonia water and deionized water, and then slowly adding 7.5-15 mL of TEOS;
(4) adding acetone after hydrolyzing for 1-48 h for demulsification, and centrifuging;
(5) drying the sample at 50-120 ℃ for 12-24 h, and calcining at 500-800 ℃ at a rate of 1-5 ℃/min in an air atmosphere. The total content of Ni-Cu (Co) in the obtained catalyst is 10-20 wt.%, the particle size of Ni-Cu (Co) bimetallic particles is 1-4 nm, the capsule cavity is (6.5-7.5) nm x (15-60) nm, and the shell thickness is 5.5 +/-3 nm.
The surfactant in the step (1) is one or two of polyoxyethylene (10) cetyl ether and polyethylene glycol mono-4-nonyl phenyl ether.
The Ni-Co salt mixed solution in the step (2) is a mixed solution of nickel nitrate and cobalt nitrate, a mixed solution of nickel chloride and cobalt chloride or a mixed solution of nickel acetylacetonate and cobalt acetylacetonate; the Ni-Cu salt mixed solution is a mixed solution of nickel nitrate and copper nitrate, a mixed solution of nickel chloride and copper chloride or a mixed solution of nickel acetylacetonate and copper acetylacetonate.
The hydrazine hydrate in the step (2) has multiple functions, and has the functions of a reducing agent, a coupling agent and a foaming agent.
And (4) the content of the concentrated ammonia water in the mixed solution in the step (3) is 1-3 mL.
The nanocapsule catalyst can be applied to biomass gas reforming reaction, the reaction is carried out in a plug flow fixed bed reactor, and the conditions of the reforming reaction are preferably as follows: the pressure is normal pressure, the reduction temperature is 650-750 ℃, the reaction temperature is 700-850 ℃, and the gas space velocity GHSV is 12-48 L.g-1·h-1Molar composition of biomass gasIs CH4:CO2:N2＝1.1～1.4:1:1～5。
The special capsule structure of the catalyst of the invention now has its unique principle of preparation (see fig. 1): 1) the micro sol system adopted by the invention has wide concentration range of an oil-water stable system and small micelle particles, and the particle size of Ni can be stably controlled to be 1-4 nm by adjusting preparation parameters; 2) the bimetallic auxiliary agents Cu and Co introduced by the invention not only can not destroy the micelle stability of a microemulsion system, but also can reduce the reduction electrode potential of Ni precursor salt and promote the rapid formation of metal cores in the micelle; 3) the slightly soluble colloid system adopted by the invention not only can realize monodispersed uniform coating of the oil phase relative to the water phase, but also can realize coating of the self-generated gas phase (derived from decomposition of the reduction coupling agent) in the oil phase relative to the micelle, and the reduction coupling agent N is reduced in the reduction process of the water phase nickel precursor in the self-assembly coating process of the material2H4Will generate a small amount of N2、NH3Or H2When the bubbles exist stably in the slightly soluble micelle system, the original spherical micelles are expanded to the columnar capsules orderly above the liquid level under the pushing of the directional acting force of the buoyancy of the bubbles, so that the growth process of the ordered capsule coating structure is realized.
Compared with the prior art, the invention has the following beneficial effects:
(1) the unique nanocapsule structure of the catalyst prepared by the invention can be used as a microreactor, so that enough space is provided for the reaction of reaction gas and active sites, and the monodisperse structural state avoids the mutual interference of the catalyst under high-temperature reaction;
(2) the Cu or Co metal introduced into the catalyst prepared by the invention can form alloy nano particles with Ni, so that the electronic effect and the geometric effect of the catalyst can be improved while the Ni metal sites are separated, the particle size of the metal particles is reduced, and the catalytic activity and the stability are improved;
(3) the content of active metal in the catalyst prepared by the method is 10-20 wt%, the average particle diameter is less than 4nm, so that the active site has a large exposed surface area, the conversion rate of methane and carbon dioxide is higher in unit time, and meanwhile, the small active metal particles can effectively inhibit the generation of carbon deposition in the high-temperature reaction process;
(4) the catalyst prepared by the invention can strictly anchor the active metal on the inner layer of the silicon dioxide capsule structure, limit the migration and aggregation of the active metal in the high-temperature reaction process and ensure that the active sites are not reduced. And the anchored active metal is not easy to lead the formation of coated carbon which inactivates active sites due to the strong physical action with the carrier;
(5) the capsule catalyst prepared by the invention has a unique double-stage pore passage structure (figure 2), wherein pores with the diameter of 3-4 nm are from penetrating pore passages of a shell layer to promote reaction gas diffusion, and pores with the diameter of 12-15 nm are from hollow cavities of the capsule to promote reaction gas to react on the inner surface of the capsule;
(6) the slightly soluble colloid system adopted by the preparation method can realize the monodispersed uniform coating of the oil phase relative to the water phase and the coating of the self-generated gas phase in the oil phase relative to the micelle, and a small amount of N can be generated in the reduction process of the water phase nickel precursor in the self-assembly coating process of the material2、NH3Or H2When the bubbles exist stably in the slightly soluble micelle system, the original spherical micelles are expanded to the columnar capsules orderly above the liquid level under the pushing of the directional acting force of the buoyancy of the bubbles, so that the growth process of the ordered capsule coating structure is realized.
(7) The preparation method disclosed by the invention is wide in concentration range of an oil-water stable system, the formation of a monodisperse capsule structure can be still realized when the concentration of the Ni-based bimetal mixed salt is 1.5-2.0 mol/L, the preparation process is simple, and the batch yield is high.
Drawings
FIG. 1 is a schematic diagram of the preparation of Ni-based bimetallic nanocapsule catalyst of the present invention.
Fig. 2 is a pore size distribution diagram of the Ni-based bimetallic nanocapsule catalyst of example 2.
Fig. 3 is a TEM image of the Ni-based bimetallic nanocapsule catalyst of example 3.
Fig. 4 is an XRD pattern of the Ni-based bimetallic nanocapsule catalyst of example 4.
Fig. 5 is a reaction evaluation graph of the Ni-based bimetal nanocapsule catalyst of example 3.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and do not limit the scope of the present invention.
Example 1: 10g of polyoxyethylene (10) cetyl ether are weighed into a conical flask, cyclohexane is added to 100mL, and heating and stirring are carried out at 40 ℃. When the solution is observed to be clear, 5mL of 2.0mol/L nickel nitrate and copper nitrate mixed solution (the molar ratio of Ni to Cu is 1:1) is added, and after stirring and mixing uniformly, 2mL of hydrazine hydrate is added. And aging for 0.5h, increasing the rotating speed, adding a mixed solution of 2mL of concentrated ammonia water (25 wt.%) and 13mL of deionized water, slowly adding 10mL of TEOS, hydrolyzing for 1h, adding isopropanol, demulsifying, and centrifuging. And finally, drying the obtained sample at 110 ℃ for 12h, and then calcining the dried sample at 500 ℃ at the speed of 1 ℃/min in an air atmosphere to obtain the bimetallic nanocapsule catalyst 1.
Tabletting and sieving calcined catalyst 1, taking 0.1g of 20-40-mesh catalyst, uniformly mixing the catalyst with quartz sand, putting the mixture into a reaction tube, introducing a nitrogen-hydrogen mixed gas at 650 ℃ for reduction for 1h, and then introducing methane, carbon dioxide and N2The gas undergoes catalytic reforming reaction, CH4:CO2:N21.2:1:5, and the total space velocity of gas is 12L g-1·h-1The reaction temperature was 700 ℃ and the product was analyzed by gas chromatography. The conversion of methane and carbon dioxide stabilized at 71% and 79% over a reaction time of 200 h.
Example 2: 20g of polyoxyethylene (10) cetyl ether are weighed into a conical flask, cyclohexane is added to 100mL, and heating and stirring are carried out at 45 ℃. When the solution is observed to be clear, 7mL of 1.8mol/L mixed solution of nickel nitrate and cobalt nitrate (the molar ratio of Ni to Co is 2:1) is added, and after stirring and mixing uniformly, 3mL of hydrazine hydrate is added. And aging for 1.5h, increasing the rotating speed, adding a mixed solution of 1.5mL of concentrated ammonia water and 13.5mL of deionized water, slowly adding 12.5mL of TEOS, hydrolyzing for 6h, adding isopropanol to demulsify, and centrifuging. Finally, the obtained sample is dried at 80 ℃ for 24h, and then calcined at 600 ℃ at the speed of 1.5 ℃/min under the air atmosphere, so as to obtain the bimetallic nanocapsule catalyst 2.
Tabletting and sieving the calcined catalyst 2, taking 0.1g of 40-60-mesh catalyst, uniformly mixing the catalyst with quartz sand, putting the mixture into a reaction tube, introducing a nitrogen-hydrogen mixed gas at 680 ℃ for reduction for 1h, and then introducing methane, carbon dioxide and N2The gas undergoes catalytic reforming reaction, CH4:CO2:N21.3:1:2, and the total space velocity of gas is 24L g-1·h-1The reaction temperature was 750 ℃ and the product was analyzed by gas chromatography. The conversion of methane and carbon dioxide stabilized at 81% and 88% over a reaction time of 200 h.
Example 3: 34g of polyoxyethylene (10) cetyl ether are weighed into a conical flask, cyclohexane is added to 100mL, and heating and stirring are carried out at 50 ℃. When the solution is observed to be clear, 5mL of 1.5mol/L mixed solution of nickel nitrate and copper nitrate (Ni: Cu molar ratio is 4:1) is added, and after stirring and mixing uniformly, 4mL of hydrazine hydrate is added. And aging for 3h, increasing the rotating speed, adding a mixed solution of 1mL of concentrated ammonia water and 14mL of deionized water, slowly adding 10mL of TEOS, adding isopropanol after hydrolyzing for 12h, demulsifying, and centrifuging. Finally, the obtained sample is dried at 100 ℃ for 12h, and then calcined at 700 ℃ at the speed of 2 ℃/min under the air atmosphere, so as to obtain the bimetallic nanocapsule catalyst 3.
Tabletting and sieving calcined catalyst 3, taking 0.1g of 20-40 mesh catalyst, uniformly mixing the catalyst with quartz sand, putting the mixture into a reaction tube, introducing a nitrogen-hydrogen mixed gas at 700 ℃ for reduction for 1h, and then introducing methane, carbon dioxide and N2The gas undergoes catalytic reforming reaction, CH4:CO2:N21.2:1:3, and the total space velocity of gas is 48L g-1·h-1The reaction temperature was 800 ℃ and the product was analyzed by gas chromatography. The conversion of methane and carbon dioxide stabilized at 90% and 94% over a reaction time of 600 h.
Example 4: 40g of polyoxyethylene (10) cetyl ether are weighed into a conical flask, cyclohexane is added to 100mL, and heating and stirring are carried out at 60 ℃. When the solution is observed to be clear, 10mL of 1.5mol/L mixed solution of nickel acetylacetonate and cobalt acetylacetonate (Ni: Co molar ratio is 3:1) is added, and after stirring and mixing, 6mL of hydrazine hydrate is added. And aging for 6h, increasing the rotating speed, adding a mixed solution of 1mL of concentrated ammonia water and 14mL of deionized water, slowly adding 15mL of TEOS, adding isopropanol after hydrolyzing for 24h, demulsifying, and centrifuging. And finally, drying the obtained sample at 120 ℃ for 16h, and then calcining at 800 ℃ at the speed of 3 ℃/min in an air atmosphere to obtain the bimetallic nanocapsule catalyst 4.
Tabletting and sieving calcined catalyst 4, taking 0.1g of 40-60-mesh catalyst, uniformly mixing the catalyst with quartz sand, putting the mixture into a reaction tube, introducing a nitrogen-hydrogen mixed gas at 750 ℃ for reduction for 1h, and then introducing methane, carbon dioxide and N2The gas undergoes catalytic reforming reaction, CH4:CO2:N21.1:1:5, and the total space velocity of gas is 36L g-1·h-1The reaction temperature was 850 ℃ and the product was analyzed by gas chromatography. The conversion of methane and carbon dioxide stabilized at 97% and 99% over a reaction time of 400 h.
Example 5: 50g of polyoxyethylene (10) cetyl ether are weighed into a conical flask, cyclohexane is added to 100mL, and heating and stirring are carried out at 50 ℃. When the solution is observed to be clear, 8mL of 2.0mol/L mixed solution of nickel chloride and cobalt chloride (the molar ratio of Ni to Co is 3:1) is added, and after stirring and mixing uniformly, 8mL of hydrazine hydrate is added. And aging for 12h, increasing the rotating speed, adding a mixed solution of 1.5mL of concentrated ammonia water and 13.5mL of deionized water, slowly adding 15mL of TEOS, adding isopropanol after hydrolyzing for 48h, demulsifying, and centrifuging. Finally, the obtained sample is dried at 60 ℃ for 20h, and then calcined at 650 ℃ at a rate of 4 ℃/min under an air atmosphere to obtain the bimetallic nanocapsule catalyst 5.
Tabletting and sieving calcined catalyst 5, taking 0.1g of 20-40-mesh catalyst, uniformly mixing the catalyst with quartz sand, putting the mixture into a reaction tube, introducing a nitrogen-hydrogen mixed gas at 700 ℃ for reduction for 1h, and then introducing methane, carbon dioxide and N2The gas undergoes catalytic reforming reaction, CH4:CO2:N21.4:1:1, and the total space velocity of gas is 32L g-1·h-1Reaction temperatureThe degree was 800 ℃ and the product was analyzed by gas chromatography. The conversion of methane and carbon dioxide stabilized at 91% and 95% over a reaction time of 200 h.
Example 6: 10g of polyethylene glycol mono-4-nonylphenyl ether and 10g of polyoxyethylene (10) cetyl ether were weighed into a Erlenmeyer flask, cyclohexane was added to 100mL, and the mixture was heated and stirred at 50 ℃. When the solution is observed to be clear, 6mL of 1.5mol/L mixed solution of nickel acetylacetonate and copper acetylacetonate (Ni: Cu molar ratio is 4:1) is added, and after stirring and mixing, 5mL of hydrazine hydrate is added. And aging for 18h, increasing the rotating speed, adding a mixed solution of 2.5mL of concentrated ammonia water and 12.5mL of deionized water, slowly adding 10mL of TEOS, hydrolyzing for 30h, adding isopropanol, demulsifying, and centrifuging. Finally, the obtained sample is dried at 70 ℃ for 12h, and then calcined at 700 ℃ at the speed of 5 ℃/min under the air atmosphere, so as to obtain the bimetallic nanocapsule catalyst 6.
Tabletting and sieving calcined catalyst 6, taking 0.1g of 40-60-mesh catalyst, uniformly mixing the catalyst with quartz sand, putting the mixture into a reaction tube, introducing a nitrogen-hydrogen mixed gas at 650 ℃ for reduction for 1h, and then introducing methane, carbon dioxide and N2The gas undergoes catalytic reforming reaction, CH4:CO2:N21.3:1:4, and the total space velocity of gas is 48L g-1·h-1The reaction temperature was 750 ℃ and the product was analyzed by gas chromatography. The conversion of methane and carbon dioxide stabilized at 77% and 85% over a reaction time of 200 h.
Example 7: 20g of polyethylene glycol mono-4-nonylphenyl ether and 10g of polyoxyethylene (10) cetyl ether are weighed into a conical flask, cyclohexane is added to 100mL, and heating and stirring are carried out at 50 ℃. When the solution is observed to be clear, 5mL of 2mol/L mixed solution of nickel chloride and copper chloride (the molar ratio of Ni to Cu is 1:1) is added, and after stirring and mixing uniformly, 7mL of hydrazine hydrate is added. And aging for 24h, increasing the rotating speed, adding a mixed solution of 3mL of concentrated ammonia water and 12mL of deionized water, slowly adding 7.5mL of TEOS, adding isopropanol after hydrolyzing for 40h, demulsifying, and centrifuging. Finally, the obtained sample is dried at 50 ℃ for 24h, and then calcined at 750 ℃ at the speed of 2 ℃/min under the air atmosphere, so as to obtain the bimetallic nanocapsule catalyst 7.
Tabletting and sieving calcined catalyst 7, taking 0.1g of 20-40 mesh catalyst, uniformly mixing the catalyst with quartz sand, putting the mixture into a reaction tube, introducing a nitrogen-hydrogen mixed gas at 700 ℃ for reduction for 1h, and then introducing methane, carbon dioxide and N2The gas undergoes catalytic reforming reaction, CH4:CO2:N21.2:1:2, and the total space velocity of gas is 18L g-1·h-1The reaction temperature was 750 ℃ and the product was analyzed by gas chromatography. The conversion of methane and carbon dioxide stabilized at 78% and 86% over a reaction time of 200 h.
Table 1 structural property parameters of catalysts in each example
Claims (4)
1. The Ni-based bimetallic nanocapsule catalyst is characterized by consisting of a capsule shell layer and a metal core; the shell layer of the capsule is silicon oxide, and the metal core is bimetallic nickel-copper or nickel-cobalt particles; the total content of nickel and copper or nickel and cobalt in the nano capsule catalyst is 10-20 wt%, the particle size of nickel and copper or nickel and cobalt bimetallic particles is 1-4 nm, the capsule cavity is (6.5-7.5) nm x (15-60) nm, and the thickness of a capsule shell layer is 5.5 +/-3 nm; the nano-capsule catalyst has a two-stage pore channel structure, wherein pores with the diameter of 3-4 nm are from penetrating pore channels of a shell layer, and pores with the diameter of 12-15 nm are from a hollow cavity of a capsule;
the preparation method of the nano capsule catalyst is characterized by comprising the following steps:
(1) weighing 10-50 g of surfactant in a container, adding cyclohexane to 100mL, heating at 40-60 ℃, and stirring;
(2) adding 5-10 mL of 1.5-2.0 mol/L Ni-Co salt mixed solution or Ni-Cu salt mixed solution, wherein the molar ratio of Ni-Co or Ni-Cu is 4-1: 1, stirring to mix uniformly, and adding 2-8 mL of hydrazine hydrate;
(3) after aging for 0.5-24 h, increasing the stirring speed, adding 15mL of mixed solution of concentrated ammonia water and deionized water, and then slowly adding 7.5-15 mL of TEOS;
(4) adding acetone after hydrolyzing for 1-48 h for demulsification, and centrifuging;
(5) drying the sample at the last step at 50-120 ℃ for 12-24 h, and then calcining at 500-800 ℃ at a rate of 1-5 ℃/min in an air atmosphere;
the surfactant in the step (1) is one or two of polyoxyethylene (10) cetyl ether and polyethylene glycol mono-4-nonyl phenyl ether;
and (4) the amount of the concentrated ammonia water in the mixed solution in the step (3) is 1-3 mL.
2. The nanocapsule catalyst of claim 1, wherein the Ni — Co salt mixed solution in the step (2) is a mixed solution of nickel nitrate and cobalt nitrate, a mixed solution of nickel chloride and cobalt chloride, or a mixed solution of nickel acetylacetonate and cobalt acetylacetonate; the Ni-Cu salt mixed solution is a mixed solution of nickel nitrate and copper nitrate, a mixed solution of nickel chloride and copper chloride or a mixed solution of nickel acetylacetonate and copper acetylacetonate.
3. Use of the nanocapsule catalyst of claim 1 in a biogas reforming reaction.
4. The use of claim 3, wherein the biomass gas has a molar composition of CH4 : CO2 : N2=1.1~1.4 : 1 : 1~5。
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