CN115385401B - Porous three-dimensional reticular structure lanthanum iron nickel perovskite material, preparation method and application thereof - Google Patents
Porous three-dimensional reticular structure lanthanum iron nickel perovskite material, preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 99
- WSZBCXXFBOTXDC-UHFFFAOYSA-N [Fe].[Ni].[La] Chemical compound [Fe].[Ni].[La] WSZBCXXFBOTXDC-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 168
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 54
- 229910052760 oxygen Inorganic materials 0.000 claims description 54
- 239000001301 oxygen Substances 0.000 claims description 54
- 238000010438 heat treatment Methods 0.000 claims description 29
- 150000002815 nickel Chemical class 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 16
- 150000002603 lanthanum Chemical class 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 150000002505 iron Chemical class 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 5
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical group O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 3
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical group O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 claims description 3
- 229960004106 citric acid Drugs 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 38
- 239000000047 product Substances 0.000 abstract description 26
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 239000012265 solid product Substances 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 4
- 239000002041 carbon nanotube Substances 0.000 abstract description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 34
- 238000001833 catalytic reforming Methods 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 238000001816 cooling Methods 0.000 description 15
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- 239000012071 phase Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 239000002243 precursor Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
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- 238000010521 absorption reaction Methods 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011240 wet gel Substances 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 150000004706 metal oxides Chemical group 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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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
- 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
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- B01J35/394—
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- B01J35/40—
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- B01J35/56—
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- B01J35/60—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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Abstract
The invention belongs to the technical field of composite catalysis, and particularly relates to a porous three-dimensional reticular structure lanthanum iron nickel perovskite material, a preparation method and application thereof. The porous three-dimensional reticular lanthanum iron nickel perovskite material provided by the invention has the advantages of high stability, good catalytic performance, stable toluene removal effect, high purity and low impurity content. The results of the examples show that the porous three-dimensional reticular lanthanum iron nickel perovskite material provided by the invention has good toluene removal rate and three-phase product controllability in catalytic cracking, the toluene conversion rate is kept above 82.275%, the yield of easily recovered condensable components can reach 89.304% of the total mass of the product, the yield of solid products and gas products produced by catalytic cracking is small, and only a small amount of harmless noncondensable gas and solid carbon nanotubes are produced.
Description
Technical Field
The invention belongs to the technical field of composite catalysis, and particularly relates to a porous three-dimensional reticular structure lanthanum iron nickel perovskite material, a preparation method and application thereof.
Background
Toluene is a highly carbonaceous aromatic hydrocarbon compound, is flammable and can form an explosive mixture with steam or air, and meanwhile, has low toxicity and carcinogenic properties, is widely used in pyrolysis oil gas, and is often used as a tar model compound for evaluating the performance of a catalyst in catalyzing reforming tar. In order to reduce the impact of toluene on the environment and equipment operation stability, it is necessary to purify and treat the toluene.
Perovskite oxides have unique adjustable volume and various surface characteristics, have been widely applied to the fields of photocatalysis, electrocatalysis, catalytic oxidation and the like, and have good effects in the aspects of organic matter degradation, methane and carbon dioxide reforming, VOCs high-efficiency removal and the like. The perovskite oxide has a regular octahedral structure, so that the atom positions can be effectively limited, the active metal particles with good dispersion can reduce the formation of larger metal clusters on the surface of the catalyst, and the sintering of the deposited carbon and active metal atoms is effectively avoided; the perovskite catalyst has high thermal stability in a wide temperature range, so that the service life of the catalyst is longer, and the use cost is reduced; the perovskite oxide has good lattice oxygen migration and conversion capability, can realize the effective removal of carbon deposited on the surface of the material, and can be used for the regeneration of oxygen or air in the environment when the oxygen-deficient non-stoichiometric ratio exists in the perovskite oxide.
The existing perovskite catalyst for catalytic reforming of toluene mainly realizes catalytic oxidation or steam reforming of toluene under the condition of introducing oxygen or steam as a gasifying agent so as to obtain high-heat-value combustible gas. However, pyrolysis oil gas components are complex, sulfur-containing and nitrogen-containing gas components can affect the catalytic stability of the existing catalytic reforming technology, and the toluene removal rate is unstable.
Disclosure of Invention
The invention aims to provide a porous three-dimensional network lanthanum-iron-nickel perovskite material, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a porous three-dimensional reticular structure lanthanum iron nickel perovskite material, which comprises the following steps:
(1) Heating and mixing soluble lanthanum salt, soluble nickel salt, soluble ferric salt, dispersing agent and water to obtain premix;
(2) Adding the premix into a closed container, heating to perform hydrothermal reaction to obtain suspension;
(3) And sequentially carrying out solid-liquid separation and calcination on the suspension to obtain the porous three-dimensional reticular lanthanum iron nickel perovskite material.
Preferably, the mass ratio of the soluble lanthanum salt to the soluble nickel salt is 2.14-21.4:1; the mass ratio of the soluble nickel salt to the soluble iron salt is 0.068-5.544:1.
Preferably, the ratio of the dispersant to the total molar amount of the soluble lanthanum salt, the soluble iron salt and the soluble nickel salt is 1-1.5:1; the ratio of the total molar amount of the water to the soluble lanthanum salt, the soluble iron salt and the soluble nickel salt is 20-60:1.
Preferably, the temperature of the hydrothermal reaction is 170-190 ℃, and the heat preservation time is 9-10 h.
Preferably, the calcining temperature is 700-1000 ℃ and the heat preservation time is 2-6 h.
Preferably, the soluble lanthanum salt is lanthanum nitrate hexahydrate; the soluble nickel salt is nickel acetate tetrahydrate; the soluble ferric salt is ferric nitrate nonahydrate.
Preferably, the heating and mixing are performed under the condition of stirring, the stirring speed is 400-500 r/min, the heating and mixing comprises a first stage and a second stage which are sequentially performed, the temperature of the first stage is room temperature, the time is 30-90 min, the temperature of the second stage is 45-60 ℃, and the time is 30-60 min.
The invention also provides the porous three-dimensional network lanthanum-iron-nickel perovskite material obtained by the preparation method, wherein the surface of the porous three-dimensional network lanthanum-iron-nickel perovskite material contains oxygen species, the oxygen species comprise adsorbed oxygen and lattice oxygen, the adsorbed oxygen accounts for 58.5-58.7% of the total amount of the oxygen species, and the lattice oxygen accounts for 37.6-37.8% of the total amount of the oxygen species.
The invention also provides application of the porous three-dimensional reticular lanthanum iron nickel perovskite material in catalytic cracking of toluene.
Preferably, the toluene concentration is 400g/Nm or less 3 The catalytic cracking temperature is more than or equal to 700 ℃.
The invention provides a preparation method of a porous three-dimensional reticular structure lanthanum iron nickel perovskite material. According to the invention, the porous three-dimensional network lanthanum-iron-nickel perovskite material is prepared by a solvothermal method, and the dispersibility of the metal active component in the preparation process is improved by the high dispersion and expansion characteristics of the hot solvent in the closed space, so that the hard agglomeration phenomenon of particles is avoided, the construction of the porous three-dimensional network lanthanum-iron-nickel perovskite material is promoted, and the catalytic performance of the catalytic material is improved; meanwhile, the high-concentration liquid phase reaction space improves the crystallinity and dispersity of the material, so that the particle size of the catalytic material is reduced and stabilized to be within the range of 100-200 nm, and solvent oxygen in the liquid phase can further participate in the construction of crystals and is converted into material lattice oxygen and surface adsorption oxygen; in addition, the preparation method provided by the invention is safe and efficient, simple in steps and convenient to operate.
The invention also provides the porous three-dimensional network lanthanum-iron-nickel perovskite material obtained by the preparation method, wherein the surface of the porous three-dimensional network lanthanum-iron-nickel perovskite material contains oxygen species, the oxygen species comprise adsorbed oxygen and lattice oxygen, the adsorbed oxygen accounts for 58.5-58.7% of the total amount of the oxygen species, and the lattice oxygen accounts for 37.6-37.8% of the total amount of the oxygen species. The porous three-dimensional network lanthanum iron nickel perovskite material provided by the invention has a uniform, stable and regular controllable porous three-dimensional network perovskite structure, a crystal network is composed of 100-200 nm uniform particles, the surface of the material is rich in adsorbed oxygen and crystallized oxygen species, the adsorbed oxygen accounts for 58.59% of the total amount of oxygen species, the lattice oxygen accounts for 37.66% of the total amount of oxygen species, the oxygen species can participate in a toluene catalytic oxidation process and a material surface carbon deposition removal process, the gas production process in the toluene catalytic reforming process is limited by the specific particle size of the porous three-dimensional network lanthanum iron nickel perovskite material and the rich surface adsorbed oxygen, the generation of solid products is reduced, the catalytic cracking toluene is converted into small molecular organic matters, the yield ratio of easily-recovered condensable components produced by catalytic reforming toluene is improved, and the selective regulation of three-phase products is realized. The porous three-dimensional reticular lanthanum iron nickel perovskite material provided by the invention has the advantages of high stability, good catalytic performance, stable toluene removal effect, high purity and low impurity content.
The invention also provides application of the porous three-dimensional reticular lanthanum iron nickel perovskite material in catalytic cracking of toluene. The porous three-dimensional network lanthanum iron nickel perovskite material provided by the invention has good catalytic stability and catalytic activity when being used for catalytic cracking of toluene, and the selectivity of three-phase products and gas products of the catalytic cracking of toluene does not obviously fluctuate or change in a 24-hour continuous experiment at 700 ℃, so that the porous three-dimensional network lanthanum iron nickel perovskite material has obvious advantages in catalytic stability. In addition, the porous three-dimensional reticular lanthanum iron nickel perovskite material provided by the invention has good toluene removal rate and three-phase product controllability, the toluene conversion rate is kept above 82.275%, the yield of easily recovered condensable components can reach 89.304% of the total mass of the product, the yield of solid products and gas products produced by catalytic pyrolysis is small, only a small amount of harmless noncondensable gas and solid carbon nanotubes are produced, the environment is not polluted and harmfulness is not possessed, and the porous three-dimensional reticular lanthanum iron nickel perovskite material has good application and popularization prospects.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern of a porous three-dimensional network lanthanum iron nickel perovskite material prepared in example 1 of the invention;
FIG. 2 is an SEM image of a porous three-dimensional network lanthanum iron nickel perovskite material prepared according to example 1 of the present invention;
FIG. 3 is an XPS test oxygen species spectrum of a porous three-dimensional network lanthanum iron nickel perovskite material prepared by example 1 of the invention;
FIG. 4 shows the toluene conversion rate and the total three-phase product yield of 24h catalytic reforming of the porous three-dimensional network lanthanum-iron-nickel perovskite material prepared in example 1 of the invention;
FIG. 5 shows the relative volume ratio (within 24 h) of each component of the catalytic reforming toluene oil gas synthesis gas of the porous three-dimensional network lanthanum iron nickel perovskite material prepared in the embodiment 1 of the invention;
FIG. 6 shows a porous three-dimensional network lanthanum-iron-nickel perovskite material prepared according to example 1 of the invention and LaFe prepared according to comparative example 1 0.5 Ni 0.5 O 3 SEM profile of catalytic material.
Detailed Description
The invention provides a preparation method of a porous three-dimensional reticular structure lanthanum iron nickel perovskite material, which comprises the following steps:
(1) Heating and mixing soluble lanthanum salt, soluble nickel salt, soluble ferric salt, dispersing agent and water to obtain premix;
(2) Adding the premix into a closed container, heating to perform hydrothermal reaction to obtain suspension;
(3) And sequentially carrying out solid-liquid separation and calcination on the suspension to obtain the porous three-dimensional reticular lanthanum iron nickel perovskite material.
The invention heats and mixes the soluble lanthanum salt, the soluble nickel salt, the soluble ferric salt, the dispersing agent and the water to obtain the premix. In the present invention, the soluble lanthanum salt is preferably lanthanum nitrate hexahydrate; the soluble nickel salt is preferably nickel acetate tetrahydrate; the soluble iron salt is preferably ferric nitrate nonahydrate; the dispersant preferably comprises one or both of citric acid monohydrate and citric acid; the water is preferably distilled water; the mass ratio of the soluble lanthanum salt to the soluble nickel salt is preferably 2.14-21.4:1, more preferably 4.2-4.4:1; the mass ratio of the soluble nickel salt to the soluble iron salt is preferably 0.068-5.544:1, more preferably 0.60-0.63:1; the ratio of the dispersant to the total molar amount of the soluble lanthanum salt, the soluble iron salt and the soluble nickel salt is preferably 1 to 1.5:1, more preferably 1.2 to 1.5:1, and even more preferably 1.5:1; the ratio of the water to the total molar amount of soluble lanthanum salt, soluble iron salt and soluble nickel salt is preferably 20 to 60:1, more preferably 25 to 30:1. In the specific embodiment of the invention, the adopted nickel acetate tetrahydrate is a non-explosive drug, has low cost, and can strengthen the dispersibility of nickel salt in water phase by combining the nickel acetate tetrahydrate and a dispersing agent so as to obtain the catalytic material with high purity and uniform active component distribution. In the specific embodiment of the invention, the addition proportion of the dispersing agent is limited, so that the dispersibility of the metal salt precursor in water can be enhanced, other links for enhancing the dispersibility of the metal salt are reduced, meanwhile, other additives except the dispersing agent are not required to be added, pH adjustment is not required, the use of alkali is reduced, the introduction of other elements is avoided, and the safety of the preparation process and the purity of the porous three-dimensional reticular lanthanum iron nickel perovskite material are improved. The porous three-dimensional reticular lanthanum-iron-nickel perovskite material provided by the invention has a perovskite structure, and the limited nickel-iron atomic ratio is favorable for forming nickel-iron alloy in the reaction process of the material, so that the material has high activity and strong stability.
In the present invention, the heating and mixing means is preferably stirring; the stirring speed is preferably 400-500 r/min, more preferably 420-460 r/min; the heated mixing preferably comprises a first stage and a second stage which are carried out sequentially; the temperature of the first stage is preferably room temperature, and the time is preferably 30-90 min, more preferably 45-70 min; the temperature of the second stage is preferably 45 to 60 ℃, more preferably 50 to 55 ℃, and the time is preferably 30 to 60min, more preferably 30 to 45min. In the present invention, the premixed liquid is preferably cooled after the heating and mixing are finished; the final temperature of the cooling is preferably room temperature; the cooling is preferably natural cooling. In the specific embodiment of the invention, the stirring speed is adopted to continuously stir, so that the dispersibility of the metal salt in the water phase is improved, element aggregation is avoided, and the dispersibility of the generated material elements is improved.
After the premix is obtained, the premix is added into a closed container to be heated for hydrothermal reaction, so that a suspension is obtained. In the present invention, the temperature of the hydrothermal reaction is preferably 170 to 190 ℃, more preferably 180 to 185 ℃, and the holding time is preferably 9 to 10 hours, more preferably 9 to 9.5 hours.
After the suspension is obtained, the suspension is subjected to solid-liquid separation and calcination in sequence, so that the porous three-dimensional reticular structure lanthanum iron nickel perovskite material is obtained. In the present invention, the separation method is preferably centrifugation; the number of times of the centrifugation is preferably 3 to 4 times, more preferably 4 times, to rapidly obtain a uniform precipitated component; the rotation speed of the centrifugation is preferably 4000-4500 r/min, more preferably 4200-4500 r/min, and the time is preferably 10-15 min, more preferably 12-15 min; after each centrifugation, the solid product obtained is preferably washed; after the last centrifugation is completed, preferably drying the obtained washed solid product to obtain a dry substance; the washing reagent is preferably water and ethanol; the drying is preferably drying; the drying device is preferably a blast drying oven; the drying temperature is preferably 100 to 105 ℃, more preferably 105 ℃, and the drying time is preferably 18 to 24 hours, more preferably 20 to 22 hours.
In the present invention, the calcination temperature is preferably 700 to 1000 ℃, more preferably 800 to 900 ℃, and the holding time is preferably 2 to 6 hours, more preferably 2 to 4 hours. In the present invention, the calcination preferably includes: heating a muffle furnace to a calcination temperature for calcination, and cooling and grinding sequentially after the calcination is finished; the final temperature of the cooling is preferably room temperature; the cooling mode is preferably natural cooling. The invention is helpful for the evacuation of gas in porous three-dimensional network structure lanthanum iron nickel perovskite material pore canal and the formation of composite metal oxide structure through calcination.
The invention also provides the porous three-dimensional network lanthanum-iron-nickel perovskite material obtained by the preparation method, and the surface of the porous three-dimensional network lanthanum-iron-nickel perovskite material contains oxygen species, wherein the oxygen species comprise 58.5-58.7% of adsorbed oxygen and 37.6-37.8% of lattice oxygen. In the present invention, the oxygen species includes adsorbed oxygen of 58.5 to 58.7%, preferably 58.59%; the oxygen species comprises from 37.6 to 37.8%, preferably 37.66% lattice oxygen. In the invention, the porous three-dimensional network lanthanum-iron-nickel perovskite material is preferably LaFe 0.5 Ni 0.5 O 3 。
The invention also provides application of the porous three-dimensional reticular lanthanum iron nickel perovskite material in catalytic cracking of toluene.
In the present invention, the application preferably includes:adding the porous three-dimensional reticular lanthanum iron nickel perovskite material into a vertical quartz tube, and then introducing carrier gas and toluene oil gas to carry out catalytic reforming reaction. In the invention, the molar ratio of the porous three-dimensional network lanthanum iron nickel perovskite material to the toluene oil gas is preferably 0.52-0.53:1, more preferably 0.524-0.526:1; the carrier gas is preferably nitrogen; the flow rate of the carrier gas is preferably 100 to 300SCCM, more preferably 150SCCM; the flow rate of the toluene vapor is preferably 3.5-3.7 g/h, more preferably 3.6L/h; the toluene concentration in the toluene oil gas is preferably less than or equal to 400g/Nm 3 More preferably 50 to 400g/Nm 3 The method comprises the steps of carrying out a first treatment on the surface of the The toluene oil gas is preferably continuously fed through a syringe pump with pipeline auxiliary heat, and the temperature of the feed is preferably 180-250 ℃, more preferably 190-210 ℃; the temperature of the catalytic reforming reaction is preferably more than or equal to 700 ℃, more preferably 700-900 ℃, and even more preferably 750-850 ℃; the temperature of the catalytic reforming reaction is preferably controlled by a vertical tube furnace, and the temperature of the catalyst layer in the vertical quartz tube is preferably constant at the temperature of the catalytic reforming reaction. In the present invention, the post-treatment is preferably performed after the catalytic reforming reaction is completed; the post-treatment preferably comprises: absorbing unreacted toluene by an absorption liquid; the absorption liquid preferably comprises one or two of methanol and n-hexane.
At the temperature limiting the catalytic reforming reaction, the yield of solid products and gas products generated by the catalytic reforming is low, and the toluene conversion rate is high; when the temperature is too high, the proportion of the gaseous products which are liable to cause catalytic cracking is increased, and when the temperature is too low, the toluene conversion rate is reduced.
The following detailed description of the embodiments of the invention is provided in connection with the accompanying drawings and examples to further illustrate the invention, but should not be construed as limiting the scope of the invention.
Example 1
Preparation method of porous three-dimensional reticular lanthanum-iron-nickel perovskite material, and 50mmol LaFe is prepared 0.5 Ni 0.5 O 3 The preparation steps of the catalytic material are as follows:
(1) 21.6505g were added sequentially to 50mL of distilled waterLa (NO) 3 ) 3 ·6H 2 O, 10.1000g of Fe (NO) 3 ) 3 ·9H 2 O, 6.2210g of Ni (CH) 3 COO) 2 ·4H 2 O and 30.0g citric acid monohydrate, and stirring the mixture at a constant speed for 30min under the condition of 430r/min to obtain a homogeneous precursor solution;
(2) Continuously heating the homogenized precursor solution to 50 ℃, stirring for 60min, cooling and transferring to a hydrothermal reaction kettle;
(3) Heating the hydrothermal reaction kettle to 180 ℃, and controlling the temperature to react for 9.5 hours to obtain a suspension;
(4) Transferring the suspension into a centrifuge tube, centrifuging for 10min at 4000r/min, centrifuging for 3 times continuously, and washing with water and ethanol to obtain a precipitate;
(5) Transferring the precipitate to a 105 ℃ blast drying oven, and drying for 24 hours to constant weight to obtain a dry substance;
(6) Placing the dry matter into a muffle furnace, heating to 800 ℃ at a heating rate of 1 ℃/min, calcining for 2 hours at a constant temperature, cooling, taking out, grinding to below 10 meshes, and obtaining the impurity-free porous LaFe 0.5 Ni 0.5 O 3 Catalytic material.
Example 2
Preparation method of porous three-dimensional reticular lanthanum-iron-nickel perovskite material, and 40mmol LaFe is prepared 0.5 Ni 0.5 O 3 The catalytic material comprises the following steps:
(1) 17.32g of La (NO) was added sequentially to 40mL of distilled water 3 ) 3 ·6H 2 O, 8.08g of Fe (NO) 3 ) 3 ·9H 2 O, 4.9768g of Ni (CH) 3 COO) 2 ·4H 2 O and 25.2g of citric acid monohydrate, and uniformly stirring the mixture for 30min under the condition of 430r/min to obtain a homogeneous precursor solution;
(2) Continuously heating the homogenized precursor solution to 50 ℃, stirring for 60min, cooling and transferring to a hydrothermal reaction kettle;
(3) Heating the hydrothermal reaction kettle to 180 ℃, and controlling the temperature to react for 9.5 hours to obtain a suspension;
(4) Transferring the suspension into a centrifuge tube, centrifuging for 10min at 4000r/min, centrifuging for 3 times continuously, and washing with water and ethanol to obtain a precipitate;
(5) Transferring the precipitate to a 105 ℃ blast drying oven, and drying for 24 hours to constant weight to obtain a dry substance;
(6) Placing the dry matter into a muffle furnace, heating to 800 ℃ at a heating rate of 1 ℃/min, calcining for 2 hours at a constant temperature, cooling, taking out, grinding to below 10 meshes, and obtaining the impurity-free porous LaFe 0.5 Ni 0.5 O 3 Catalytic material.
Example 3
Preparation method of porous three-dimensional reticular lanthanum-iron-nickel perovskite material, and 80mmol LaFe is prepared 0.5 Ni 0.5 O 3 The catalytic material comprises the following steps:
(1) 34.64g of La (NO) was added sequentially to 80mL of distilled water 3 ) 3 ·6H 2 O, 16.16g of Fe (NO) 3 ) 3 ·9H 2 O, 9.9536g of Ni (CH) 3 COO) 2 ·4H 2 O and 50.4g of citric acid monohydrate, and stirring the mixture at a constant speed for 60min under the condition of 450r/min to obtain a homogeneous precursor solution;
(2) Continuously heating the homogenized precursor solution to 55 ℃, stirring for 60min, cooling and transferring to a hydrothermal reaction kettle;
(3) Heating the hydrothermal reaction kettle to 190 ℃, and controlling the temperature to react for 10 hours to obtain a suspension;
(4) Transferring the suspension into a centrifuge tube, centrifuging for 10min at 4000r/min, centrifuging for 3 times continuously, and washing with water and ethanol to obtain a precipitate;
(5) Transferring the precipitate to a blast drying oven at 105 ℃, and drying for 24 hours to constant weight to obtain a dry substance;
(6) Placing the dry matter into a muffle furnace, heating to 800 ℃ at a heating rate of 1 ℃/min, calcining for 2 hours at a constant temperature, cooling, taking out, grinding to below 10 meshes, and obtaining the impurity-free porous LaFe 0.5 Ni 0.5 O 3 Catalytic material.
Comparative example 1
Sol-gel processPreparation of LaFe 0.5 Ni 0.5 O 3 The preparation method comprises the following steps:
(1) 21.6505g of La (NO) was added sequentially to 50mL of distilled water 3 ) 3 ·6H 2 O, 10.1000g of Fe (NO) 3 ) 3 ·9H 2 O, 6.2210g of Ni (CH) 3 COO) 2 ·4H 2 O, 25.2170g of citric acid monohydrate and 2.976g of ethylene glycol, and uniformly stirring the mixture for 30min under the condition of 430r/min to obtain a homogeneous precursor solution;
(2) Heating the homogeneous precursor solution to 80 ℃, and stirring at a constant temperature of 430r/min for 1.5h to obtain a viscous wet gel;
(3) Transferring the viscous wet gel into a 105 ℃ forced air drying box, and drying for 24 hours to constant weight to obtain xerogel;
(4) Grinding the xerogel, sieving with a 10-mesh sieve to obtain xerogel powder, placing the xerogel powder into a muffle furnace, heating to 700 ℃ at a heating rate of 5 ℃/min, calcining at constant temperature for 4 hours, cooling to 500 ℃, continuing to keep at constant temperature for 2 hours, and cooling to normal temperature to obtain impurity-free LaFe 0.5 Ni 0.5 O 3 Catalytic material.
Example 4
The application of porous three-dimensional network lanthanum iron nickel perovskite material in catalytic cracking toluene to produce easily recovered condensable components comprises the following specific steps:
(1) LaFe obtained in example 1 0.5 Ni 0.5 O 3 5g of catalytic material are placed in a vertical quartz tube (60 mm. Times.1000 mm);
(2) Nitrogen is used as toluene oil gas carrier gas, the nitrogen flow rate is 150SCCM, the toluene oil gas is continuously fed through an injection pump with pipeline auxiliary heat, and the toluene oil gas concentration is controlled to be 400g/Nm 3 ;
(3) Heating by a vertical tube furnace in the catalytic reforming process, and keeping the temperature of the catalyst layer constant at 700 ℃;
(4) Absorbing unreacted toluene by an absorption liquid, continuously feeding for 24 hours at the temperature of 700 ℃, and carrying out component analysis and gas production statistics on the generated combustible gas by a gas analyzer;
comparative example 1Prepared LaFe 0.5 Ni 0.5 O 3 Catalytic materials were also tested as described above.
The results are shown in Table 1.
Table 1 example 4 and comparative example 1 continuous 24h experimental product distribution
According to the table 1, the porous three-dimensional reticular lanthanum iron nickel perovskite material provided by the invention has good stability in catalytic cracking toluene, the toluene conversion rate can reach 82.28% above at the temperature, on the basis of ensuring higher toluene removal rate, the improvement of the yield of easily recovered condensable components is synchronously realized, the product ratio is improved by 52.79%, and the porous three-dimensional reticular lanthanum iron nickel perovskite material has higher selectivity of condensable components, the gas production efficiency is kept stable, the catalytic performance does not obviously fluctuate, and the catalytic material realizes design expectation; in addition, the porous three-dimensional reticular lanthanum iron nickel perovskite material provided by the invention has the advantages that the gas yield of toluene produced by catalytic pyrolysis is greatly reduced compared with that of toluene produced by a sol-gel method, the gas production process in the toluene catalytic reforming process is limited, and the three-phase product selectivity is regulated and controlled; the porous three-dimensional reticular lanthanum iron nickel perovskite material provided by the embodiment 1 of the invention has higher purity, good catalytic performance and certain popularization advantage, and can be used for selecting a preparation method of the catalytic material according to specific product requirements.
The porous three-dimensional network lanthanum iron nickel perovskite material prepared in the embodiment 1 of the invention is subjected to X-ray diffraction analysis, and the result is shown in figure 1. As can be seen from FIG. 1, the porous three-dimensional network lanthanum iron nickel perovskite material is successfully prepared.
SEM analysis was performed on the porous three-dimensional network lanthanum-iron-nickel perovskite material prepared in example 1 of the present invention, and the results are shown in FIG. 2. According to FIG. 2, the porous three-dimensional network lanthanum-iron-nickel perovskite material provided by the invention has a uniform, stable and regular controllable porous three-dimensional network perovskite structure, and a crystal network is composed of uniform particles of 100-200 nm.
XPS test is carried out on the porous three-dimensional network lanthanum iron nickel perovskite material prepared in the embodiment 1 of the invention, and the result is shown in figure 3. According to fig. 3, the porous three-dimensional network lanthanum-iron-nickel perovskite material provided by the invention has abundant oxygen adsorption and crystal oxygen species, the adsorbed oxygen accounts for 58.59% of the total oxygen species, and the lattice oxygen accounts for 37.66% of the total oxygen species.
The porous three-dimensional network lanthanum iron nickel perovskite material prepared in the embodiment 1 of the invention is detected for the conversion rate of toluene in 24h catalytic reforming and the total yield of three-phase products, and the detection method comprises the following steps: measuring the yield of the solid product by a weight difference method before and after the reaction; analyzing, detecting and metering by an automatic gas analyzer to generate the yield of the non-condensable gas component; the yield of the condensable components was obtained by mass difference method and absorption liquid quantitative determination method, and the results are shown in FIG. 4. As can be seen from FIG. 4, the porous three-dimensional network lanthanum-iron-nickel perovskite material of the invention has 24h catalytic reforming toluene, toluene conversion rate kept above 82.275%, easily recovered condensable component yield above 85% of the total mass of the product, and small solid and gaseous product yields generated by catalytic cracking, and only small CO production 2 And H 2 The porous three-dimensional network lanthanum iron nickel perovskite material has obvious advantages in catalytic stability, and has good toluene removal rate and three-phase product controllability.
The components of the catalytic reforming toluene oil gas synthesis gas of the porous three-dimensional network lanthanum iron nickel perovskite material prepared in the embodiment 1 of the invention are analyzed, and the result is shown in fig. 5. As can be seen from FIG. 5, the catalytic material prepared by the method has good catalytic stability, and the catalytic material product does not generate obvious fluctuation in 24h continuous experiments, and is prepared by CO 2 And H 2 The harmless non-condensable gas exists in the form of the like, and the high-value recycling of the synthesis gas can be considered according to the amplification of the later specific treatment scale.
Using scanning electron microscopyMirror pair example 1 high purity porous LaFe 0.5 Ni 0.5 O 3 Catalytic material and high purity LaFe prepared in comparative example 1 0.5 Ni 0.5 O 3 The catalytic material was observed and the results are shown in fig. 6. As can be seen from FIG. 6, the porous three-dimensional network lanthanum-iron-nickel perovskite material prepared in example 1 of the present invention and LaFe prepared in comparative example 1 0.5 Ni 0.5 O 3 The catalytic material has obvious difference in microscopic particle size and morphology structure, the particle size of the porous three-dimensional network lanthanum-iron-nickel perovskite material prepared by the invention is kept between 100 and 200nm, and the porous three-dimensional network material has a multi-layer porous three-dimensional network structure, which has great influence on the selectivity of the final three-phase product, while the LaFe prepared by the sol-gel method in comparative example 1 0.5 Ni 0.5 O 3 The smaller particle size of the catalytic material increases the production of gaseous products.
According to the embodiment, the porous three-dimensional reticular lanthanum iron nickel perovskite material provided by the invention has the advantages of high stability, good catalytic performance, stable toluene removal effect, high purity and low impurity content, the gas production process of catalytic reforming toluene is limited, the generation of solid products is reduced, catalytic cracking toluene is converted into small molecular organic matters, the yield ratio of easily recovered condensable components of catalytic reforming toluene is improved, the three-phase product selectivity is regulated and controlled, good catalytic stability and catalytic activity are realized, the toluene removal rate and the three-phase product controllability are good, the easily recovered condensable components are high in yield, the solid products and the gas products are low in yield, and only a small amount of harmless noncondensable gas and solid carbon nanotubes are generated.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
Claims (8)
1. A preparation method of a porous three-dimensional reticular structure lanthanum iron nickel perovskite material comprises the following steps:
(1) Heating and mixing soluble lanthanum salt, soluble nickel salt, soluble ferric salt, dispersing agent and water to obtain premix;
(2) Adding the premix into a closed container, heating to perform hydrothermal reaction to obtain suspension;
(3) Sequentially carrying out solid-liquid separation and calcination on the suspension to obtain a porous three-dimensional reticular structure lanthanum iron nickel perovskite material;
the ratio of the total molar weight of the dispersing agent to the soluble lanthanum salt, the soluble ferric salt and the soluble nickel salt is 1-1.5:1;
the soluble lanthanum salt is lanthanum nitrate hexahydrate; the soluble nickel salt is nickel acetate tetrahydrate; the soluble ferric salt is ferric nitrate nonahydrate;
the heating and mixing are carried out under the condition of stirring, the stirring speed is 400-500 r/min, the heating and mixing comprises a first stage and a second stage which are sequentially carried out, the temperature of the first stage is room temperature, the time is 30-90 min, the temperature of the second stage is 45-60 ℃, and the time is 30-60 min;
the dispersing agent is one or two of citric acid monohydrate and citric acid.
2. The preparation method of claim 1, wherein the mass ratio of the soluble lanthanum salt to the soluble nickel salt is 2.14-21.4:1; the mass ratio of the soluble nickel salt to the soluble iron salt is 0.068-5.544:1.
3. The preparation method according to claim 1, wherein the ratio of the total molar amount of water to the soluble lanthanum salt, the soluble iron salt and the soluble nickel salt is 20-60:1.
4. The preparation method according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 170-190 ℃ for a heat preservation time of 9-10 hours.
5. The preparation method of claim 1, wherein the calcination temperature is 700-1000 ℃ and the heat preservation time is 2-6 h.
6. The porous three-dimensional network lanthanum-iron-nickel perovskite material obtained by the preparation method according to any one of claims 1-5, wherein the surface of the porous three-dimensional network lanthanum-iron-nickel perovskite material contains oxygen species, the oxygen species comprise adsorbed oxygen and lattice oxygen, the adsorbed oxygen accounts for 58.5-58.7% of the total amount of the oxygen species, and the lattice oxygen accounts for 37.6-37.8% of the total amount of the oxygen species.
7. The application of the porous three-dimensional network lanthanum iron nickel perovskite material in catalytic cracking of toluene.
8. The process according to claim 7, wherein the toluene concentration is 400g/Nm or less 3 The catalytic cracking temperature is more than or equal to 700 ℃.
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化学链燃烧中LaNixFe1-xO3载氧体的性能研究;王钰佳 等;《中国稀土学报》;第31卷(第1期);第96-101页 * |
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