CN116273019A - Cerium-yttrium solid solution structured nickel-based catalyst for autothermal reforming of acetic acid to produce hydrogen - Google Patents
Cerium-yttrium solid solution structured nickel-based catalyst for autothermal reforming of acetic acid to produce hydrogen Download PDFInfo
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 183
- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 37
- 239000001257 hydrogen Substances 0.000 title claims abstract description 36
- 239000006104 solid solution Substances 0.000 title claims abstract description 36
- 238000002453 autothermal reforming Methods 0.000 title claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 17
- LENJPRSQISBMDN-UHFFFAOYSA-N [Y].[Ce] Chemical compound [Y].[Ce] LENJPRSQISBMDN-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 29
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 25
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 16
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 239000002923 metal particle Substances 0.000 claims description 8
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 8
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 238000010668 complexation reaction Methods 0.000 claims description 5
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- 238000005187 foaming Methods 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 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
- 238000002360 preparation method Methods 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 14
- 238000005245 sintering Methods 0.000 abstract description 8
- 230000008021 deposition Effects 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 6
- 239000007833 carbon precursor Substances 0.000 abstract description 3
- 230000009849 deactivation Effects 0.000 abstract description 3
- 238000003980 solgel method Methods 0.000 abstract description 3
- 238000002309 gasification Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 description 48
- 239000001301 oxygen Substances 0.000 description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 42
- 230000000694 effects Effects 0.000 description 15
- 230000002829 reductive effect Effects 0.000 description 13
- 239000011148 porous material Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 239000002028 Biomass Substances 0.000 description 6
- -1 cerium cation Chemical class 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000027756 respiratory electron transport chain Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000000629 steam reforming Methods 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000001833 catalytic reforming Methods 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- CKJRQPWAXMFUCK-UHFFFAOYSA-N methane;propan-2-one Chemical compound C.CC(C)=O CKJRQPWAXMFUCK-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000012360 testing method Methods 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
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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
- B01J23/83—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 rare earths or actinides
-
- 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
-
- 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
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- 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
Abstract
The invention relates to a cerium-yttrium solid solution nickel-based catalyst for preparing hydrogen by autothermal reforming of acetic acid. Aiming at the problems of catalyst structure change, sintering, carbon deposition and other deactivation existing in the acetic acid autothermal reforming reaction of the existing catalyst, the invention adopts a sol-gel method, takes Ni as an active component, and introduces Y into CeO 2 Lattice synthesis of Ce 1‑ x Y x O 2‑δ The solid solution nickel-based catalyst forms an active center of Ni-Ce-Y-O, promotes the efficient conversion of acetic acid molecules, promotes the gasification of carbon precursor, reduces the formation of byproducts such as acetone and the like, and obviously improves the carbon deposit resistance, sintering resistance and hydrogen yield of the catalyst. The catalyst of the invention has the chemical composition of (NiO) a (CeO 2 ) b (YO 1.5 ) c Wherein a is 027-0.29, b is 0.51-0.72, c is 0-0.20 and c is not 0.
Description
Technical Field
The invention relates to a cerium-yttrium solid solution structure nickel-based catalyst for autothermal reforming of acetic acid to prepare hydrogen, belonging to the field of autothermal reforming of acetic acid to prepare hydrogen.
Background
Hydrogen is a clean renewable energy source with unit energy densities up to 122kJ/kg and is considered an alternative energy source to conventional fossil fuels. At present, hydrogen can be produced by fossil raw materials, electrolyzed water, biomass and the like, and the fossil raw materials, electrolyzed water, biomass and the like are main production sources of the hydrogen, but the problems of low energy conversion rate, high production cost and the like exist. Biomass sources are wide and renewable, biomass oil can be obtained through fast pyrolysis, and the water phase of the biomass oil takes acetic acid as a main component, so that the acetic acid can be used as a good raw material for reforming hydrogen production by biomass derivation.
The hydrogen production by acetic acid catalytic reforming is mainly divided into: steam reforming of acetic acid to produce hydrogen, partial oxidation of acetic acid to produce hydrogen, and autothermal reforming of acetic acid to produce hydrogen. Steam reforming hydrogen production is a strong endothermic reaction that requires external heat to sustain, resulting in increased hydrogen production costs. Partial oxidation hydrogen production is an exothermic process in which acetic acid is subject to deep oxidation, resulting in reduced hydrogen yield. Unlike the former two, autothermal reforming of acetic acid introduces both oxygen and water into the feed, and by adjusting the ratio of oxygen to reactants, the heat balance of the reaction (CH 3 COOH+xH 2 O+yO 2 →aCO 2 +bCO+cH 2 ，ΔH＝0kJmol -1 ) The method comprises the steps of carrying out a first treatment on the surface of the At the same time, oxygen may oxidize carbonaceous species to inhibit the production of char.
The catalyst is the key of acetic acid reforming reaction, and can influence the reaction path of raw materials, reduce the reaction activation energy and accelerate the reaction rate. At present, noble metal catalysts (such as Pt, pd, ph and the like) have excellent catalytic activity in catalytic reforming hydrogen production, can efficiently convert acetic acid and improve the hydrogen yield, but have limited wide application due to high price. The Ni-based catalyst is used as a non-noble metal catalyst, has stronger capacity of activating C-C, C-H, C-O and O-H bonds in the autothermal reforming process of acetic acid, and can promote the conversion of acetic acid molecules and the generation of hydrogen, so that the Ni-based catalyst is more suitable for the autothermal reforming process of acetic acid.
In the autothermal reforming of acetic acid, acetic acid is dehydized to produce CH 3 COO and the like intermediate, CH 3 COO further deoxo generates CH 3 CO, etc. intermediate, when the reaction continuesCH 3 CO and the like will continue to scavenge H and CO to form CH and CH 3 * And CH 3 * Is the main source of coking and CH 3 The CO and other intermediates are hydrogenated in combination with CH on the Ni metal surface to form acetone (CH 3 CO*+CH 3 *→CH 3 COCH 3 ) The carbon-containing species such as acetone, ketene and the like further undergo polycondensation reaction to generate carbon deposit which is deposited on the surface of the catalyst to cover Ni active sites, so that contact between reactants and the catalyst is reduced, and the activity of the catalyst is reduced. In addition, the acetic acid autothermal reforming reaction raw material contains oxygen, the oxygen mainly reacts at the front end of the catalytic bed layer, so that the partial reaction temperature at the front end of the reactor can reach 1000 ℃, the active components can be oxidized in the oxygen atmosphere, and meanwhile, the high-temperature environment also causes collapse of the internal structure of the catalyst, so that small-particle metal on the catalyst is aggregated and sintered to lose the catalytic activity.
In order to solve the deactivation problems of Ni-based catalyst sintering, oxidation and the like in the autothermal reforming process of acetic acid, the invention introduces Ce and Y components, takes Ni as an active component and creates Ce taking Ni-Ce-Y-O as an active center 1-x Y x O 2-δ Solid solution structured catalysts. The main component of the solid solution is CeO 2 Is an excellent oxygen storage material, and the electronic structure of cerium (i.e. [ Xe ]]4f 1 5d 1 6s 2 ) Make it at Ce 4+ And Ce (Ce) 3+ The reversible charge transfer is easier to carry out between Ce 4+ To Ce 3+ The conversion of (a) results in the formation of oxygen vacancies, favoring the formation of lattice oxygen (O) 2- ) And migrate toward the surface, inhibiting deposition of carbon on the catalyst surface. However, ceO 2 The performance of oxygen transfer capacity during autothermal reforming of acetic acid is not ideal due to CeO 2 The crystal is usually fluorite phase, each cerium cation in the crystal lattice is coordinated by eight oxygen anions, each oxygen anion coordinates four cerium cations to form a crystal lattice stable tetrahedral coordination structure, the formation of oxygen vacancies needs to break four Ce-O bonds, and the oxygen anions are in a very stable state, which inhibits Ce to a certain extent 4+ And Ce (Ce) 3+ The conversion between the two limits the release and migration of lattice oxygen, so that the energy of removing carbon depositThe force is affected. In view of the above problems, ceO can be improved by introducing other low-valence metal oxides 2 Is a performance of the (c).
In order to solve the defect of cerium oxide, the catalyst of the invention introduces rare earth metal Y into CeO 2 Lattice construction of Ce 1- x Y x O 2-δ Solid solution structured nickel-based catalysts. On the one hand, because the coordination numbers of the Y-O bond and the Ce-O bond are different, the Ce-O bond can be activated, the release of lattice oxygen is promoted, more oxygen vacancies are formed, and the CH derived from acetic acid in the autothermal reforming process of acetic acid 3-x * Gasifying carbon-containing species such as C and CO, and improving CO/CO 2 Selectivity (CH) 3 *→C*+O*→CO*+O*→CO/CO 2 ) Carbon deposition in the reaction process is reduced; on the other hand, the catalyst forms an active center of Ni-Ce-Y-O and adsorbs CH generated by acetic acid activation 3 CO and promote its direction to CH 3 * Iso-intermediate small molecule Conversion (CH) 3 COOH→CH 3 CO*→CH 3 * ) Thereby remarkably inhibiting the formation of carbon precursor such as acetone, ketene and the like, and further improving the yield of hydrogen. At the same time, a pair of unique Ce is obtained through the introduction of Y 4+ /Ce 3 + And Y 3+ /Y 2+ Redox electron pair
Electrons are transferred through a "Ce-O-Y" bridge structure, ce 3+ Oxygen vacancy adsorption O 2 Transmitting electrons to generate O - And Ce (Ce) 4+ At the same time O 2 Also in Y direction 3+ Transmitting electrons to generate O and Y 2+ The flow-through of the oxygen-containing species is further improved. In addition, since the d-orbital electrons of the metal element Ni are unsaturated, and CeO 2 Electron is easy to lose, active component Ni and the catalyst Ce 1-x Y x O 2-δ Solid solution structural body CeO 2 Electron transfer occurs between them to form strong interaction
Ce 3+ An increase in the content (i.e., formation of oxygen vacancies) brings the redox balance toward formation of Ni 0 The species direction is carried out, so that NiO species can be activated, and electron transfer is promoted to form high-activity Ni 0 Species, increased active sites, better adsorption conversion of acetic acid. Finally, BJH pore size distribution diagram (figure 2) analysis shows that the catalyst is a typical mesoporous material, the porous structure of the catalyst is favorable for diffusion and transmission of product molecules and reactant molecules, polymerization of carbon deposition precursor ketene for autothermal reforming of acetic acid is inhibited, and carbon deposition formation is reduced; on the other hand, the introduction of Y increases the specific surface area, pore diameter and pore volume of the catalyst, and the high specific surface area ensures that the active component Ni species are highly dispersed in Ce 1-x Y x O 2-δ The solid solution is supported, so that the catalytic activity of the catalyst for autothermal reforming of acetic acid to produce hydrogen is improved.
The innovation of the catalyst in the aspects of composition and structure improves the carbon deposit resistance and sintering resistance of the catalyst in the autothermal reforming reaction of acetic acid; the activity test result of the catalyst applied to the autothermal reforming reaction of acetic acid also shows that the catalyst has excellent activity, selectivity and stability.
Disclosure of Invention
The invention aims to solve the technical problems of low activity, poor stability, more carbon deposit and no sintering resistance of the existing Ni catalyst in the acetic acid autothermal reforming reaction, and the deactivation of the catalyst, and provides a novel catalyst with stable structure, sintering resistance, carbon deposit resistance and stable activity. The invention takes Ni as an active component, introduces Ce and Y components, synthesizes Y-introduced CeO by adopting a sol-gel method 2 Ce formed by crystal structure 1-x Y x O 2-δ The nickel-based catalyst with solid solution structure forms an active center of Ni-Ce-Y-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 the reaction temperature of 700 ℃, and the hydrogen yield is stable at 2.58mol-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 prepares the cerium-yttrium solid solution structure nickel-based catalyst by a sol-gel method,improves the dispersity of the active components and has the characteristics of sintering resistance, carbon deposit resistance and thermal stability. The composition of the invention is (NiO) a (CeO 2 ) b (YO 1.5 ) c Wherein a is 0.27-0.29, b is 0.51-0.72, c is 0-0.20 and c is not 0; the weight percentage composition in terms of oxide is: the content of nickel oxide (NiO) is 14.2% -16.4%, and cerium oxide (CeO) 2 ) The content is 66.3-85.8 percent, and the Yttrium Oxide (YO) 1.5 ) The content is 0% -17.3% and does not contain 0%, and the sum of the weight percentages of the components is 100%.
The specific preparation and reaction method comprises the following steps:
1) Preparing a mixed solution of metal nitrate: according to the mole ratio (NiO) of each component in the catalyst a (CeO 2 ) b (YO 1.5 ) c Wherein a is 0.27-0.29, b is 0.51-0.72, c is 0-0.20 and c is not 0, respectively weighing a certain amount of nickel nitrate, cerium nitrate and yttrium nitrate, and adding deionized water to prepare a metal salt mixed solution #1;
2) The molar ratio according to the sum of the amounts of citric acid and metal cationic species is 1:1, weighing a certain amount of citric acid, and adding deionized water to prepare a citric acid solution #2; slowly dripping the solution #1 into the solution #2 under the condition of 70 ℃ water bath stirring, and carrying out reaction complexation for 0.5h; according to the mole ratio of glycol to citric acid of 1:1, weighing a proper amount of ethylene glycol, slowly dripping the ethylene glycol into the mixed solution to form sol, maintaining water bath at 60 ℃ and stirring for 3 hours to form gel, then placing the gel in a baking oven at 60 ℃ for drying for 6 hours to remove water, and then raising the temperature to 105 ℃ for foaming;
3) Placing the dried sample obtained in the step 2) into a tube furnace, heating to 700 ℃ at a heating rate of 10 ℃/min, and keeping for 4 hours to obtain the cerium-yttrium solid solution structured nickel-based catalyst, wherein the typical crystal form structure is shown as an X-ray diffraction pattern (figure 1), and the characteristic is that the CeO is introduced into the component Y 2 The crystal structure forms NiO to be loaded on the cubic phase Ce 1-x Y x O 2-δ The solid solution structure is subjected to hydrogen reduction treatment, and the X-ray diffraction diagram of the sample is shown in figure 3, so that Ni metal particles with mesoporous structure are formedEmbedded cubic phase Ce 1-x Y x O 2-δ Ni/Ce taking Ni-Ce-Y-O as active center on solid solution carrier 1-x Y x O 2-δ The typical mesoporous BJH pore size distribution of the cerium yttrium solid solution structured nickel-based catalyst is shown in figure 2;
4) The catalyst obtained is reacted at 600-800 ℃ under H 2 The intermediate reduction is carried out for 1h, nitrogen is used as carrier gas for reaction, mixed gas with the molar ratio of acetic acid/water/oxygen=1/(1.3-5.0)/(0.2-0.5) is introduced, and the 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 invention takes Ni as an active component, introduces Ce component and Y component, creates Ce with Ni-Ce-Y-O as an active center 1-x Y x O 2-δ Solid solution structured catalysts. The inventors introduced Y into CeO 2 In which a cubic phase Ce is formed 1-x Y x O 2-δ Solid solution structure, proved by DFT theoretical calculation results of the inventor, significantly changes CeO 2 The relaxation structure of (2) shortens the bond length of the part of Ce-O in solid solution, reduces the binding capacity to oxygen, reduces the oxygen vacancy forming energy and obviously weakens Ce 1-x Y x O 2-δ The combination of the oxygen on the surface of the solid solution and the lattice oxygen in the carrier accelerates the migration of O in the reaction process; meanwhile, when an oxygen vacancy of the upper layer is formed, the lower layer Ce-O is driven to break, so that an oxygen atmosphere is continuously provided; at the same time, compared with pure CeO 2 The introduction of Y significantly reduces Ce 1-x Y x O 2-δ The adsorption energy of the carrier to acetic acid effectively improves the adsorption capacity of the catalyst to acetic acid, improves the acetic acid conversion rate, and simultaneously can increase CH generated by adsorbing and activating acetic acid by the active center of Ni-Ce-Y-O 3 CO and promote its direction to CH 3 * Iso-intermediate small molecule Conversion (CH) 3 COOH→CH 3 CO*→CH 3 * ) Thereby remarkably inhibiting the formation of carbon precursor such as acetone and ketene, further improving the yield of hydrogen, reducing the influence of carbon deposition on the activity of the catalyst and remarkably improving the activity of the catalyst.
2) Ce constructed according to the invention 1-x Y x O 2-δ Solid solution structured catalyst, ceO is changed by introducing Y 2 The formation of oxygen vacancies is also effectively promoted. This is due to Y 3+ And Ce (Ce) 4+ The ionic radii of (a) are respectively
And->
Y of smaller radius 3+ Entering CeO 2 The lattice spacing and lattice shrinkage are reduced when the unit cell is formed, and the unit cell parameters are changed from those before Y is not introduced
Reduced to->
This makes the space atoms more active (calculated as the optimal catalyst CDUT-NCY 10), improving electron transfer properties. In addition, Y 3+ Substituted part Ce 4+ The post-formation of lattice defects increases oxygen vacancies, on the one hand, promotes the release of lattice oxygen, so that the influence of the C species covering the surface of the active site on the catalyst activity is reduced (c+o→co, c+2o→co) 2 ) Meanwhile, the method is also beneficial to eliminating carbon deposit on the surface of the catalyst; on the other hand, oxygen vacancies can capture gaseous oxygen molecules, forming more active surface oxygen species, resulting in an increased concentration of surface oxygen species, which further increases the anti-coking capacity of the catalyst.
3) The invention obtains the unique Ce through the introduction of Y 4+ /Ce 3+ And Y 3+ /Y 2+ Redox electron pair
The electron donating ability of Y is stronger to lead electrons to Ce 4+ Enrichment of Ce 4+ Reduction to Ce 3 + And Ce (Ce) 3+ The higher the concentration of ions, the greater the proportion of oxygen vacancies, indicating that the introduction of Y significantly increases the electron transfer efficiency; in addition, oxygen ions can be transferred through the redox electron pair, so that oxygen in the air phase is promoted to be adsorbed on oxygen vacancies to generate O - Isoxygen species, via Ce 3+ To O - Electron transfer to form O 2- Whereas CeO 2 By releasing O 2- The Ce valence state is reduced so as to regenerate oxygen vacancies, thus further improving the oxygen mobility, constructing oxygen circulation in the catalyst and keeping the whole catalyst in the oxidation-reduction atmosphere all the time; finally, Y in solid solution 3+ Ion simultaneous orientation Ni 2+ Electrons are transferred, so that more Ni can be reduced, the problem that Ni is difficult to reduce is solved, and meanwhile, the oxidation resistance of the catalyst is improved.
4) The invention is implemented on CeO 2 On introduction of Y component to form Ce 1-x Y x O 2-δ Solid solution, ce 1-x Y x O 2-δ Solid solution as carrier to load active component Ni particles, and a large number of oxygen vacancies generated near the Ni particles can be used as O 2- Is of origin of O 2- The anti-overflow of ions on the surface of Ni metal particles makes them build up an oxygen charge layer [ O ] around the Ni metal particles δ- ，δ + ]Flowing O species and char precursor CH generated during autothermal reforming of acetic acid x (x=0-3) in combination, promotes gasification of char and reduces by-product CH 4 And CO, thereby achieving the effect of cleaning the carbon deposit on the surface of the catalyst. In addition, excess O 2- Anti-overflow results in double layer [ O ] δ- ，δ + ]Is formed of double layer [ O δ- ，δ + ]Providing the Ni species with a net negative charge, resulting in electrostatic repulsion between Ni metal particles, helps control Ni particle size, and thus enhances the sintering resistance of the catalyst.
5) The result of the autothermal reforming reaction of acetic acid shows that the catalyst of the invention can realize the efficient conversion of acetic acid in the acetic acid conversion process, the conversion rate of acetic acid (HAc) is close to 100 percent, and the hydrogen yield is stable at 2.58mol-H 2 /mol-HAc and so on. And the methanation and acetonation reactions in the reforming reaction can be effectively inhibited, and the catalyst has the characteristics of carbon deposition resistance, stable activity and the like.
Drawings
Fig. 1: x-ray diffraction pattern of the roasted catalyst
Fig. 2: BJH pore size distribution diagram of the catalyst of the invention
Fig. 3: x-ray diffraction pattern of the catalyst after reduction treatment
Detailed Description
Reference example 1
2.329g of Ni (NO) 3 ) 2 ·6H 2 O, 8.075g of Ce (NO) 3 ) 3 ·6H 2 O and 0.339g of Y (NO) 3 ) 3 ·6H 2 O, adding 27ml of deionized water to prepare a solution #1; weighing 5.775g of citric acid in a 250ml beaker, adding 27ml of deionized water, stirring and dissolving by using a magnetic stirrer to prepare solution #2; placing the solution #2 in a water bath at 70 ℃ for stirring, slowly dripping the solution #1 into the solution #2, and carrying out reaction complexation for 0.5h; weighing 1.706g of ethylene glycol solution, slowly dripping the ethylene glycol solution into the mixed solution, stirring the mixed solution for 3 hours in a constant-temperature water bath at 60 ℃ to form gel, placing the gel into an oven at 60 ℃ to dry for 6 hours, and then raising the temperature to 105 ℃ to foam; and (3) grinding the dried and foamed sample, placing the ground sample into a tube furnace, heating to 700 ℃ at a heating speed of 10 ℃/min, and continuously roasting for 4 hours to obtain the CDUT-NCY5 catalyst. The catalyst has the molar composition (NiO) 0.28 (CeO 2 ) 0.66 (YO 1.5 ) 0.06 The weight percentage composition in terms of oxide is: the nickel oxide is 14.8%, the cerium oxide is 80.3%, and the yttrium oxide is 4.9%.
Performing activity evaluation of acetic acid autothermal reforming reaction in a continuous flow fixed reactor, grinding, tabletting and crushing the catalyst, sieving to obtain catalyst particles of 20-40 meshes, weighing 0.1-0.2g, putting into the reactor, and reducing in a hydrogen atmosphere at 700 ℃ for 1h; then injecting the acetic acid-water mixed solution into a vaporizer by a high-pressure constant-flow pump for vaporization, mixing oxygen and taking nitrogen as an internal standard gas to form a catalyst with the molar ratio of CH 3 COOH/H 2 O/O 2 The reaction raw material gas of 1/(1.3-5.0)/(0.2-0.5) is led into the reaction bed layer of the fixed bed reactor, the reaction condition is 600-800 ℃, the normal pressure and the space velocity are 10000-80000 ml/(g-catalyst.h), and the reaction tail gas is analyzed on line by a gas chromatograph.
The activity of the CDUT-NCY5 catalyst is examined through acetic acid autothermal reforming reaction, the reaction temperature is 700 ℃, the reaction space velocity is 50667 mL/(g-catalyst h), and the feeding mole ratio is CH 3 COOH/H 2 O/O 2 =1/4.0/0.28. The catalyst had an initial conversion of acetic acid of 100% and then dropped to 88% and a hydrogen yield of 2.01mol-H 2 /mol-HAc，CO 2 And the selectivity of CO is about 63% and 35% respectively, and the selectivity of byproduct methane is about 1.2%, so that a small amount of byproduct acetone is generated; the CDUT-NCY5 catalyst is subjected to nitrogen low-temperature physical adsorption characterization, and the result is that: specific surface area of 9.6m 2 Per gram, pore volume of 0.068cm 3 The average pore diameter was 11.6nm.
Example 1
2.329g of Ni (NO) 3 ) 2 ·6H 2 O, 7.570g of Ce (NO) 3 ) 3 ·6H 2 O and 0.679g of Y (NO) 3 ) 3 ·6H 2 O, adding 27ml of deionized water to prepare a solution #1; weighing 5.717g of citric acid in a 250ml beaker, adding 27ml of deionized water, stirring and dissolving by using a magnetic stirrer to prepare solution #2; placing the solution #2 in a water bath at 70 ℃ for stirring, slowly dripping the solution #1 into the solution #2, and carrying out reaction complexation for 0.5h; 1.689g of ethylene glycol solution is weighed, slowly added into the mixed solution in a dropwise manner, stirred for 3 hours in a constant-temperature water bath at 60 ℃ to form gel, and then placed into an oven at 60 ℃ to be dried for 6 hours; then raising the temperature to 105 ℃ for foaming; grinding the dried and foamed sample, placing the ground sample into a tube furnace, heating to 700 ℃ at a heating speed of 10 ℃/min, and continuously roasting for 4 hours to form nickel oxide species loaded on Y and introduced with CeO 2 Cubic phase c-Ce formed by lattice 1-x Y x O 2-δ Solid solution structure, whose typical crystal form structure is shown in figure 1, has strong cubic phase c-Ce at 28.6 °, 33.1 °, 47.6 °, 56.5 °, 59.2 °, 69.6 °, 76.9 ° and 79.3 ° 1-x Y x O 2-δ Characteristic peaks; after the sample is reduced in hydrogen, the crystal form structure is shown in figure 3, and the cubic phase c-Ce 1-x Y x O 2-δ The characteristic peak remained stable, while being based on Ni at 44.5 DEG 0 Peak, through Shelle formula calculation, reduced Ni is obtained 0 The particle diameter of the catalyst is only 21.3nm, which indicates that the Ni metal particles of the active component are highly dispersed in the cubic phase Ce of the catalyst 1-x Y x O 2-δ On the solid solution carrier, ni metal particles are embedded into Ce 1-x Y x O 2-δ Ni/Ce taking Ni-Ce-Y-O as active center on solid solution carrier 1-x Y x O 2-δ The cerium yttrium solid solution structured nickel-based catalyst is the catalyst CDUT-NCY10. The inventor carries out DFT simulation calculation, and the result shows that Y introduces CeO 2 Ce formed after lattice 1-x Y x O 2-δ The solid solution structure has the advantages that the adsorption energy of acetic acid is reduced to 58kJ/mol from 88kJ/mol before the acetic acid is not introduced, and the oxygen vacancy formation energy is reduced to 34kJ/mol from 121kJ/mol before the acetic acid is not introduced, so that the catalyst has good acetic acid adsorption capacity, can promote the adsorption and activation of oxygen species, and has strong carbon deposit resistance. The CDUT-NCY10 catalyst is subjected to nitrogen low-temperature physical adsorption characterization, and the result is that: specific surface area of 15.4m 2 Per gram, pore volume of 0.111cm 3 And/g, the average pore diameter is 12.5nm, and a mesoporous structure is formed, and the typical mesoporous structure characteristics are shown in figure 2. The CDUT-NCY10 catalyst has the molar composition of (NiO) 0.27 (CeO 2 ) 0.60 (YO 1.5 ) 0.13 The weight percentage composition in terms of oxide is: the nickel oxide is 14.8%, the cerium oxide is 74.8%, and the yttrium oxide is 10.4%.
The activity of the CDUT-NCY10 catalyst is examined through acetic acid autothermal reforming reaction, the reaction temperature is 700 ℃, the reaction space velocity is 50667 mL/(g-catalyst h), and the feeding mole ratio is CH 3 COOH/H 2 O/O 2 =1/4.0/0.28. The catalyst has the acetic acid conversion rate stabilized at 100% and the hydrogen yield at 2.58mol-H 2 about/mol-HAc, CO 2 The selectivity of (2) is about 62%, the selectivity of CO is about 33%, and no byproducts methane and acetone are generated.
Example two
2.329g of Ni (NO) 3 ) 2 ·6H 2 O, 7.065g of Ce (NO) 3 ) 3 ·6H 2 O and 1.018g of Y (NO) 3 ) 3 ·6H 2 O, adding 27ml of deionized water to prepare a solution #1; weighing 5.659g of citric acid in a 250ml beaker, adding 27ml of deionized water, stirring and dissolving by using a magnetic stirrer to prepare solution #2; placing the solution #2 in a water bath at 70 ℃ for stirring, slowly dripping the solution #1 into the solution #2, and carrying out reaction complexation for 0.5h; 1.672g of ethylene glycol solution is weighed, slowly added into the mixed solution in a dropwise manner, stirred for 3 hours in a constant-temperature water bath at 60 ℃ to form gel, and then placed into an oven at 60 ℃ to be dried for 6 hours; then raising the temperature to 105 ℃ for foaming; grinding the dried and foamed sample, placing the ground sample into a tube furnace, heating to 700 ℃ at a heating speed of 10 ℃/min, continuously roasting for 4 hours, and dispersing nickel metal particles into a cubic phase Ce after reduction 1-x Y x O 2-δ The nickel-based catalyst with a solid solution structure and an active center structure of Ni-Ce-Y-O, namely a CDUT-NCY15 catalyst. The catalyst has the molar composition (NiO) 0.27 (CeO 2 ) 0.55 (YO 1.5 ) 0.18 The weight percentage composition in terms of oxide is: the nickel oxide is 14.8%, the cerium oxide is 70.0%, and the yttrium oxide is 15.2%.
The activity of the CDUT-NCY15 catalyst is examined through acetic acid autothermal reforming reaction, the reaction temperature is 700 ℃, the reaction space velocity is 50667 mL/(g-catalyst h), and the feeding mole ratio is CH 3 COOH/H 2 O/O 2 =1/4.0/0.28. The acetic acid conversion rate of the catalyst reaches 94.2 percent, and the hydrogen yield reaches 2.19mol-H 2 /mol-HAc，CO 2 The selectivity is about 60%, the CO selectivity is about 38%, the methane selectivity is about 2%, and no byproduct methane acetone is generated; the CDUT-NCY15 catalyst is subjected to nitrogen low-temperature physical adsorption characterization, and the result is that: specific surface area of 7.1m 2 Per gram, pore volume of 0.042cm 3 The average pore diameter was 9.9nm.
Claims (3)
1. Cerium yttrium solid solution nickel-based catalyst in acetic acidThe application in the process of autothermal reforming is characterized in that: the catalyst is subjected to H at 600-800 DEG C 2 Reducing for 1h in atmosphere, introducing the molar ratio of CH 3 COOH/H 2 O/O 2 The mixed gas of 1/(1.3-5.0)/(0.2-0.5) is subjected to acetic acid autothermal reforming reaction through a catalyst bed, and the reaction temperature is 600-800 ℃; the preparation method of the catalyst comprises the following steps: according to chemical composition, nickel nitrate, cerium nitrate and yttrium nitrate are dissolved in deionized water to prepare a metal salt solution #1; preparing citric acid solution #2 according to the mole ratio of citric acid to the sum of the amounts of metal cation substances of 1:1; slowly dripping the solution #1 into the solution #2 under the condition of 70 ℃ water bath stirring, and carrying out reaction complexation for 0.5h; according to the mol ratio of glycol to citric acid being 1:1, weighing glycol and slowly dripping the glycol into the mixed solution to form sol, maintaining water bath at 60 ℃ for stirring for 3 hours to form gel, then drying the gel in an oven at 60 ℃ for 6 hours to remove water, heating the temperature to 105 ℃ for foaming, heating the obtained dried sample in a tube furnace to 700 ℃ at a heating speed of 10 ℃/min, and keeping the temperature for 4 hours to obtain Y-introduced CeO 2 Lattice formation of NiO supported on Ce 1-x Y x O 2-δ Solid solution structure, after hydrogen reduction, ni metal particles with mesoporous structure are formed to be embedded into Ce 1-x Y x O 2-δ Ni/Ce taking Ni-Ce-Y-O as active center on solid solution carrier 1-x Y x O 2-δ Nickel-based catalyst with cerium yttrium solid solution structure and chemical composition of (NiO) a (CeO 2 ) b (YO 1.5 ) c Wherein a is 0.27-0.29, b is 0.51-0.72, c is 0-0.20 and c is not 0; the weight percentage composition in terms of oxide is: the nickel oxide NiO is 14.2-16.4%, and the cerium oxide CeO 2 66.3-85.8 percent of yttrium oxide YO 1.5 0% -17.3% and not 0%, and the sum of the weight percentages of the components is 100%.
2. The use of the cerium yttrium solid solution nickel-based catalyst according to claim 1 in the autothermal reforming of acetic acid to produce hydrogen, characterized in that: the catalyst comprises the following components in percentage by weight in terms of oxide: the nickel oxide is 14.8%, the cerium oxide is 74.8%, and the yttrium oxide is 10.4%.
3. The use of the cerium yttrium solid solution nickel-based catalyst according to claim 1 in the autothermal reforming of acetic acid to produce hydrogen, characterized in that: the catalyst comprises the following components in percentage by weight in terms of oxide: the nickel oxide is 14.8%, the cerium oxide is 70.0%, and the yttrium oxide is 15.2%.
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