CN117861671A - Zircon derivative nickel-based catalyst for autothermal reforming of acetic acid to prepare hydrogen - Google Patents
Zircon derivative nickel-based catalyst for autothermal reforming of acetic acid to prepare hydrogen Download PDFInfo
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- CN117861671A CN117861671A CN202410017448.8A CN202410017448A CN117861671A CN 117861671 A CN117861671 A CN 117861671A CN 202410017448 A CN202410017448 A CN 202410017448A CN 117861671 A CN117861671 A CN 117861671A
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002453 autothermal reforming Methods 0.000 title claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 16
- 239000001257 hydrogen Substances 0.000 title claims abstract description 14
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical class [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 title claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 229910052845 zircon Inorganic materials 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 4
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 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 2
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052799 carbon Inorganic materials 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 12
- 238000005245 sintering Methods 0.000 abstract description 12
- 238000003980 solgel method Methods 0.000 abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 abstract description 5
- 229910052777 Praseodymium Inorganic materials 0.000 abstract description 4
- 230000009849 deactivation Effects 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000001737 promoting effect Effects 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007833 carbon precursor Substances 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 238000010744 Boudouard reaction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Classifications
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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
- 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
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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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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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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 relates to a zircon type derivative nickel-based catalyst for preparing hydrogen by autothermal reforming of acetic acid. Aiming at the deactivation problem of the existing catalyst in the acetic acid autothermal reforming process, the invention provides a novel catalyst with carbon deposit resistance, sintering resistance and high activity. The catalyst of the invention has the chemical composition of (NiO) a (PrO 1.5 ) b (VO 2.5 ) c Wherein a is 0.75-0.86, b is 1.19-1.39, and c is 1.24-1.57. The invention adopts a sol-gel method, takes Ni as an active component, introduces Pr and V elements, prepares the Ni species supported on zircon type PrVO 4 Novel catalyst on derivative and forming Ni-Pr-V-O active center, effectively improving acetic acid autothermal reformingAnd (3) preparing hydrogen reaction activity.
Description
Technical Field
The invention relates to a zircon type derivative nickel-based catalyst for autothermal reforming of acetic acid to prepare hydrogen, belonging to the field of preparing hydrogen by autothermal reforming of acetic acid.
Background
Biomass is pyrolyzed to obtain biomass oil, the acetic acid content in the water phase component of the biomass oil can reach 33wt%, and the acetic acid is converted into hydrogen through an autothermal reforming reaction, so that the biomass oil is a potential hydrogen production path.
The nickel-based catalyst has the activity equivalent to that of a noble metal catalyst, but has low cost, can effectively crack C-H bonds, and can be used for autothermal reforming reaction of acetic acid. However, oxygen introduced in the acetic acid autothermal reforming system can form an oxidation zone of up to 1100 ℃ at the front end of the catalyst bed, which is extremely prone to collapse of the catalyst internal structure, causing agglomeration sintering of the active component nickel species; meanwhile, the front end of the catalytic bed layer is in an oxygen atmosphere, which can lead to active species Ni 0 Oxidation to Ni 2+ Losing the ability to convert the reactant acetic acid; in addition, acetone, CHx and other intermediates generated in the dissociation process of acetic acid molecules can be further dehydrogenated to generate carbon precursor, if the carbon precursor cannot be timely oxidized into CO and CO 2 Carbon deposits are formed to cover the active sites, resulting in a decrease in catalyst activity. Therefore, the development of a catalyst with stable structure, excellent sintering resistance and excellent carbon deposit resistance is a key point for improving acetic acid conversion activity.
Aiming at the problems of sintering and carbon deposition of the catalyst in the autothermal reforming conversion process of acetic acid, the invention prepares zircon-type PrVO by a sol-gel method 4 The derivative-supported nickel-based catalyst forms an active center of Ni-Pr-V-O and is used in the autothermal reforming hydrogen production process of acetic acid.
On one hand, the PrVO constructed by the invention aims at the directional conversion problem of acetic acid, water and oxygen which are reactants in the autothermal reforming process of acetic acid 4 Having a tetragonal zircon structure and I4 1 An/amd space group feature in which Pr ions occupy D 2d Symmetry, coordination number 8, and VO tetrahedra with distorted PrO 8 The dodecahedron shares corners and edges, and the tetragonal zircon structure can stabilize metal cations even in an oxidizing environment and prevent sintering in the autothermal reforming process of acetic acid; meanwhile, prVO of the invention 4 The multiple oxidation states of vanadium in the structure and the rare earth element Pr have special 4f electronic configuration and energy level structure, thus endowing the structure with special structural stability and low charge transferA varistor and a plurality of oxygen vacancies; wherein V is 2 O 5 The intrinsic oxygen vacancies of (2) cause the formation of a large number of defect planes between the valence and conduction bands, facilitating the separation of electrons and holes, while O in the electron or hole environment 2 And H 2 The reaction between O can generate hydroxyl radical OH and oxygen radical O, which effectively gasifies CH 3 * CO/CO generation 2 At the same time inhibit its combination with H to generate CH 4 Increase the reaction product H 2 Selectivity of (2); in addition, will be in contact with V 5+ Pr (0.0735 nm) with larger difference in ionic radius 3+ (0.113 nm) introduction of V 2 O 5 In (a) inducing lattice expansion, thereby creating local mismatch in the structure and compensating for the overall charge imbalance by creating charge imbalance in the crystal, during which process a large number of oxygen vacancies are created, thereby promoting adsorption and generating a large number of surface active O 2 Molecules, which increase the mobility of the active oxygen species O, effectively oxidize CH 3 CH formed by deoh of COOH molecule 3 CO intermediate to form CO and CO 2 Carbon-containing product, preventing carbon precursor from covering active site Ni 0 。
On the other hand, the redox couple formed during the reactionPromote charge circulation at the reaction interface, thereby forming more oxygen vacancies (O v ) Improves the oxidation-reduction capability of the catalyst and the transfer efficiency of oxygen species (O), and is beneficial to the carbon oxidation reaction (CH) 3 *→C*+O*→CO*+O*→CO/CO 2 ) To promote elimination of carbon deposit on the surface of the catalyst; simultaneously utilizing the alkalinity of the rare earth element Pr and the central action of Lewis acid, adjusting the quantity and intensity of the Lewis alkalinity to inhibit dehydration and polymerization reaction of dehydrogenation species adsorbed in the reaction process (the reaction leads to the formation of unsaturated compounds ethylene and the like), and inhibiting ketonization reaction of acetic acid (2 CH 3 COOH→CH 3 COCH 3 +H 2 O+CO 2 ) Is carried out while enhancing the CO 2 Is activated by adsorption driving the Boudouard reaction in reverse (CO 2 +C.fwdarw.2CO) to further reduce the occurrence of carbon depositionRaw materials.
In addition, pr 2 O 3 Configuration of the valence band of itself ([ Xe)] 54 4f 3 6s 2 ) The lewis base can provide electrons, and a rich Pr-O-V interface can be established in the system through the action of interface covalent bonds, so that electrons are transferred from a V site to a Pr site, the d energy band center of the V site moves downwards relative to the Fermi level, the lower the d energy band center of the metal surface is, and the metal d orbit is connected with O 2 The smaller the 2p orbit overlap, the higher the bond-forming orbit, the smaller the adsorption energy, thereby effectively promoting the charge transfer efficiency and the oxygen-containing intermediate (CH) 3 COO*、CH 3 CO*、CH 2 CO, O, etc.).
The innovation of the catalyst structure and components improves the carbon deposition resistance, the thermal stability and the sintering resistance of the Ni-based catalyst in the autothermal reforming reaction of acetic acid.
Disclosure of Invention
The invention solves the technical problems that the existing catalyst is easy to accumulate carbon and sinter in the autothermal reforming reaction of acetic acid, has poor stability and causes the deactivation of the catalyst, and provides a novel catalyst with high thermal stability and sintering resistance.
The invention takes Ni as an active component, introduces Pr and V components, adopts a sol-gel method to prepare zircon PrVO 4 The derivative-supported nickel-based catalyst forms an active center of Ni-Pr-V-O. The catalyst of the invention is used in the reaction of autothermal reforming of acetic acid to produce hydrogen, the conversion rate of acetic acid (HAc) is close to 100% at 700 ℃, and the hydrogen yield is stable at 2.57mol-H 2 about/mol-HAc.
The technical scheme of the invention is as follows:
aiming at the characteristic of autothermal reforming of acetic acid, the invention adopts a sol-gel method to prepare zircon PrVO 4 Derivative supported nickel-based catalysts. The molar composition of the catalyst according to the invention is (NiO) a (PrO 1.5 ) b (VO 2.5 ) c Wherein a is 0.75-0.86, b is 1.19-1.39, c is 1.24-1.57; the weight percentage composition in terms of oxide is: 14.0% -16% of nickel oxide.0 percent, 49.1 to 57.3 percent of praseodymium oxide, 28.2 to 35.6 percent of vanadium pentoxide and 100 percent of the sum of the weight percentages of the components.
The specific preparation method comprises the following steps:
1) Based on the molar composition of the components of the catalyst (NiO) a (PrO 1.5 ) b (VO 2.5 ) c Wherein a is 0.75-0.86, b is 1.19-1.39, c is 1.24-1.57, weighing a proper amount of nickel nitrate, praseodymium nitrate and ammonium metavanadate, adding a proper amount of deionized water, and continuously stirring until all the materials are dissolved to obtain a 1# solution;
2) Weighing citric acid with the total molar ratio of 1:1 to metal cations, dissolving the citric acid in deionized water, uniformly stirring to obtain a No. 2 solution, and weighing ethylene glycol with the total molar ratio of 1:1 to metal cations to obtain a No. 3 solution;
3) Slowly dripping the No. 2 solution into the No. 3 solution, slowly dripping the mixed solution into the No. 1 solution under the water bath condition of 65 ℃, stirring to form gel, and then drying in an oven of 105 ℃ for 12 hours to obtain a catalyst precursor;
4) Placing the dried precursor sample into a tube furnace, heating to 700-800 ℃ at a heating rate of 10 ℃/min, and roasting at the temperature for 4 hours to obtain PrVO 4 Nickel-based catalyst as carrier, its crystal structure is shown in figure 1, forming zircon PrVO 4 Phase and NiO phase, and form Ni/PrVO 4 An interface, and a mesoporous structure is constructed, wherein the typical BJH pore size distribution is shown in figure 2; the catalyst is subjected to H at 600-800 DEG C 2 Reducing for 1 hour in the atmosphere; nitrogen is used as carrier gas, mixed gas with the mol ratio of acetic acid/water/oxygen=1/(3.0-5.0)/(0.2-0.5) is introduced, and acetic acid autothermal reforming reaction is carried out through a catalyst bed layer, wherein the reaction temperature is 600-800 ℃.
The invention has the beneficial effects that:
1) The catalyst of the invention takes Ni as an active component, introduces Pr and V components, and prepares zircon PrVO by adopting a sol-gel method 4 Derivative nickel-based catalyst, active component Ni is highly dispersed in PrVO 4 Structural derivatives promote the formation of Ni-Pr-V-O active centerThe catalyst has high activity, high carbon deposit resistance and high sintering resistance.
2) (1) zircon-based PrVO formed by the catalyst of the invention 4 The structure has obvious structural stability, is favorable for separating electrons and holes, and is acetic acid autothermal reforming reactant O 2 And H 2 O generates hydroxyl radical OH and oxygen radical O in the environment, effectively gasifying acetic acid-derived CH 3 * Species, which can improve the carbon deposit resistance of the catalyst and inhibit the combination of H and H to generate CH 4 And a high OH mobility favors the WGS reaction (co+h 2 O→CO 2 +H 2 ) Increase the H of 2 Selectivity of (2);
(2) on the active center of Ni-Pr-V-O formed by the catalyst, the alkaline of the rare earth element Pr and the center action of L acid are utilized to adjust the number and the intensity of L alkaline in the system, thereby promoting the acidic reactant molecule CH 3 Adsorption activation of COOH and driving the Boudouard reaction in reverse (CO 2 +C.fwdarw.2CO), reducing catalyst carbon deposit;
(3) at the same time, introduce and V 5+ Pr with larger ion radius difference 3+ Inducing lattice expansion in PrVO 4 A plurality of oxygen vacancies are generated in the structure, thereby adsorbing and generating a plurality of surface active O 2 Molecules, thereby improving the mobility of active oxygen species O, effectively oxidizing carbon-containing intermediates such as CHx, C and the like, and avoiding carbon deposition precursors from covering active sites Ni 0 。
3) Carrier PrVO in the present invention 4 Pr and V species in the derivative have various valence states and are formed in the reaction processAnd +.>Electron transfer promotes the circulation of reaction interface charges, effectively inhibits dehydration and polymerization reaction in the reaction process, and simultaneously forms more oxygen vacancies in the process, thereby being beneficial to the elimination of carbon deposit on the surface of the catalyst.
4) The catalyst has rich Pr-O-V interface to promote electrons from V site to V sitePr site transfer whereby the d-band center of the V site moves downward relative to the Fermi level, further promoting charge transfer efficiency and oxygen-containing intermediates (CH 3 COO*、CH 3 CO, O, etc.), while the active component Ni 0 The interaction with Pr-O-V interface can inhibit migration and agglomeration of nickel particles under high temperature condition, and improve sintering resistance of catalyst in autothermal reforming process of acetic acid.
5) The result of the autothermal reforming reaction of acetic acid shows that the catalyst can induce the efficient conversion of reactant acetic acid molecules in the acetic acid conversion process, effectively inhibit the production of byproducts such as methane, acetone and the like, improve the hydrogen selectivity, and has the characteristics of carbon deposit resistance, stable activity, sintering resistance and the like.
Drawings
Fig. 1: x-ray diffraction pattern of the catalyst of the invention
Fig. 2: BJH pore size distribution diagram of the catalyst of the invention
Detailed Description
Reference example 1
1.175g of Ni (NO) 3 ) 2 ·6H 2 O and 12.497g of Al (NO) 3 ) 3 ·9H 2 Pouring O into a beaker, adding a proper amount of deionized water, and fully stirring until the deionized water is dissolved to obtain a No. 1 solution; then weighing 7.849g of citric acid, dissolving in deionized water, and uniformly stirring to obtain a No. 2 solution; 2.318g of ethylene glycol is weighed to obtain a 3# solution; slowly dripping the No. 2 solution into the No. 3 solution, slowly dripping the mixed solution into the No. 1 solution under the water bath condition of 70 ℃, stirring to form gel, and then drying in an oven of 105 ℃ for 24 hours to obtain a catalyst precursor; the precursor sample is put into a tube furnace, heated to 750 ℃ at a heating rate of 5 ℃/min, and baked for 4 hours at the temperature to obtain a CDUT-NA catalyst, thus forming a catalyst loaded on Al 2 O 3 A Ni-based catalyst thereon; the catalyst comprises the following components in percentage by weight in terms of oxide: nickel oxide (NiO) 15.1%, alumina (AlO) 1.5 ) 84.9%.
The acetic acid autothermal reforming reactivity evaluation was performed in a continuous flow fixed bed reactor. Grinding the catalystGrinding and tabletting, sieving to obtain 20-40 mesh granules, weighing 0.1-0.2g of tabletted catalyst, mixing with quartz sand, loading into reactor, and standing at 600-800deg.C under H 2 Reducing for 1h; then injecting the acetic acid-water mixed solution into a vaporizer by a constant flow pump for vaporization, mixing with nitrogen, and forming a catalyst with the molar ratio of CH by taking the nitrogen as an internal standard gas 3 COOH/H 2 O/O 2 The reaction raw material gas of 1/(3.0-5.0)/(0.2-0.5) is introduced into a reaction bed, the reaction condition is 600-800 ℃, the normal pressure and the airspeed are 20000-60000 mL/(g-catalyst.h), and the reaction tail gas is analyzed on line by a gas chromatograph.
The activity of the CDUT-NA catalyst is examined by acetic acid autothermal reforming reaction, the space velocity is 25000 mL/(g-catalyst.h), the reaction temperature is 650 ℃, and the feeding mole ratio is CH 3 COOH/H 2 O/O 2 Under the reaction condition of 1/4.0/0.28, the initial conversion rate of the catalyst to acetic acid is 99.6%, the conversion rate of acetic acid after 10 hours of reforming reaction is reduced to 64.6%, and H 2 The yield gradually drops to 0.65mol-H 2 /mol-HAc，CO 2 The selectivity fluctuates at about 49.0%, the selectivity of CO fluctuates at about 38.5%, the selectivity of byproduct methane fluctuates at about 5.6%, and the selectivity of byproduct acetone increases to about 35.7%. The XRD and other characterization results show that the catalyst has low activity and more byproducts in the autothermal reforming process of acetic acid, and has the phenomena of sintering and carbon deposition in the reaction process, so that the overall stability is poor.
Example 1
1.161g of Ni (NO) 3 ) 2 ·H 2 O, 2.893g Pr (NO) 3 ) 3 ·6H 2 O,0.778g NH 4 VO 3 Adding a proper amount of deionized water, and uniformly stirring to obtain a No. 1 solution; then weighing 3.634g of citric acid, dissolving in deionized water, and uniformly stirring to obtain a No. 2 solution; 1.074g of ethylene glycol is weighed to obtain a 3# solution; slowly dripping the No. 2 solution into the No. 3 solution, slowly dripping the mixed solution into the No. 1 solution under the water bath condition of 65 ℃, stirring to form gel, and then drying in an oven of 105 ℃ for 12 hours to obtain a catalyst precursor; placing the sample into a tube furnaceThe catalyst CDUT-NPV of the invention is obtained after heating to 800 ℃ at a heating rate of 10 ℃/min and roasting for 4 hours at the temperature, and the typical crystal structure of the catalyst is shown in the attached figure 1, and significant PrVO is formed at 24.4 DEG, 32.8 DEG and 48.5 DEG 4 Diffraction peaks of NiO appear at 37.2 °, 43.3 ° and 62.9 °, to give zircon-type PrVO 4 Derivative nickel-based catalyst forming Ni/PrVO with Ni-Pr-V-O active center 4 A structure; the nitrogen low-temperature physical adsorption and desorption test result shows that the pore diameter of the catalyst is intensively distributed at 11.1nm, and the typical mesoporous structure is shown in figure 2; the molar composition of the catalyst is (NiO) 0.79 (PrO 1.5 ) 1.33 (VO 2.5 ) 1.33 The weight percentage composition in terms of oxide is: 14.9% of nickel oxide, 54.9% of praseodymium oxide and 30.2% of vanadium pentoxide.
The activity of the CDUT-NPV catalyst is examined through acetic acid autothermal reforming reaction, the space velocity is 25000 mL/(g-catalyst.h), the reaction temperature is 700 ℃, and the feeding mole ratio is CH 3 COOH/H 2 O/O 2 Under the reaction condition of 1/4.0/0.28, the conversion rate of the catalyst to acetic acid is stabilized at 100%, H 2 The yield was stabilized at 2.57mol-H 2 about/mol-HAc, CO 2 The selectivity is about 58.6%, the CO selectivity is maintained about 41.3%, byproducts of methane and acetone are not detected, and the catalyst activity is kept stable and is not deactivated. The physical adsorption and desorption results of low-temperature nitrogen indicate that the specific surface area of the catalyst is 8.0m 2 Per gram, pore volume of 0.05cm 3 The average pore diameter per gram is 11.1nm, the most probable pore diameter is 2.3nm, and the mesoporous material belongs to mesoporous materials. The characterization result shows that the catalyst has no obvious carbon deposition and no sintering phenomenon, has high and stable acetic acid conversion rate, can effectively inhibit the production of byproducts methane and acetone, and has higher activity of autothermal reforming hydrogen production of acetic acid.
Claims (2)
1. Use of a zircon derivative nickel-based catalyst in an autothermal reforming process of acetic acid, characterized in that: 0.1-0.2g of catalyst is reacted with H at 600-800 ℃ before acetic acid autothermal reforming 2 Reducing for 1h in atmosphere, and introducing acetic acid in a molar ratio ofThe mixed gas of water/oxygen=1/(3.0-5.0)/(0.2-0.5) is subjected to acetic acid autothermal reforming reaction through a catalyst bed layer, and the reaction temperature is 600-800 ℃; the preparation method of the catalyst comprises the following steps: weighing a certain amount of nickel nitrate, praseodymium nitrate and ammonium metavanadate according to chemical compositions, adding a proper amount of deionized water, and uniformly stirring at normal temperature to obtain a 1# solution; weighing citric acid with the total molar ratio of 1:1 to metal cations, dissolving the citric acid in deionized water, and uniformly stirring to obtain a No. 2 solution; weighing glycol with the total molar ratio of metal cations of 1:1 to obtain a 3# solution; slowly dripping the No. 2 solution into the No. 3 solution, slowly dripping the mixed solution into the No. 1 solution under the water bath condition of 65 ℃, stirring to form gel, then drying in an oven of 105 ℃ for 12 hours, putting into a tube furnace, heating to 700-800 ℃ at the heating rate of 10 ℃/min, and roasting at the temperature for 4 hours to obtain zircon PrVO 4 Derivative nickel-based catalyst, ni/PrVO with Ni-Pr-V-O as active center is formed 4 The chemical molar composition of the structure is (NiO) a (PrO 1.5 ) b (VO 2.5 ) c Wherein a is 0.75-0.86, b is 1.19-1.39, c is 1.24-1.57; the weight percentage composition in terms of oxide is: 14.0 to 16.0 percent of nickel oxide, 49.1 to 57.3 percent of praseodymium oxide, 28.2 to 35.6 percent of vanadium pentoxide and 100 percent of the sum of the weight percentages of the components.
2. Use of a zircon-derivative nickel-based catalyst according to claim 1 for autothermal reforming of acetic acid to produce hydrogen, wherein: the catalyst comprises the following components in percentage by weight in terms of oxide: 14.9% of nickel oxide, 54.9% of praseodymium oxide and 30.2% of vanadium pentoxide.
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