CN115385401A - Lanthanum-iron-nickel perovskite material with porous three-dimensional network structure and preparation method and application thereof - Google Patents
Lanthanum-iron-nickel perovskite material with porous three-dimensional network structure and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 97
- WSZBCXXFBOTXDC-UHFFFAOYSA-N [Fe].[Ni].[La] Chemical compound [Fe].[Ni].[La] WSZBCXXFBOTXDC-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 171
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 54
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- 238000000926 separation method Methods 0.000 claims description 5
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- 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
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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Images
Classifications
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- 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
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- 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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- C01P2002/00—Crystal-structural characteristics
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- C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention belongs to the technical field of composite catalysis, and particularly relates to a lanthanum-iron-nickel perovskite material with a porous three-dimensional network structure, and a preparation method and application thereof. The lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure provided by the invention has the advantages of high stability, good catalytic performance, stable toluene removal effect, high purity and low impurity content. The embodiment result shows that the catalytic cracking toluene with the porous three-dimensional network structure lanthanum-iron-nickel perovskite material 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 generated by catalytic cracking is small, and only a small amount of harmless non-condensable gas and solid carbon nano tubes are generated.
Description
Technical Field
The invention belongs to the technical field of composite catalysis, and particularly relates to a lanthanum-iron-nickel perovskite material with a porous three-dimensional network structure, and a preparation method and application thereof.
Background
Toluene is a high carbon-containing aromatic compound, is flammable, can form an explosive mixture with steam or air, has low toxicity and carcinogenic characteristics, is widely present in pyrolysis oil gas, and is often used as a tar model compound for evaluating the performance of catalytic reforming tar of a catalyst. In order to reduce the influence of toluene on the environment and the operation stability of equipment, the toluene needs to be purified and treated.
The perovskite oxide has unique adjustable volume and various surface characteristics, is widely applied to the fields of photocatalysis, electrocatalysis, catalytic oxidation and the like, and has good effects on the aspects of organic matter degradation, methane and carbon dioxide reforming, efficient removal of VOCs and the like. The perovskite oxide has a regular octahedral structure, the atomic position can be effectively limited, the formation of larger metal clusters on the surface of the catalyst can be reduced by well-dispersed active metal particles, and the sintering of 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 capacity, can realize effective removal of carbon on the surface of a material, and the oxygen-deficient non-stoichiometric ratio in the perovskite oxide can be used for oxygen or air regeneration in the environment.
The existing perovskite catalyst for catalytically reforming toluene realizes the catalytic oxidation or steam reforming of toluene mainly under the condition of introducing oxygen or water vapor as a gasifying agent so as to obtain high-heat-value combustible gas. But the pyrolysis oil gas has complex components, sulfur-containing and nitrogen-containing gas components can influence the catalytic stability of the existing catalytic reforming technology, and the removal rate of toluene is unstable.
Disclosure of Invention
The invention aims to provide a lanthanum-iron-nickel perovskite material with a porous three-dimensional net structure, and a preparation method and application thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a preparation method of a lanthanum-iron-nickel perovskite material with a porous three-dimensional network structure, which comprises the following steps:
(1) Heating and mixing soluble lanthanum salt, soluble nickel salt, soluble iron salt, a dispersing agent and water to obtain a premixed solution;
(2) Adding the premixed solution into a closed container, heating and carrying out hydrothermal reaction to obtain a suspension;
(3) And sequentially carrying out solid-liquid separation and calcination on the turbid liquid to obtain the lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure.
Preferably, the mass ratio of the soluble lanthanum salt to the soluble nickel salt is 2.14-21.4; the mass ratio of the soluble nickel salt to the soluble iron salt is 0.068-5.544.
Preferably, the ratio of the dispersant to the total molar weight of the soluble lanthanum salt, the soluble iron salt and the soluble nickel salt is 1-1.5; the ratio of the water to the total molar amount of the soluble lanthanum salt, the soluble ferric salt and the soluble nickel salt is 20-60.
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 carried out under the condition of stirring, the stirring speed is 400-500 r/min, the heating and mixing comprise 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 invention also provides the lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure, which is obtained by the preparation method in the scheme, wherein the surface of the lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure 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 lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure in catalytic cracking of toluene.
Preferably, the concentration of the toluene is less than or equal to 400g/Nm 3 The temperature of the catalytic cracking is more than or equal to 700 ℃.
The invention provides a preparation method of a lanthanum-iron-nickel perovskite material with a porous three-dimensional network structure. According to the method, the lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure is prepared by a solvothermal method, and the high dispersion and expansion characteristics of a hot solvent in a closed space improve the dispersibility of metal active components in the preparation process, avoid the hard agglomeration phenomenon of particles, promote the construction of the lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure and improve the catalytic performance of a catalytic material; meanwhile, the high-concentration liquid phase reaction space improves the material crystallization dispersion degree, so that the particle size of the catalytic material is reduced and stabilized to be within the range of 100-200 nm, and the solvent oxygen in the liquid phase can further participate in crystal construction 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 lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure, which is obtained by the preparation method in the scheme, wherein the surface of the lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure 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 lanthanum, iron and nickel perovskite material with the porous three-dimensional network structure provided by the invention has a uniform, stable and regular controllable porous three-dimensional network perovskite structure, a crystal network is formed by 100-200 nm uniform particles, oxygen and crystalline oxygen species adsorbed on the surface of the material are abundant, the adsorbed oxygen accounts for 58.59% of the total amount of the oxygen species, and lattice oxygen accounts for 37.66% of the total amount of the oxygen species, the oxygen species can participate in a toluene catalytic oxidation process and a material surface carbon deposit removal process, the specific particle size and the abundant surface adsorbed oxygen of the lanthanum, iron and nickel perovskite material with the porous three-dimensional network structure limit a gas production process in a toluene catalytic reforming process, reduce the generation of solid products, convert the catalytic cracking toluene into small-molecule organic matters, improve the yield ratio of easily-recovered condensable components in the toluene catalytic reforming process, and realize the regulation and control of the selectivity of three-phase products. The lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure 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 lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure in catalytic cracking of toluene. The lanthanum, iron and nickel perovskite material with the porous three-dimensional network structure provided by the invention has good catalytic stability and catalytic activity when being used for catalytic cracking of toluene, and in a 24-hour continuous experiment at 700 ℃, the three-phase product and gas product selectivity of the catalytic cracking of toluene are not obviously fluctuated and changed, so that the lanthanum, iron and nickel perovskite material with the porous three-dimensional network structure has obvious advantages in catalytic stability. In addition, the catalytic cracking toluene of the lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure has good toluene removal rate and three-phase product controllability, the toluene conversion rate is kept above 82.275%, the yield of condensable components can reach 89.304% of the total mass of the product, the yield of solid products and gas products generated by catalytic cracking is small, only a small amount of harmless non-condensable gas and solid carbon nano tubes are generated, the pollution and the hazard to the environment are avoided, and the application and popularization prospect is good.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
Fig. 1 is an XRD spectrum of the lanthanum-iron-nickel perovskite material with a porous three-dimensional network structure prepared in example 1 of the present invention;
FIG. 2 is an SEM spectrum of a lanthanum-iron-nickel perovskite material with a porous three-dimensional network structure prepared in example 1 of the invention;
FIG. 3 is an XPS test oxygen species spectrum of a lanthanum-iron-nickel perovskite material with a porous three-dimensional network structure prepared in example 1 of the invention;
FIG. 4 shows the toluene conversion rate and total three-phase product yield in 24h catalytic reforming of the porous three-dimensional network-structure lanthanum-iron-nickel perovskite material prepared in example 1 of the present invention;
FIG. 5 shows the relative volume ratio (within 24 h) of each component of the toluene oil-gas synthesis gas catalytically reformed by the porous lanthanum-iron-nickel perovskite material with a three-dimensional network structure prepared in example 1 of the present invention;
FIG. 6 shows a lanthanum-iron-nickel perovskite material with a porous three-dimensional network structure prepared in example 1 of the invention and LaFe prepared in comparative example 1 0.5 Ni 0.5 O 3 SEM spectra of catalytic materials.
Detailed Description
The invention provides a preparation method of a lanthanum-iron-nickel perovskite material with a porous three-dimensional net structure, which comprises the following steps:
(1) Heating and mixing soluble lanthanum salt, soluble nickel salt, soluble iron salt, a dispersing agent and water to obtain a premixed solution;
(2) Adding the premixed solution into a closed container, heating and carrying out hydrothermal reaction to obtain a suspension;
(3) And sequentially carrying out solid-liquid separation and calcination on the turbid liquid to obtain the lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure.
The method comprises the steps of heating and mixing soluble lanthanum salt, soluble nickel salt, soluble iron salt, a dispersing agent and water to obtain a premixed solution. 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, more preferably 4.2-4.4; the mass ratio of the soluble nickel salt to the soluble iron salt is preferably 0.068-5.544, more preferably 0.60-0.63; 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 1-1.5, more preferably 1.2-1.5; the ratio of the water to the total molar amount of the soluble lanthanum salt, the soluble iron salt and the soluble nickel salt is preferably 20 to 60, more preferably 25 to 30. In the embodiment of the invention, the adopted nickel acetate tetrahydrate is a non-explosive drug and has low cost, and the nickel acetate tetrahydrate and the dispersant are combined mutually to strengthen the dispersibility of nickel salt in a water phase so as to obtain the catalytic material with high purity and uniformly distributed active components. In the specific embodiment of the invention, the adding proportion of the dispersing agent is limited, so that the dispersibility of the metal salt precursor in water can be enhanced, and other links for enhancing the dispersibility of the metal salt are reduced, meanwhile, other additives except for the dispersing agent are not required to be added, the pH is not required to be adjusted, 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 lanthanum, iron and nickel perovskite material with the porous three-dimensional net structure are improved. The lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure provided by the invention has a perovskite structure, and the limited ferronickel atomic ratio is favorable for the material to form ferronickel alloy in the reaction process, so that the material shows high activity and high stability.
In the present invention, the heating and mixing is preferably performed by stirring; the stirring speed is preferably 400-500 r/min, and more preferably 420-460 r/min; the heating and mixing preferably comprises a first stage and a second stage which are sequentially carried out; the temperature of the first stage is preferably room temperature, the time is preferably 30-90 min, and 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, after the heating and mixing are completed, the premixed liquid is preferably cooled; the final temperature of the cooling is preferably room temperature; the cooling is preferably natural cooling. In the specific embodiment of the invention, the continuous stirring at the stirring speed is adopted, so that the dispersibility of the metal salt in the water phase is improved, the element aggregation is avoided, and the dispersibility of the generated material elements is improved.
After the premixed solution is obtained, the premixed solution is added into a closed container to be heated for hydrothermal reaction, and 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 obtaining the turbid liquid, sequentially carrying out solid-liquid separation and calcination on the turbid liquid to obtain the lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure. In the present invention, the method of separation is preferably centrifugation; the number of the centrifugation is preferably 3 to 4, more preferably 4, to rapidly obtain a uniform precipitated fraction; the rotation speed of the centrifugation is preferably 4000-4500 r/min, more preferably 4200-4500 r/min, the time is preferably 10-15 min, more preferably 12-15 min; after each centrifugation, the solid product obtained is preferably washed; after the final centrifugation is completed, preferably drying the 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 time is preferably 18 to 24 hours, more preferably 20 to 22 hours.
In the present invention, the temperature of the calcination 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 calcining temperature by a program for calcining, and sequentially cooling and grinding after calcining; the final temperature of the cooling is preferably room temperature; the cooling is preferably natural cooling. The invention is beneficial to the evacuation of gas in pore channels of the lanthanum, iron, nickel and perovskite material with the porous three-dimensional network structure and the formation of a composite metal oxide structure through calcination.
The invention also provides the lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure, which is obtained by the preparation method in the scheme, wherein the surface of the lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure contains oxygen species, and 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 comprise adsorbed oxygen 58.5 to 58.7%, preferably 58.59%; the oxygen species comprises lattice oxygen 37.6 to 37.8%, preferably 37.66%. In the invention, the lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure is preferably LaFe 0.5 Ni 0.5 O 3 。
The invention also provides application of the lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure in catalytic cracking of toluene.
In the present invention, the application preferably includes: adding the lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure into a vertical quartz tube, and then introducing carrier gas and toluene oil gas for catalytic reforming reaction. In the invention, the mol ratio of the lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure to the toluene oil gas is preferably 0.52-0.53, more preferably 0.524-0.526; the carrier gas is preferably nitrogen; the flow rate of the carrier gas is preferably 100-300 SCCM, more preferably 150SCCM; the flow rate of the toluene oil gas is preferably 3.5-3.7 g/h, and more preferably 3.6L/h; the concentration of toluene in the toluene oil gas is preferably less than or equal to 400g/Nm 3 More preferably 50 to 400g/Nm 3 (ii) a The toluene oil gas is preferably continuously fed through an injection pump with pipeline auxiliary heat, and the feeding temperature is preferably 180-250 ℃, and more preferably 190-210 ℃; the temperature of the catalytic reforming reaction is preferably more than or equal to 700 ℃, more preferably 700-900 ℃, and further preferably 750-850 ℃; the temperature of the catalytic reforming reaction is preferably in the vertical directionThe tube furnace is controlled, and it is preferable that the temperature of the catalyst layer in the vertical quartz tube is kept constant at the temperature of the catalytic reforming reaction. In the present invention, after the catalytic reforming reaction is completed, post-treatment is preferably performed; 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.
Under the temperature limited by the catalytic reforming reaction, the yield of solid products and gas products generated by catalytic reforming is small, and the conversion rate of toluene is high; when the temperature is too high, the proportion of the catalytic cracking gas product tends to increase, and when the temperature is too low, the toluene conversion rate tends to decrease.
In order to further illustrate the invention, the following detailed description of the embodiments of the invention is given with reference to the accompanying drawings and examples, which are not to be construed as limiting the scope of the invention.
Example 1
Preparation method of lanthanum-iron-nickel perovskite material with porous three-dimensional network structure, and preparation method of 50mmol LaFe 0.5 Ni 0.5 O 3 The preparation steps of the catalytic material are as follows:
(1) 21.6505g La (NO) was added to 50mL distilled water in sequence 3 ) 3 ·6H 2 O, 10.1000g Fe (NO) 3 ) 3 ·9H 2 O, 6.2210g of Ni (CH) 3 COO) 2 ·4H 2 O and 30.0g of citric acid monohydrate, and uniformly stirring the mixture for 30min at the speed of 430r/min to obtain a homogeneous precursor solution;
(2) Continuously heating the homogeneous 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 the rotating speed of 4000r/min, continuously centrifuging for 3 times, and washing with water and ethanol to obtain a precipitate;
(5) Transferring the precipitate to a 105 ℃ forced air drying oven, and drying for 24 hours to constant weight to obtain dry matter;
(6) Placing the dry matter in a muffle furnace, heating to 800 ℃ at the heating rate of 1 ℃/min, calcining at constant temperature for 2h, cooling, taking out, grinding to below 10 meshes to obtain the porous LaFe without impurities 0.5 Ni 0.5 O 3 A catalytic material.
Example 2
Preparation method of lanthanum-iron-nickel perovskite material with porous three-dimensional network structure, 40mmol of LaFe is prepared 0.5 Ni 0.5 O 3 The steps of catalyzing the material are as follows:
(1) To 40mL of distilled water were added in order 17.32g of La (NO) 3 ) 3 ·6H 2 O, 8.08g 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 at the speed of 430r/min to obtain a homogeneous precursor solution;
(2) Continuously heating the homogeneous 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 the rotating speed of 4000r/min, continuously centrifuging for 3 times, and washing with water and ethanol to obtain a precipitate;
(5) Transferring the precipitate to a 105 ℃ forced air drying oven, and drying for 24h to constant weight to obtain a dry matter;
(6) Placing the dry matter in a muffle furnace, heating to 800 ℃ at the heating rate of 1 ℃/min, calcining at constant temperature for 2h, cooling, taking out, grinding to below 10 meshes to obtain the porous LaFe without impurities 0.5 Ni 0.5 O 3 A catalytic material.
Example 3
Preparation method of lanthanum-iron-nickel perovskite material with porous three-dimensional network structure, and preparation method of 80mmol LaFe 0.5 Ni 0.5 O 3 The steps of catalyzing the material are as follows:
(1) To 80mL of distilled water were added 34.64g of La (NO) in order 3 ) 3 ·6H 2 O, 16.16g 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 uniformly stirring the mixture for 60min under the condition of 450r/min to obtain a homogeneous precursor solution;
(2) Continuously heating the homogeneous precursor solution to 55 ℃, stirring for 60min, cooling and transferring to a hydrothermal reaction kettle;
(3) Heating the hydrothermal reaction kettle to 190 ℃, and reacting for 10 hours at a controlled temperature to obtain a suspension;
(4) Transferring the suspension into a centrifugal tube, centrifuging for 10min at the rotating speed of 4000r/min, continuously centrifuging for 3 times, and washing with water and ethanol to obtain a precipitate;
(5) Transferring the precipitate to a 105 ℃ forced air drying oven, and drying for 24h to constant weight to obtain dry matter;
(6) Placing the dry matter in a muffle furnace, heating to 800 ℃ at a heating rate of 1 ℃/min, calcining at a constant temperature for 2h, cooling, taking out, grinding to below 10 meshes to obtain the porous LaFe without impurities 0.5 Ni 0.5 O 3 A catalytic material.
Comparative example 1
Preparation of LaFe by sol-gel method 0.5 Ni 0.5 O 3 The preparation method comprises the following steps:
(1) 50mL of distilled water was sequentially charged with 21.6505g of La (NO) 3 ) 3 ·6H 2 O, 10.1000g Fe (NO) 3 ) 3 ·9H 2 O, 6.2210g of Ni (CH) 3 COO) 2 ·4H 2 O, 25.2170g citric acid monohydrate and 2.976g 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 the constant temperature of 430r/min for 1.5h to obtain viscous wet gel;
(3) Transferring the viscous wet gel into a 105 ℃ forced air drying oven, and drying for 24h to constant weight to obtain dry gel;
(4) Grinding the dry gel, sieving the ground dry gel by a 10-mesh sieve to obtain dry gel powder, and placing the dry gel powder in a muffle furnaceHeating to 700 ℃ at the heating rate of 5 ℃/min, calcining at constant temperature for 4h, cooling to 500 ℃, keeping the temperature for 2h, and cooling to normal temperature to obtain the impurity-free LaFe 0.5 Ni 0.5 O 3 A catalytic material.
Example 4
The application of the porous three-dimensional network structure lanthanum, iron, nickel and perovskite material in catalytic cracking of 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 the catalytic material was placed in a vertical quartz tube (60 mm. Times.1000 mm);
(2) Nitrogen is taken 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 concentration of the toluene oil gas is controlled to be 400g/Nm 3 ；
(3) Heating by using a vertical tubular furnace in the catalytic reforming process, and keeping the temperature of a catalyst layer constant at 700 ℃;
(4) Absorbing unreacted toluene by 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;
LaFe prepared in comparative example 1 0.5 Ni 0.5 O 3 The catalytic material was also subjected to the above test.
The results are shown in Table 1.
TABLE 1 product distribution from example 4 and comparative example 1 run over 24h
According to table 1, the catalytic cracking toluene with the porous three-dimensional network structure lanthanum-iron-nickel perovskite material provided by the invention has good stability, the toluene conversion rate at the temperature can reach more than 82.28%, on the basis of ensuring higher toluene removal rate, the yield of easily-recovered condensable components is synchronously improved, the product proportion is improved by 52.79%, the reaction process is proved to have higher condensable component selectivity, the gas production efficiency is kept stable, the catalytic performance is not obviously fluctuated, and the catalytic material realizes design expectation; moreover, the gas production rate of the catalytic cracking toluene by using the porous three-dimensional network structure lanthanum-iron-nickel perovskite material is greatly reduced compared with that of a sol-gel method, the gas production process in the toluene catalytic reforming process is limited, and the selectivity of a three-phase product is regulated and controlled; the lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure provided by the embodiment 1 of the invention has high purity, good catalytic performance and certain popularization advantages, and the preparation method of the catalytic material can be selected according to the specific product requirements.
The X-ray diffraction analysis of the lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure prepared in example 1 of the present invention is shown in fig. 1. As can be seen from figure 1, the lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure is successfully prepared and obtained by the method.
SEM analysis is carried out on the lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure prepared in the embodiment 1 of the invention, and the result is shown in FIG. 2. As can be seen from FIG. 2, the lanthanum-iron-nickel perovskite material with a porous three-dimensional network structure provided by the invention has a uniform, stable and regularly controllable porous three-dimensional network perovskite structure, and the crystal network is composed of uniform particles of 100-200 nm.
XPS test is carried out on the lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure prepared in the embodiment 1 of the invention, and the result is shown in figure 3. According to fig. 3, the lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure provided by the invention has rich oxygen and crystalline oxygen species adsorbed on the surface, the adsorbed oxygen accounts for 58.59% of the total amount of the oxygen species, and the lattice oxygen accounts for 37.66% of the total amount of the oxygen species.
The method for detecting the conversion rate of the lanthanum, iron and nickel perovskite material with the porous three-dimensional network structure, which is prepared in the embodiment 1 of the invention, in toluene catalytically reformed for 24 hours and the total output of three-phase products comprises the following steps: determining the yield of the solid product by a weight difference method before and after the reaction; the yield of the non-condensable gas components is analyzed, detected and metered through an automatic gas analyzer; by mass difference methodThe yield of the condensable component was determined by quantitative determination with an absorption solution, and the results are shown in FIG. 4. As can be seen from FIG. 4, the lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure can be used for catalytically reforming toluene for 24 hours, the conversion rate of the toluene is kept above 82.275%, the yield of easily-recovered condensable components is above 85% of the total mass of the product, the yields of solid products and gaseous products generated by catalytic cracking are small, and only a small amount of CO is generated 2 And H 2 And the like, harmless noncondensable gas and solid carbon nano tubes, and the lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure has obvious advantages in catalytic stability, and has good toluene removal rate and three-phase product controllability.
The components of the toluene oil gas synthesis gas catalytically reformed by the porous lanthanum-iron-nickel-perovskite material with a three-dimensional network structure prepared in example 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 in a 24-hour continuous experiment, the catalytic material product does not fluctuate obviously and is all in the form of CO 2 And H 2 And the like exist in a harmless non-condensable gas form, and high-value recycling of the synthesis gas can be considered according to amplification of a specific treatment scale in the later stage.
High purity porous LaFe of example 1 using scanning electron microscope 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 lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure prepared in example 1 of the invention and the 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 lanthanum, iron and nickel perovskite material with the porous three-dimensional network structure prepared by the invention is kept between 100 and 200nm, and the material has a multilayer porous three-dimensional network structure, which greatly influences the selectivity of a final three-phase product, while the LaFe prepared by the sol-gel method in the comparative example 1 0.5 Ni 0.5 O 3 Smaller particle sizes of the catalytic material increase the production of gaseous products.
The embodiments show that the porous lanthanum-iron-nickel perovskite material with a three-dimensional network structure provided by the invention has the advantages of high stability, good catalytic performance, stable toluene removal effect, high purity, low impurity content, limitation of the gas production process of catalytic reforming toluene, reduction of the generation of solid products, conversion of catalytic cracking toluene into small molecular organic matters, improvement of the yield ratio of easily-recovered condensable components in the catalytic reforming toluene production, realization of regulation and control of the selectivity of three-phase products, good catalytic stability and catalytic activity, good toluene removal rate and three-phase product controllability, high yield of easily-recovered condensable components, small yield of solid products and gas products, and only generation of a small amount of harmless noncondensable gas and solid carbon nanotubes.
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. A preparation method of a lanthanum-iron-nickel perovskite material with a porous three-dimensional network structure comprises the following steps:
(1) Heating and mixing soluble lanthanum salt, soluble nickel salt, soluble iron salt, a dispersing agent and water to obtain a premixed solution;
(2) Adding the premixed solution into a closed container, heating and carrying out hydrothermal reaction to obtain a suspension;
(3) And sequentially carrying out solid-liquid separation and calcination on the turbid liquid to obtain the lanthanum-iron-nickel perovskite material with the porous three-dimensional network structure.
2. The preparation method according to claim 1, wherein the mass ratio of the soluble lanthanum salt to the soluble nickel salt is 2.14 to 21.4; the mass ratio of the soluble nickel salt to the soluble iron salt is 0.068-5.544.
3. The method according to claim 1, wherein 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 to 1.5; the ratio of the water to the total molar weight of the soluble lanthanum salt, the soluble iron salt and the soluble nickel salt is 20-60.
4. The preparation method according to claim 1, wherein the temperature of the hydrothermal reaction is 170-190 ℃ and the holding time is 9-10 h.
5. The preparation method of claim 1, wherein the calcining temperature is 700-1000 ℃ and the holding time is 2-6 h.
6. The method of preparation according to claim 1 or 2, wherein the soluble lanthanum salt is lanthanum nitrate hexahydrate; the soluble nickel salt is nickel acetate tetrahydrate; the soluble ferric salt is ferric nitrate nonahydrate.
7. The preparation method according to claim 1, wherein the heating and mixing are carried out under stirring at a speed of 400 to 500r/min, and the heating and mixing comprise a first stage and a second stage which are sequentially carried out, wherein the temperature of the first stage is room temperature and the time is 30 to 90min, and the temperature of the second stage is 45 to 60 ℃ and the time is 30 to 60min.
8. The porous three-dimensional network structure lanthanum iron nickel perovskite material obtained by the preparation method of any one of claims 1 to 7, wherein the surface of the porous three-dimensional network structure lanthanum iron nickel perovskite material contains oxygen species, the oxygen species comprises adsorbed oxygen and lattice oxygen, the adsorbed oxygen accounts for 58.5 to 58.7 percent of the total amount of the oxygen species, and the lattice oxygen accounts for 37.6 to 37.8 percent of the total amount of the oxygen species.
9. Use of the porous three-dimensional network structure lanthanum iron nickel perovskite material as defined in claim 8 in catalytic cracking of toluene.
10. Use according to claim 9, wherein the toluene concentration is ≤ 400g/Nm 3 The temperature of the catalytic cracking is more than or equal to 700 ℃.
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